CA2326845A1 - Ionomers and ionically conductive compositions - Google Patents
Ionomers and ionically conductive compositions Download PDFInfo
- Publication number
- CA2326845A1 CA2326845A1 CA002326845A CA2326845A CA2326845A1 CA 2326845 A1 CA2326845 A1 CA 2326845A1 CA 002326845 A CA002326845 A CA 002326845A CA 2326845 A CA2326845 A CA 2326845A CA 2326845 A1 CA2326845 A1 CA 2326845A1
- Authority
- CA
- Canada
- Prior art keywords
- ionomer
- liquid
- conductive composition
- ionically conductive
- backbone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 229920000554 ionomer Polymers 0.000 title claims abstract description 62
- 239000000203 mixture Substances 0.000 title claims abstract description 54
- -1 fluoroalkyl sulfonate Chemical compound 0.000 claims abstract description 17
- 229920000098 polyolefin Polymers 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 66
- 238000000034 method Methods 0.000 claims description 35
- 239000007788 liquid Substances 0.000 claims description 34
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 18
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 15
- 239000007772 electrode material Substances 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000006229 carbon black Substances 0.000 claims description 10
- 239000011737 fluorine Substances 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 230000009021 linear effect Effects 0.000 claims description 9
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 150000005677 organic carbonates Chemical class 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229920006254 polymer film Polymers 0.000 claims description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 229940006487 lithium cation Drugs 0.000 claims description 3
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 2
- 239000010954 inorganic particle Substances 0.000 claims 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 17
- 229920000642 polymer Polymers 0.000 description 73
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 51
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 37
- 239000010408 film Substances 0.000 description 36
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 26
- 239000000243 solution Substances 0.000 description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 239000003054 catalyst Substances 0.000 description 23
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 16
- 239000012528 membrane Substances 0.000 description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 12
- 239000000523 sample Substances 0.000 description 12
- 239000005977 Ethylene Substances 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 239000002243 precursor Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 8
- 238000010348 incorporation Methods 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920002313 fluoropolymer Polymers 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 4
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 239000000010 aprotic solvent Substances 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- IJSDUKZKUCXMRL-UHFFFAOYSA-L dichlorozirconium;1-[2-(1h-inden-1-yl)ethyl]-1h-indene Chemical compound Cl[Zr]Cl.C1=CC2=CC=CC=C2C1CCC1C2=CC=CC=C2C=C1 IJSDUKZKUCXMRL-UHFFFAOYSA-L 0.000 description 3
- OIBMEBLCOQCFIT-UHFFFAOYSA-N ethanesulfonyl fluoride Chemical compound CCS(F)(=O)=O OIBMEBLCOQCFIT-UHFFFAOYSA-N 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000004763 sulfides Chemical class 0.000 description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- 239000005041 Mylar™ Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 2
- 229910000071 diazene Inorganic materials 0.000 description 2
- 229940117389 dichlorobenzene Drugs 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229920000831 ionic polymer Polymers 0.000 description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 2
- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical class [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- HFSKWPUHEMGYMQ-UHFFFAOYSA-N 1,3-dioxolan-2-one Chemical compound O=C1OCCO1.O=C1OCCO1 HFSKWPUHEMGYMQ-UHFFFAOYSA-N 0.000 description 1
- TUFKHKZLBZWCAW-UHFFFAOYSA-N 2-(1-ethenoxypropan-2-yloxy)ethanesulfonyl fluoride Chemical compound C=COCC(C)OCCS(F)(=O)=O TUFKHKZLBZWCAW-UHFFFAOYSA-N 0.000 description 1
- YXYFONWVDGFHJH-UHFFFAOYSA-N 3-fluoro-4-fluorosulfonyloxybut-1-ene Chemical class C=CC(F)COS(F)(=O)=O YXYFONWVDGFHJH-UHFFFAOYSA-N 0.000 description 1
- 229920003026 Acene Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 101000941356 Nostoc ellipsosporum Cyanovirin-N Proteins 0.000 description 1
- 241001282736 Oriens Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical group OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- UZZWBUYVTBPQIV-UHFFFAOYSA-N dme dimethoxyethane Chemical compound COCCOC.COCCOC UZZWBUYVTBPQIV-UHFFFAOYSA-N 0.000 description 1
- CETRZFQIITUQQL-UHFFFAOYSA-N dmso dimethylsulfoxide Chemical compound CS(C)=O.CS(C)=O CETRZFQIITUQQL-UHFFFAOYSA-N 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- VFLSKPVDUGINNC-UHFFFAOYSA-N ethenoxyethane;sulfuryl difluoride Chemical compound CCOC=C.FS(F)(=O)=O VFLSKPVDUGINNC-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000006005 fluoroethoxy group Chemical group 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-M fluorosulfonate Chemical compound [O-]S(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-M 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- 238000007527 glass casting Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000002946 graphitized mesocarbon microbead Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- COTNUBDHGSIOTA-UHFFFAOYSA-N meoh methanol Chemical compound OC.OC COTNUBDHGSIOTA-UHFFFAOYSA-N 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- VWBWQOUWDOULQN-UHFFFAOYSA-N nmp n-methylpyrrolidone Chemical compound CN1CCCC1=O.CN1CCCC1=O VWBWQOUWDOULQN-UHFFFAOYSA-N 0.000 description 1
- 229920006120 non-fluorinated polymer Polymers 0.000 description 1
- 230000009022 nonlinear effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical class [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 150000003461 sulfonyl halides Chemical class 0.000 description 1
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical group FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/122—Ionic conductors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Disclosed are ionomers comprising functionalized polyolefins having fluoroalkyl sulfonate pendant groups and ionically conductive compositions formed therefrom by the addition of solvents.
Description
TITLE
IONOMERS AND IONICALLY CONDUCTIVE COMPOSITIONS
FIELD OF THE INVENTION
This invention relates to ionomers comprising functionalized polyolefins having fluoroalkyl sulfonate pendant groups and to ionically conductive compositions formed therefrom by the addition of solvents thereto. The ionically conductive compositions of the invention are useful in batteries, fuel cells, electrolysis cells, ion exchange membranes, sensors, electrochemical capacitors, and modified electrodes.
It has long been known in the art to form ionically conducting membranes and gels from organic polymers containing ionic pendant groups. Such polymers are known as ionomers. Particularly well-known ionomer membranes in widespread commercial use are Nafion~ Membranes available from E. I. du Pont de Nemours and Company. Nafion~ is formed by copolymerizing tetra-fluoro ethylene (TFE) with perfluoro(3,6-dioxa-4-methyl-7-octenesulfonyl fluoride), as disclosed in U.S. Patent 3,282,875. Also known are copolymers of TFE with perfluoro (3-oxa-4-pentene sulfonyl fluoride), as disclosed in U.S. Patent 4,358,545. The copolymers so formed are converted to the ionomeric form by hydrolysis, typically by exposure to an appropriate aqueous base, as disclosed in U.S. Patent 3,282,875. Lithium, sodium and potassium are all well known in the art as suitable cations for the above cited ionomers.
In the polymers above-cited, the fluorine atoms provide more than one benefit. The fluorine groups on the carbons proximate to the sulfonyl group in the pendant side chain provide the electronegativity to render the cation sufficiently labile so as to provide high ionic conductivity. Replacement of those fluorine atoms with hydrogen results in a considerable reduction in ionic mobility and consequent loss of conductivity.
The remainder of the fluorine atoms afford the chemical and thermal stability to the polymer normally associated with fluorinated polymers. This has proven to be of considerable value in such applications as the well-known "chlor-alkali" process. However, highly fluorinated polymers also have disadvantages where there is less need for high chemical and thermal stability. The fluorinated monomers are more expensive than their olefin counterparts, require higher processing temperatures, and often require expensive corrosion resistant processing equipment. Furthermore, it is difficult to form solutions and dispersions of fluoropolymers. Additionally, it is difficult to form strong adhesive bonds with fluoropolymers. In materials employed in electrochemical cells, for example, it may be advantageous to have better processibility at some cost to chemical and thermal stability. Thus, there is an incentive to develop ionomers with highly labile canons having non-fluorinated polymer backbones.
Numerous publications disclose polyethers with either proximal ionic species in the polymer or in combination with ionic salts. Conductivities are in S the range of 10-5 S/cm and less. Le Nest et al., Polymer Communications 28, (1987) disclose a composition of polyether glycol oligomers joined by phosphate or thiophosphate moieties hydrolyzed to the related lithium ionomer. In combination with propylene carbonate, conductivity in the range of I-10 x10-4 S/cm was realized. A review of the related art is found in Fauteux et al., Electrochimica Acta 40, 2185 (1995).
Benrabah et al, Electrochimica Acta, 40, 2259 (1995) disclose polyethers crosslinked by lithium oxytetrafluorosulfonates and derivatives. No aprotic solvents are incorporated. With the addition of lithium salts conductivity of < 10-4 S/cm was achieved.
Armand et al., United States Patent 5,627,292 disclose copolymers formed from vinyl fluoroethoxy sulfonyl fluorides or cyclic ethers having fluoroethoxy sulfonyl fluoride groups with polyethylene oxide, acrylonitrile, pyridine and other monomers. Lithium sulfonate ionomers are formed. No aprotic solvents are incorporated. Conductivity was <10-4 S/cm.
Narang et al., United States Patent 5,633,098 disclose acrylate copolymers having a functionalized polyolefin backbone and pendant groups containing tetrafluoroethoxy lithium sulfonate groups. The comonomers containing the sulfonate groups are present in molar ratios of 50-100%. Compositions are disclosed comprising the polymer and a solvent mixture consisting of propylene carbonate, ethylene carbonate, and dimethoxyethane. Ionic conductivity of those compositions was in the range of 10-4-10-3 S/cm.
Brookhart et al., WO 9623010A2, discloses a copolymer formed from ethene and 1,1,2,2-tetrafluoro-2-[( l, I ,2,2,3,3,4,4 - octafluoro-9-decenyl)oxy]
ethanesulfonyl fluoride via a catalyzed reaction employing diimine-transition metal complexes. The polymer so-formed comprises a polyethylene backbone having randomly distributed pendant groups of 1,1,2,2-tetrafluoro-2-[(1,1,2,2,3,3,4,4-octafluoro-(mostly)octoxy] ethanesulfonyl fluoride, as well as alkyl branches.
SUMMARY OF THE INVENTION
This invention provides for an ionomer comprising a backbone and pendant groups, the backbone consisting essentially of methylene units and the pendant groups comprising ionic radicals of the formula -R~-R~CF2CF2-S02-X-(SOZRf)a M+
where M+ is a univalent metal cation; the Rf groups are independently selected from the group consisting of linear or branched perfluoroalkylene radicals.
perfluoroalkylene radicals containing O or C1, and perfluoroaryl radicals; R
is hydrocarbyl where n = 0 or I; a = 0-2; and X = O, N or C; said ionic radicals being further limited in that a = 0 when X = O, a = I when X = N, and a = 2 when X=C.
This invention further provides for an ionically conductive composition comprising said ionomer described above and a liquid imbibed therewithin.
This invention also discloses a process for forming an ionomer, the process comprising contacting a polyolefin comprising a backbone and pendant groups, the backbone consisting essentially of methylene and methine units and the pendant groups comprising ionic radicals of the formula XS02-CF~CF~-R~-R"-where X is F or Cl, Rp is a linear or branched perfluoroalkylene, perfluoroalkylene containing O or C1, or perfluoroaryl radical, and R is hydrocarbyl where n = 0 or I , with a solution of an alkali metal base.
Further disclosed is a process for forming a conductive composition the process comprising contacting the above ionomer with a liquid.
Also included herein is an electrode comprising at least one electrode active material, the ionomer disclosed herein mixed therewith, and a liquid imbibed therewithin.
Further disclosed is an electrochemical cell comprising a positive electrode, a negative electrode, a separator disposed between the positive and negative electrodes, and a means for connecting the cell to an outside load or source wherein at least one of the group consisting of the separator, the cathode, and the anode, comprises the above ionomer.
DETAILED DESCRIPTION
In a preferred embodiment of the polyolefin ionomer of the invention, the backbone consists essentially of olefmic radicals whereof I-20 mol-% have pendant groups in the form of a radical of the formula M+ -S03-CF2CF~-O-[(CFRICF2)X-Oy]n-(CH2)z' (I) where M+ is an alkali metal cation, R~ is perfluoroalkyl or fluorine, x =
0,1,2, or 3, y = 0 or 1, n = 0,1,2, or 3, and z is an integer in the range of 2 to 6.
Most preferably M+ is a lithium cation, RI is fluorine, x = l, y = 0, n = 1 or 2, z = 4.
35 The olefinic radicals making up the backbone of the polyolefin ionomer of the invention are substantially unsubstituted except that I-20 mol% of the olefinic radicals of the backbone in a preferred embodiment of the invention have a pendant group in the form of the radical (I). In a most preferred embodiment, 2-10 mol-% of the olefinic radicals of the backbone have a pendant group in the form of the radical (I).
As is known in the art, the degree and type of branching in a polyolefin depends upon the monomers employed in the polymerization and the method by which the polymerization is achieved. Ethylene polymerized by various catalytic methods exhibits short chain branches at a frequency of < 1 to ca. 150 per methylene groups in the backbone depending upon the catalyst employed and reaction conditions. The short chain branches so formed are mostly methyl or ethyl groups.
10 When the olefin monomer polymerized is higher than ethylene, the number of branches increases considerably, since there is then at least one side chain inherent in each monomer unit.
It is found in the practice that chain branching has a significant effect on the ionic conductivity of the conductive compositions of the present invention. In order to achieve the highest conductivity, branching frequency of 5-90 methyl branches per 1000 methylenes is preferred when the ionomer of the invention is produced from polymers synthesized by the catalytic routes herein described. A
greater degree of branching appears to be tolerable when the ionomer is made by the graft polymer route hereinbelow described.
20 The preferred ionomers of the invention are conveniently produced according to methods known in the art, by contacting a non-ionic sulfonyl halide precursor with a solution of an alkali metal hydroxide thereby hydrolyzing the polymer to the alkali metal salt. It is found in the practice of the invention, that the acid form of the ionomer of the invention is most easily produced by first 25 subjecting the non-ionic precursor to a solution of an alkali metal hydroxide followed by ion-exchange with an aqueous acid. Other univalent metals, such as copper or silver, can be exchanged for the alkali metal ion by methods of ion exchange known in the art.
The precursor polymers preferred for the practice of the invention can be 30 formed by copolymerization of one or more olefins, preferably ethylene, and a substituted olefin comonomer preferably of the formula FSOrCF2CF2-O-[(CFRtCF2)X-Oy]"-(CH2)Z CH=CH2 where R~ is perfluoroalkyl or fluorine, x = 0,1,2, or 3, y = 0 or l, n =
0,1,2, or 3 and z is an integer in the range of 2 to 6. Most preferably, R1 is fluorine, x = 1, 35 y = 0, n = 1 or 2, and z = 4. Such copolymerizations are known in the art, and are readily achievable using known catalytic methods such as that in Brookhart et al, W09623010A2, and as hereinbelow shown.
Diimine-transition metal complexes as disclosed by Brookhart, and as hereinbelow exemplified, are preferred catalysts for forming the non-ionic precursor polymers preferred for the process of the invention. In the polymer so-formed, the backbone consists essentially of olefinic radicals whereof 1-20 mol-%, preferably 2-10 mol-%, have pendant groups of 1,1,2,2-tetrafluoro-[(1,1,2,2,3,3,4,4-octafluoro-(mostly)octoxy] ethanesulfonyl fluoride, the polymer having fewer than 150, preferably S-90, alkyl, mostly methyl and ethyl, branches per 1000 methylenes. Catalyst structure has a determining effect on number of chain branches. Other catalysts suitable for the practice of the invention include metallocene and Ziegler-Natta catalysts. The most preferred catalysts are the nickel diimine catalysts represented by the structures B and D in Table 2 hereinbelow in combination with PMAO. These catalysts offer a desirable combination of good rates of comonomer incorporation, branching levels in the preferred range all with high polymer yield.
In the case of the preferred diimine nickel catalysts, it has been found in the practice of the present invention that a higher degree of polymer branching results from the use of bulkier catalysts. Less bulky catalysts are associated with higher incorporation of the sulfonyl-containing substituted olefin comonomer.
The degree of branching achieved in metallocene catalyzed copolymerizations (see, for example, Yang et al, J.Am. Chem. Soc. 116, pp. 1001 Sff, 1994) of the preferred comonomers of the invention is generally low with concomitant lower conductivity. However, use of a termonomer, preferably an olefin having three or more carbons in the chain, in combination with a metallocene or Ziegler-Natta catalyst can increase the degree of branching in the resulting polymer with higher resulting ionic conductivity.
Other means are also suitable for forming the ionomers of the invention.
These include forming the ionomer of the present invention by grafting to a substantially unsubstituted polyolefin, preferably polyethylene, a radical of the formula FS02-CF2CF2-O-[(CFR ~ CF~)a-Oy]"-(CH2)Z
where R1 is perfluoroalkyl or fluorine, x = 0,1,2, or 3, y = 0 or 1, n =
0,1,2, or 3 and z is an integer in the range of 2 to 6, is grafted to polyethylene.
Preferably, R 1 is fluorine, x = 1, y=0, n= 1, and z = 2. Numerous methods of grafting onto poiyolefins are known in the art. One method found to be suitable is hereinbelow exemplified.
In another embodiment a polymer having a backbone consisting essentially of olefinic radicals whereof 1-20 mol-% have pendant groups in the form of a radical of the formula XS02-CF2CF2-R~R"-S
where X is F or C1, Ry is a linear or branched perfluoroalkylene, perfluoroalkylene containing O or C1, or perfluoroaryl radical, and R is hydrocarbyl where n = 0 or 1, is reacted with Rf-S02-N(Na)SiMe3 according to the methods taught by Desmarteau, in J. Fluorine Chem., 52, pp.
7ff, 1991. The resulting polymer has a backbone of substantially unsubstituted olefinic radicals whereof 1-20 mol-% have pendant groups in the form of a radical of the formula -Rn Rf-CF2CF2-SO2-~ -S02Rf INa+
10 where the Rf and Rf groups are linear or branched perfluoroalkylene, perfluoroalkylene containing O or Cl, or perfluoroaryl radical, and need not all be the same, R is hydrocarbyl where n = 0 or 1. The sodium ion can be replaced by eg. lithium ion by simple canon exchange procedures known in the art.
In yet another embodiment, a polymer having a backbone consisting essentially of olefinic radicals whereof 1-20 mol% have pendant groups in the form of a radical of the formula X502-CF2CF2-R~R~-where X is F or Cl, Rf is a linear or branched perfluoroalkylene, perfluoroalkylene containing O or Cl, or perfluoroaryl radical, and R is hydrocarbyl where n = 0 or 1, is reacted with (Rf-S02)2-C(MgBr)2 prepared by the method of Seppelt, Inorg. Chem. 27, pp. 2135 ff, 1988, by combining in THF solution and stirring at room temperature overnight, followed by solvent removal and treatment with aqueous HCl for several hours. The 25 solution is then filtered, washed in water, and then treated with a solution of alkali metal base. The resulting polymer has a backbone of substantially unsubstituted olefinic radicals whereof 1-20 mol-% have pendant groups in the form of a radical of the formula -Rn-Rf-CF2CF2-S02-~--(S02Rf)2 M
where M+ is an alkali metal, the Rf and Rf groups are linear or branched perfluoroalkylene, perfluoroalkylene containing O or C1, or perfluoroaryl radical, and need not all be the same, R is hydrocarbyl where n = 0 or 1.
It has been found in the practice of the invention that the degree of comonomer incorporation has a profoundly non-linear effect on the conductivity of the conductive compositions of the invention. For comonomer concentrations below ca. 2 mol-%, conductivity ranges from 0 to ca. 10-5 S/cm, almost independent of the degree of branching or the liquid employed. Conductive compositions exhibiting conductivity of 10-5 Slcm or less are of relatively limited utility.
5 At comonomer incorporation of ca. 2-3 mol-%, ionic conductivity increases considerably, exhibiting strong dependence upon branching and the choice of liquids employed for forming the conductive composition. In the range of ca. 3-10 mol-% conductivities in the range of 10-5 to 10-2 S/cm are achieved while a moderate dependence upon comonomer concentration is observed. Little additional benefit is obtained at comonomer concentrations of ca. 10 mol%
versus ca. 6-7 mol-%. It is believed by the inventors that one reason for this "diminishing returns" effect is that the catalysts required to achieve higher comonomer incorporation into the polymer also produce less-branched polymer so that the two effects are somewhat self cancelling. Nevertheless. conductivity well 15 above 10-5 S/cm is observed in conductive compositions of the invention wherein propylene carbonate is employed as the liquid, at comonomer concentrations in the polymer of less than 10 mol%, in stark contrast to the teachings of the art.
In a preferred embodiment of the present invention, the ionic functionality is present in the ionomer preferably at a concentration of 1-10 mol-%, most preferably 3-7 mol-%.
While there is no limit to the shape or proportions of an article formed from the ionomers of the invention, thin films or membranes are of particular utility. The ionomers of the invention are not fully thermoplastic and are not as readily processible as the non-ionic precursor polymers from which they derive.
25 Thus it is found convenient to form membranes of the precursor polymers by methods generally known in the art and as hereinbelow described. It is particularly convenient to extrude films using a screw extruder and a flat die.
Alternatively, films can be melt pressed. And, in an additional alternative, films may be cast from solutions or dispersions of the precursor polymers by casting 30 onto a substrate and coagulating. No particular method is preferred over another, and the specific method will be chosen according to the needs of the particular practitioner.
The ionomers of the present invention exhibit room temperature ionic conductivity of ca. 10-x-10-6 S/em when dry. However, it is found in the practice 35 of the invention that numerous liquids when imbibed into the ionomer of the invention enhance the conductivity by orders of magnitude. Thus it has been found desirable in order to achieve the most useful embodiments of the present invention to form conductive compositions wherein liquids are imbibed into the ionomer of the invention.
The liquid employed will be dictated by the application. In general terms, it has been found in the practice of the invention that conductivity of the liquid-containing ionomer increases with increasing % weight uptake. increasing liquid dielectric constant, and increasing Lewis basicity of the liquid. while conductivity 5 has been observed to decrease with increasing viscosity and increasing molecular size of the liquid employed. Thus, a highly basic solvent of low viscosity and small molecular size but low dielectric constant may provide superior conductivity in a given membrane than a larger, more viscous, less basic solvent of very high dielectric constant. Of course, other considerations come into play as well.
For example, excessive solubility of the ionomer in the liquid may be undesirable.
Or, the liquid may be electrochemically unstable in the intended use.
One particularly preferred embodiment comprises the lithium ionomer combined with aprotic solvents, preferably organic carbonates, which are useful in lithium batteries.
15 The preferred electrode of the invention comprises a mixture of one or more electrode active materials in particulate form, the ionomer of the invention, at least one electron conductive additive, and at least one organic carbonate.
Examples of useful anode active materials include, but are not limited to, carbon (graphitic, coke-type, mesocarbons, polyacenes, and the like) and lithium-20 intercalated carbon, lithium metal nitrides such as Li2.6Cop.4N, tin oxide, based glasses, lithium metal, and lithium alloys, such as alloys of lithium with aluminum, tin, magnesium, silicon, tin, manganese, iron, and zinc. Lithium intercalation anodes employing carbon are preferred. Useful cathode active materials include, but are not limited to, transition metal oxides and sulfides, 25 lithiated transition metal oxides and sulfides, and organosulfur compounds.
Examples of such are cobalt oxides. manganese oxides, molybdenum oxides, vanadium oxides, sulfides of titanium, molybdenum and niobium, lithiated oxides such as spinet lithium manganese oxides Lii+XMn2-X04, chromium-doped spinet lithium manganese oxides LiXCryMnZ04, LiCo02, LiNi02, LiNiXCo 1 _X02 where 30 x is 0 < x < 1, with a preferred range of 0.5 < x < 0.95, LiCoV04, and mixtures thereof. LiNiXCo~-X02 is preferred. A highly preferred electron conductive aid is carbon black, preferably Super P carbon black, available from the MMM S.A.
Carbon, Brussels, Belgium, in the concentration range of 1-10%. Preferably, the volume fraction of the lithium ionomer in the finished electrode is between 4 and 35 40%.
The electrode of the invention may conveniently be made by dissolution of all polymeric components into a common solvent and mixing together with the carbon black particles and electrode active particles. For cathodes the preferred electrode active material is LiNi,;Co~_XO~ wherein 0 < x < 1, while for anodes the preferred electrode active material is graphitized mesocarbon microbeads. For example, a preferred lithium battery electrode of the invention can be fabricated by dissolving ionomer of the invention in a mixture of acetone and dimethyl formamide, followed by addition of particles of electrode active material and carbon black, followed by deposition of a film on a substrate and drying. The resultant preferred electrode will comprise electrode active material, conductive carbon black, and ionomer of the invention, where, preferably, the weight ratio of ionomer to electrode active material is between 0.05 and 0.8 and the weight ratio of carbon black to electrode active material is between 0.01 and 0.2. Most preferably the weight ratio of ionomer to electrode active material is between 0.1 and 0.25 and the weight ratio of carbon black to electrode active material is between 0.02 and 0.1. This electrode can then be cast from solution onto a suitable support such as a glass plate or current collector metal foil, and formed into a film using techniques well-known in the art. The electrode film thus IS produced can then be incorporated into a mufti-layer electrochemical cell structure by lamination, as hereinbelow described.
It may be desirable to incorporate into the separator composition of the invention such adjuvants as may be useful for such purposes as improving the binding of the components thereof, or providing improved structural integrity of an article fabricated therefrom. One particularly preferred additional material is Si02 which may be incorporated simply by dispersing the particles thereof into the same solution from which the separator is being formed, as hereinabove described. Preferred are silica particles of an average particle dimension of less than 1.0 micrometers, the silica being present in the admixture at up to 50%
by weight of the total.
In an alternative process, the dispersion of electrode-active material and optional carbon black and other adjuvants can first be cast onto a surface followed by addition of the ionomer of the invention in organic carbonate solution.
The invention is further described in the following specific embodiments.
EXAMPLES
Precursor non-ionic polymers I-XIV hereinbelow described, were formed by copolymerization of ethylene with a comonomer of the formula FS02-CF2CF2-O-(CF2)~(CH2)4CH=CHZ
where n = 2 or 4. The solvent employed was toluene, except in the case of the synthesis of Polymer XI wherein it was dichloromethane.
Referring to Table 1, polymers I-X and X1V were synthesized by combining in a Schlenk flask in a nitrogen purged drybox, the indicated amounts of the indicated catalyst, comonomer, and solvent. The structure of the designated catalyst is provided in Table 2. The mixture was then brought out of the dry box and placed under 1 atmosphere of ethylene. The mixture was purged with ethylene for 15 minutes while cooling by immersion in an ice water bath. 2.2 ml of a 7.1 % solution of polymethylalumoxane (PMAO) in toluene (4.4 mL for polymers VII and XIV) was then introduced to initiate the reaction, and the 5 mixture was agitated for the indicated time. At the end of the indicated time, 5 ml of methanol was slowly added to the reaction mixture, after which the mixture was decanted into 150 ml of methanol, followed by addition of 1.5 ml of concentrated aqueous HC1. The resulting mixture was stirred for ca. 30 minutes.
The resulting white solid polymer was filtered, washed with six 20 ml aliquots of methanol. and dried in vacuo.
Polymer XI was synthesized by combining the indicated amounts of the indicated catalyst, comonomer and dichloromethane solvent in a Schlenk flask.
Reaction was initiated by placing the mixture under 1 atmosphere of ethylene at room temperature; no PMAO was added. Reaction proceeded for 4,260 minutes 15 under agitation. The resulting polymer was an oily liquid. The reaction was filtered. To the filtrate was added 350 ml of methanol with agitation. An oil precipitate was isolated and redissolved in 100 ml of dichloromethane followed by addition of 350 ml of methanol. A light yellow oil product was isolated and dried in vacuo. The material so-produced exhibited a glass transition temperature of -66°C and no melting point.
Polymers XII and XIII were produced by combining in a Schlenk flask in a drybox the indicated amounts of the indicated catalyst, comonomer, and solvent.
The mixture was placed under 1 atmosphere of ethylene and purged with ethylene for 15 minutes. 10 ml of a 7.1 % solution of PMAO in toluene was added to 25 initiate the reaction which continued under agitation for the indicated time at the indicated temperature. 350 ml of methanol was slowly added to the reaction mixture followed by 5 ml conc. HCI. The white solid polymer was filtered, washed with methanol and dried in vacuo.
Molecular weight was determined by gel permeation chromatography using polyethylene standards. Melting points were determined by employing a DuPont model 912 Differential Scanning Calorimeter by cooling to -100°C, then heating at l OC°/min to 150°C. In the examples hereinbelow described, the polymers are designated according to Roman numerals I-XVII. The catalysts employed are designated in Table 1 by a letter designation corresponding to the catalysts listed in Table 2. The % of comonomer in the polymer was determined by a combination of proton and ~3C nuclear magnetic resonance.
O ~ N N N N ~ N O ~ OC f-~ O O
~ .-. ~
N
h ~
~ --N N O~ v W n ~ V O N ~ N
; h _ \ ~
. ~O N r ~ M ~ O vp 1 r Q N
0000 (Vv1 ~pN h V M ~ O M -\O
N - ~-N .-N M ~ N .-.-U
.0 O.. o0 C V'~ cYh O~M V'00 O~vJ V h C
~O
M M ~ V~ N O f~1f~ f1V~
O
U
> N
C U U f'J O~ v~ ~- fV V O 00 h 00 v~ M N
'_' N h O~ O pp n 4. O ...
a O O
_ 3i C
O y 00 00 O O O O O ~n O ~n O O O o0 h! M M fn M M O ~f C ~p M M N
~ N
2~ ~1' C
o n O O O O O O O O O O M M O O
E-~ N N
OG
T
C
.
C = 4-.
O ~ O ~ O O O O O O O O O ~n O v'1inO
~
- _ ~ " M f~1M M M M h N M M V1M M ~D
a U
_ _ O ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ 0 ~
_ ppv OD OWO
O O O O O O O O N Yl v1 ~ N ~ fn ~ O~
O
U ~~ N N N N N CV N N ~ ~ N N N
C
V
c N h h h h h c v h h h c ~ 0 0 0 0 0 0 0 0 0 0 - o °0 0 E ~ 0 0 0 0 0 0 0 0 0 0 0 o c o a~
Q cn U D u7 c~. D D m fn C7 ~ 2 m > > > > X x x X >C 7G
TABLE 2: Catalysts Employed in the Synthesis of Polymers I-XIV
CATALYST
DESIGNATION Catalyst A
~N
Ni r\
tar Br B
Br/ \ Br C H H
N~ /N
Ni Br Br D
N/ ~ N
Ni Br Br E i N~ ~N
\ /
Ni Br / Br F
N\ ~N
Ni Br/ \Br G Pd(CH2)3C(O)OCH3( {2,6-[CH(CH3)2]2C6fI3}2DAB(CH3)2)SbF6 H rac-ethylenebis(indenyl)zirconium (IV) dichloride Precursor non-ionic polymrs XV and XVI hereinbelow described, were formed by copolymerization of propylen with a comonomer of the formula FS02-CF2CF2-O-(CF~)2(CH2)4CH=CHI
The solvent employed was toluene.
Polymer XV was synthesized by combining in a Schlenk flask in a drybox 2.3 mg (0.0055 mmol) of the catalyst rac-ethylenebis(indenyl)zirconium (IV) dichloride, 2.72 g (7.11 mmol) CH2=CH(CH2)4(CF2)20(CF2)2S02F and 25 mL
toluene. This was placed under 3 psig of propylene in an ice-water bath and was 10 purged with propylene for 10 min. PMAO (7.2 mL 7.1 wt% toluene solution) was added to the mixture. After stirring under 3 psig of propylene at 0°C
for 1 hr, methanol (150 mL) was slowly added to the reaction mixture followed by 5 mL
conc. HCI. The white solid polymer was filtered, washed with methanol and dried in vacuo. Copolymer (1.35 g) was obtained. The polymer was isotactic based on ~ 3C NMR. ~ H NMR(TCE-d~) indicated a comonomer incorporation of 2.9 mole %. The copolymer exhibits a melting point of 133°C by differential scanning calorimetry. Gel permeation chromatography (TCB, 135°C, Polyethylene standard): Mw = 23,200; Mn = 11,000; Mw/Mn = 2.1.
Polymer XVI was synthesized by combining in a Schlenk flask in a drybox 2.3 mg (0.0055 mmol) of the catalyst rac-ethylenebis(indenyl)zirconium (IV) dichloride, 5.5 g (0.0144 mol) CH2=CH(CH2)4(CF2)20(CF2)~S02F, and 25 ml toluene. This was placed under 3 psig of propylene in an ice-water bath and was purged with propylene for 10 min. PMAO {4.0 mL 12.9 wt % toluene solution) was added to the mixture. After stirring under 3 psig of propylene at 0°C for 2 hr, methanol (5 rnL) was slowly added to the reaction mixture. The mixture was then poured into 150 mL methanol, followed by 5 mL of conc. HCI. After stirring at room temperature for 20 min, the white solid polymer was filtered, washed with methanol and dried in vacuo. Copolymer (4.6 g) was obtained. The polymer was isotactic based on ~--'C NMR. ~H NMR(TCE-d~) indicated a comonomer incorporation of 3.8 mole %. The copolymer exhibits a melting point of 124°C by differential scanning calorimetry. Gel permeation chromatography (TCB, 135°C, Polyethylene standard): Mw = 39,200; Mn = 20,900; Mw/Mn = 1.9.
10 Precursor non-ionic polymer XVII hereinbelow described was formed by grafting of CH2=CH(CF2)~O(CF~)~S02F on high density polyethylene.
Polymer XVII was synthesized by combining a solution of 13.03 g of high density polyethylene (Aldrich, Mw = 125,000) in 100 ml o-dichlorobenzene at 125°C, with 10.15 g CH2=CH(CF~)~O(CF~)~SO~F under nitrogen followed by 15 slow addition of a dichlorobenzene solution of tert-butyl peroxide(1.23 g tBu00tBu in 20 mL 0-dichlorobenzene). Addition was finished in 7 hr. The solution was then allowed to stir overnight. The solution was poured into 500 mL
methanol, and blended in a laboratory blender followed by filtration, the steps of methanol dissolution, blending, and filtration being performed a total of four 20 times. The solid polymer was then washed with methanol three times and dried in vacuo. White polymer (21.3 g) was obtained. Based on ~ H NMR, the mole percentage of comonomer incorporation was 5.4%. Based on NMR branching frequency was 7 Me/1000CI-h. GPC(TCB, i 35°C, PE standard): Mw =
65,700;
Mn = 4,820; P/D = 15.3. The copolymer has a melting point of 1 I 8°C
based on 25 DSC.
Films designated F 1-F 16, F I 9, F21-F23 of the invention were fabricated from the polymers of the invention.
Polymer VI was found to be excessively brittle to permit further handling, probably because of low molecular weight, and could not be fabricated into a free-30 standing film. Polymer XI was an oil which could not be fabricated into a free-standing film at room temperature.
All the other polymers hereinabove designated Polymer I-V and Polymer VII-X, and XII-XVII were fabricated into films. Melt-pressed films, designated in Table 3 as "MP", in the range of 3.75 cm x 3.75 cm to 7.5 cm 35 x7.5 cm were formed by placing ca. 0.25-5.0 g of the dried polymer between two sheets of Kapton~ Polyimide Film available from DuPont, Wilmington, DE, and inserted between the platens of a hydraulic press (model P218C, Pasadena Hydraulic Industries, City of Industry, CA) equipped with Omron Electronics lnc.
(Schaumburg, IL) ESCS temperature controllers. The polymer was preheated for two minutes, followed by compression for two minutes, followed by cooling under pressure. Resulting films ranged in thickness from ca. 63 to 127 micro-meters. Specific temperatures and pressures employed are provided in Table 3.
Solution cast films, designated in Table 3 as "soln", were prepared by dissolving 0.25-S.0 g of polymer into the indicated solvent by heating the solvent until the polymer dissolved, followed by casting onto a glass casting tray with 2.5 cm x 2.5 cm wells. The solvent was evaporated at room temperature leaving polymer films ranging in thickness from ca. 25-127 micrometers.
Table 3 - Formation of Polymer Films Polymer FILM SPECIMEN ~# Film Conditions IX F3 MP103 C/625psi/2min F4 MP103 C/625psi/2min VIII FS SOLN dichlorobenzene III F6 SOLN chlorobenzene F7 SOLN chlorobenzene II F10 MP240C/2500 Ibs/in' Fl 1 MP240C/2500 lbs/in2 V F12 MP240C/ 2500 lbs/in2 VII F13 MP240C/2500 lbs/in'-F14 MP240C/2500 Ibs/in2 XII F15 MP140C/2500 psi XIII F16 MP140C/2500 lbs/in2/2 Min XVI F22 MP 160C/2500 psi/2 min.
XVII F23 MP 250C/3000 psi/2 min.
Each of the film samples F I -F 16, F 19, F21-F23 described in Table 3, plus two oil aliquots of polymer XI, were hydrolyzed by treatment with a saturated t r solution of LiOH in 1:1 water methanol, followed by a rinse in I :1 water methanol at room temperature, and then heating in a fresh 1:1 water/methanol mixture.
Specimens were then dried, except where otherwise specified in a Model 1430 vacuum oven available from V WR Scientific, West Chester, PA, at a pressure of S ca. 220 torn. Table 4 provides the duration and temperature of film exposure to ' the LiOH solution, the duration of the room temperature rinse, the temperature and duration of the warm rinse, and the temperature and duration of drying of the ' hydrolyzed film.
c~
~' ~O M
,~ \ \
~
~ ~ ~
V_~M_ _V10_OI_~l_~ M_ O_0_ O O O O O O O ~ ~ O ~1 O
N
U U U U U o U o U U U
0 0 n o o o ~ ~n o o ... ~ ~ ~n o vovc ~ ~ ~t vo ~ ~O
~
ar a,ar ar ad~ w ar y x ~ .~ .~.~
,.,~ ~, ~, .~
~
~ ~, 3 -~
c O p N N
-.... ~ ~ ~ ~ ~ ~'N ~t z a ,~y x air ~.~r ~ o .b~ U U U U U U U U U U U
o o o O a O o o ~no ~n o ~n ~n o 0 o ~.
~
4 ~ ~ ~
a~
,3 a.u .~ ~ ~ an au ~ w.~ ~r ar ar ftS G~
CCS CV CC ~CCd CCSC~G~S CCi CC fC
~ ~ ~ ~ ~ .~~ ~ .~ C
N
N w0 ~O ~ . ~G N o0 ~D ~O .
eh ~O -r v0 ~-H
~r~ r.rv--y ~r O
w w w w w w r~,u~ w w W~
~.
z ..-rN M ~h'V7 ~O I~00 p~
C~ C~ C/~ C!~V7 C/~C/~C/7 i/1 ""a O
G ~
s.., E'r N O N .-~ N
U
~ ~
~ v ~ ~ C ~ v'~ ~D
C_ UU U U U U U U U
o o 0 o y.. ~ ~ 0 a c~ o G
N N 'd'~ ~h ~ -~ .x~
IONOMERS AND IONICALLY CONDUCTIVE COMPOSITIONS
FIELD OF THE INVENTION
This invention relates to ionomers comprising functionalized polyolefins having fluoroalkyl sulfonate pendant groups and to ionically conductive compositions formed therefrom by the addition of solvents thereto. The ionically conductive compositions of the invention are useful in batteries, fuel cells, electrolysis cells, ion exchange membranes, sensors, electrochemical capacitors, and modified electrodes.
It has long been known in the art to form ionically conducting membranes and gels from organic polymers containing ionic pendant groups. Such polymers are known as ionomers. Particularly well-known ionomer membranes in widespread commercial use are Nafion~ Membranes available from E. I. du Pont de Nemours and Company. Nafion~ is formed by copolymerizing tetra-fluoro ethylene (TFE) with perfluoro(3,6-dioxa-4-methyl-7-octenesulfonyl fluoride), as disclosed in U.S. Patent 3,282,875. Also known are copolymers of TFE with perfluoro (3-oxa-4-pentene sulfonyl fluoride), as disclosed in U.S. Patent 4,358,545. The copolymers so formed are converted to the ionomeric form by hydrolysis, typically by exposure to an appropriate aqueous base, as disclosed in U.S. Patent 3,282,875. Lithium, sodium and potassium are all well known in the art as suitable cations for the above cited ionomers.
In the polymers above-cited, the fluorine atoms provide more than one benefit. The fluorine groups on the carbons proximate to the sulfonyl group in the pendant side chain provide the electronegativity to render the cation sufficiently labile so as to provide high ionic conductivity. Replacement of those fluorine atoms with hydrogen results in a considerable reduction in ionic mobility and consequent loss of conductivity.
The remainder of the fluorine atoms afford the chemical and thermal stability to the polymer normally associated with fluorinated polymers. This has proven to be of considerable value in such applications as the well-known "chlor-alkali" process. However, highly fluorinated polymers also have disadvantages where there is less need for high chemical and thermal stability. The fluorinated monomers are more expensive than their olefin counterparts, require higher processing temperatures, and often require expensive corrosion resistant processing equipment. Furthermore, it is difficult to form solutions and dispersions of fluoropolymers. Additionally, it is difficult to form strong adhesive bonds with fluoropolymers. In materials employed in electrochemical cells, for example, it may be advantageous to have better processibility at some cost to chemical and thermal stability. Thus, there is an incentive to develop ionomers with highly labile canons having non-fluorinated polymer backbones.
Numerous publications disclose polyethers with either proximal ionic species in the polymer or in combination with ionic salts. Conductivities are in S the range of 10-5 S/cm and less. Le Nest et al., Polymer Communications 28, (1987) disclose a composition of polyether glycol oligomers joined by phosphate or thiophosphate moieties hydrolyzed to the related lithium ionomer. In combination with propylene carbonate, conductivity in the range of I-10 x10-4 S/cm was realized. A review of the related art is found in Fauteux et al., Electrochimica Acta 40, 2185 (1995).
Benrabah et al, Electrochimica Acta, 40, 2259 (1995) disclose polyethers crosslinked by lithium oxytetrafluorosulfonates and derivatives. No aprotic solvents are incorporated. With the addition of lithium salts conductivity of < 10-4 S/cm was achieved.
Armand et al., United States Patent 5,627,292 disclose copolymers formed from vinyl fluoroethoxy sulfonyl fluorides or cyclic ethers having fluoroethoxy sulfonyl fluoride groups with polyethylene oxide, acrylonitrile, pyridine and other monomers. Lithium sulfonate ionomers are formed. No aprotic solvents are incorporated. Conductivity was <10-4 S/cm.
Narang et al., United States Patent 5,633,098 disclose acrylate copolymers having a functionalized polyolefin backbone and pendant groups containing tetrafluoroethoxy lithium sulfonate groups. The comonomers containing the sulfonate groups are present in molar ratios of 50-100%. Compositions are disclosed comprising the polymer and a solvent mixture consisting of propylene carbonate, ethylene carbonate, and dimethoxyethane. Ionic conductivity of those compositions was in the range of 10-4-10-3 S/cm.
Brookhart et al., WO 9623010A2, discloses a copolymer formed from ethene and 1,1,2,2-tetrafluoro-2-[( l, I ,2,2,3,3,4,4 - octafluoro-9-decenyl)oxy]
ethanesulfonyl fluoride via a catalyzed reaction employing diimine-transition metal complexes. The polymer so-formed comprises a polyethylene backbone having randomly distributed pendant groups of 1,1,2,2-tetrafluoro-2-[(1,1,2,2,3,3,4,4-octafluoro-(mostly)octoxy] ethanesulfonyl fluoride, as well as alkyl branches.
SUMMARY OF THE INVENTION
This invention provides for an ionomer comprising a backbone and pendant groups, the backbone consisting essentially of methylene units and the pendant groups comprising ionic radicals of the formula -R~-R~CF2CF2-S02-X-(SOZRf)a M+
where M+ is a univalent metal cation; the Rf groups are independently selected from the group consisting of linear or branched perfluoroalkylene radicals.
perfluoroalkylene radicals containing O or C1, and perfluoroaryl radicals; R
is hydrocarbyl where n = 0 or I; a = 0-2; and X = O, N or C; said ionic radicals being further limited in that a = 0 when X = O, a = I when X = N, and a = 2 when X=C.
This invention further provides for an ionically conductive composition comprising said ionomer described above and a liquid imbibed therewithin.
This invention also discloses a process for forming an ionomer, the process comprising contacting a polyolefin comprising a backbone and pendant groups, the backbone consisting essentially of methylene and methine units and the pendant groups comprising ionic radicals of the formula XS02-CF~CF~-R~-R"-where X is F or Cl, Rp is a linear or branched perfluoroalkylene, perfluoroalkylene containing O or C1, or perfluoroaryl radical, and R is hydrocarbyl where n = 0 or I , with a solution of an alkali metal base.
Further disclosed is a process for forming a conductive composition the process comprising contacting the above ionomer with a liquid.
Also included herein is an electrode comprising at least one electrode active material, the ionomer disclosed herein mixed therewith, and a liquid imbibed therewithin.
Further disclosed is an electrochemical cell comprising a positive electrode, a negative electrode, a separator disposed between the positive and negative electrodes, and a means for connecting the cell to an outside load or source wherein at least one of the group consisting of the separator, the cathode, and the anode, comprises the above ionomer.
DETAILED DESCRIPTION
In a preferred embodiment of the polyolefin ionomer of the invention, the backbone consists essentially of olefmic radicals whereof I-20 mol-% have pendant groups in the form of a radical of the formula M+ -S03-CF2CF~-O-[(CFRICF2)X-Oy]n-(CH2)z' (I) where M+ is an alkali metal cation, R~ is perfluoroalkyl or fluorine, x =
0,1,2, or 3, y = 0 or 1, n = 0,1,2, or 3, and z is an integer in the range of 2 to 6.
Most preferably M+ is a lithium cation, RI is fluorine, x = l, y = 0, n = 1 or 2, z = 4.
35 The olefinic radicals making up the backbone of the polyolefin ionomer of the invention are substantially unsubstituted except that I-20 mol% of the olefinic radicals of the backbone in a preferred embodiment of the invention have a pendant group in the form of the radical (I). In a most preferred embodiment, 2-10 mol-% of the olefinic radicals of the backbone have a pendant group in the form of the radical (I).
As is known in the art, the degree and type of branching in a polyolefin depends upon the monomers employed in the polymerization and the method by which the polymerization is achieved. Ethylene polymerized by various catalytic methods exhibits short chain branches at a frequency of < 1 to ca. 150 per methylene groups in the backbone depending upon the catalyst employed and reaction conditions. The short chain branches so formed are mostly methyl or ethyl groups.
10 When the olefin monomer polymerized is higher than ethylene, the number of branches increases considerably, since there is then at least one side chain inherent in each monomer unit.
It is found in the practice that chain branching has a significant effect on the ionic conductivity of the conductive compositions of the present invention. In order to achieve the highest conductivity, branching frequency of 5-90 methyl branches per 1000 methylenes is preferred when the ionomer of the invention is produced from polymers synthesized by the catalytic routes herein described. A
greater degree of branching appears to be tolerable when the ionomer is made by the graft polymer route hereinbelow described.
20 The preferred ionomers of the invention are conveniently produced according to methods known in the art, by contacting a non-ionic sulfonyl halide precursor with a solution of an alkali metal hydroxide thereby hydrolyzing the polymer to the alkali metal salt. It is found in the practice of the invention, that the acid form of the ionomer of the invention is most easily produced by first 25 subjecting the non-ionic precursor to a solution of an alkali metal hydroxide followed by ion-exchange with an aqueous acid. Other univalent metals, such as copper or silver, can be exchanged for the alkali metal ion by methods of ion exchange known in the art.
The precursor polymers preferred for the practice of the invention can be 30 formed by copolymerization of one or more olefins, preferably ethylene, and a substituted olefin comonomer preferably of the formula FSOrCF2CF2-O-[(CFRtCF2)X-Oy]"-(CH2)Z CH=CH2 where R~ is perfluoroalkyl or fluorine, x = 0,1,2, or 3, y = 0 or l, n =
0,1,2, or 3 and z is an integer in the range of 2 to 6. Most preferably, R1 is fluorine, x = 1, 35 y = 0, n = 1 or 2, and z = 4. Such copolymerizations are known in the art, and are readily achievable using known catalytic methods such as that in Brookhart et al, W09623010A2, and as hereinbelow shown.
Diimine-transition metal complexes as disclosed by Brookhart, and as hereinbelow exemplified, are preferred catalysts for forming the non-ionic precursor polymers preferred for the process of the invention. In the polymer so-formed, the backbone consists essentially of olefinic radicals whereof 1-20 mol-%, preferably 2-10 mol-%, have pendant groups of 1,1,2,2-tetrafluoro-[(1,1,2,2,3,3,4,4-octafluoro-(mostly)octoxy] ethanesulfonyl fluoride, the polymer having fewer than 150, preferably S-90, alkyl, mostly methyl and ethyl, branches per 1000 methylenes. Catalyst structure has a determining effect on number of chain branches. Other catalysts suitable for the practice of the invention include metallocene and Ziegler-Natta catalysts. The most preferred catalysts are the nickel diimine catalysts represented by the structures B and D in Table 2 hereinbelow in combination with PMAO. These catalysts offer a desirable combination of good rates of comonomer incorporation, branching levels in the preferred range all with high polymer yield.
In the case of the preferred diimine nickel catalysts, it has been found in the practice of the present invention that a higher degree of polymer branching results from the use of bulkier catalysts. Less bulky catalysts are associated with higher incorporation of the sulfonyl-containing substituted olefin comonomer.
The degree of branching achieved in metallocene catalyzed copolymerizations (see, for example, Yang et al, J.Am. Chem. Soc. 116, pp. 1001 Sff, 1994) of the preferred comonomers of the invention is generally low with concomitant lower conductivity. However, use of a termonomer, preferably an olefin having three or more carbons in the chain, in combination with a metallocene or Ziegler-Natta catalyst can increase the degree of branching in the resulting polymer with higher resulting ionic conductivity.
Other means are also suitable for forming the ionomers of the invention.
These include forming the ionomer of the present invention by grafting to a substantially unsubstituted polyolefin, preferably polyethylene, a radical of the formula FS02-CF2CF2-O-[(CFR ~ CF~)a-Oy]"-(CH2)Z
where R1 is perfluoroalkyl or fluorine, x = 0,1,2, or 3, y = 0 or 1, n =
0,1,2, or 3 and z is an integer in the range of 2 to 6, is grafted to polyethylene.
Preferably, R 1 is fluorine, x = 1, y=0, n= 1, and z = 2. Numerous methods of grafting onto poiyolefins are known in the art. One method found to be suitable is hereinbelow exemplified.
In another embodiment a polymer having a backbone consisting essentially of olefinic radicals whereof 1-20 mol-% have pendant groups in the form of a radical of the formula XS02-CF2CF2-R~R"-S
where X is F or C1, Ry is a linear or branched perfluoroalkylene, perfluoroalkylene containing O or C1, or perfluoroaryl radical, and R is hydrocarbyl where n = 0 or 1, is reacted with Rf-S02-N(Na)SiMe3 according to the methods taught by Desmarteau, in J. Fluorine Chem., 52, pp.
7ff, 1991. The resulting polymer has a backbone of substantially unsubstituted olefinic radicals whereof 1-20 mol-% have pendant groups in the form of a radical of the formula -Rn Rf-CF2CF2-SO2-~ -S02Rf INa+
10 where the Rf and Rf groups are linear or branched perfluoroalkylene, perfluoroalkylene containing O or Cl, or perfluoroaryl radical, and need not all be the same, R is hydrocarbyl where n = 0 or 1. The sodium ion can be replaced by eg. lithium ion by simple canon exchange procedures known in the art.
In yet another embodiment, a polymer having a backbone consisting essentially of olefinic radicals whereof 1-20 mol% have pendant groups in the form of a radical of the formula X502-CF2CF2-R~R~-where X is F or Cl, Rf is a linear or branched perfluoroalkylene, perfluoroalkylene containing O or Cl, or perfluoroaryl radical, and R is hydrocarbyl where n = 0 or 1, is reacted with (Rf-S02)2-C(MgBr)2 prepared by the method of Seppelt, Inorg. Chem. 27, pp. 2135 ff, 1988, by combining in THF solution and stirring at room temperature overnight, followed by solvent removal and treatment with aqueous HCl for several hours. The 25 solution is then filtered, washed in water, and then treated with a solution of alkali metal base. The resulting polymer has a backbone of substantially unsubstituted olefinic radicals whereof 1-20 mol-% have pendant groups in the form of a radical of the formula -Rn-Rf-CF2CF2-S02-~--(S02Rf)2 M
where M+ is an alkali metal, the Rf and Rf groups are linear or branched perfluoroalkylene, perfluoroalkylene containing O or C1, or perfluoroaryl radical, and need not all be the same, R is hydrocarbyl where n = 0 or 1.
It has been found in the practice of the invention that the degree of comonomer incorporation has a profoundly non-linear effect on the conductivity of the conductive compositions of the invention. For comonomer concentrations below ca. 2 mol-%, conductivity ranges from 0 to ca. 10-5 S/cm, almost independent of the degree of branching or the liquid employed. Conductive compositions exhibiting conductivity of 10-5 Slcm or less are of relatively limited utility.
5 At comonomer incorporation of ca. 2-3 mol-%, ionic conductivity increases considerably, exhibiting strong dependence upon branching and the choice of liquids employed for forming the conductive composition. In the range of ca. 3-10 mol-% conductivities in the range of 10-5 to 10-2 S/cm are achieved while a moderate dependence upon comonomer concentration is observed. Little additional benefit is obtained at comonomer concentrations of ca. 10 mol%
versus ca. 6-7 mol-%. It is believed by the inventors that one reason for this "diminishing returns" effect is that the catalysts required to achieve higher comonomer incorporation into the polymer also produce less-branched polymer so that the two effects are somewhat self cancelling. Nevertheless. conductivity well 15 above 10-5 S/cm is observed in conductive compositions of the invention wherein propylene carbonate is employed as the liquid, at comonomer concentrations in the polymer of less than 10 mol%, in stark contrast to the teachings of the art.
In a preferred embodiment of the present invention, the ionic functionality is present in the ionomer preferably at a concentration of 1-10 mol-%, most preferably 3-7 mol-%.
While there is no limit to the shape or proportions of an article formed from the ionomers of the invention, thin films or membranes are of particular utility. The ionomers of the invention are not fully thermoplastic and are not as readily processible as the non-ionic precursor polymers from which they derive.
25 Thus it is found convenient to form membranes of the precursor polymers by methods generally known in the art and as hereinbelow described. It is particularly convenient to extrude films using a screw extruder and a flat die.
Alternatively, films can be melt pressed. And, in an additional alternative, films may be cast from solutions or dispersions of the precursor polymers by casting 30 onto a substrate and coagulating. No particular method is preferred over another, and the specific method will be chosen according to the needs of the particular practitioner.
The ionomers of the present invention exhibit room temperature ionic conductivity of ca. 10-x-10-6 S/em when dry. However, it is found in the practice 35 of the invention that numerous liquids when imbibed into the ionomer of the invention enhance the conductivity by orders of magnitude. Thus it has been found desirable in order to achieve the most useful embodiments of the present invention to form conductive compositions wherein liquids are imbibed into the ionomer of the invention.
The liquid employed will be dictated by the application. In general terms, it has been found in the practice of the invention that conductivity of the liquid-containing ionomer increases with increasing % weight uptake. increasing liquid dielectric constant, and increasing Lewis basicity of the liquid. while conductivity 5 has been observed to decrease with increasing viscosity and increasing molecular size of the liquid employed. Thus, a highly basic solvent of low viscosity and small molecular size but low dielectric constant may provide superior conductivity in a given membrane than a larger, more viscous, less basic solvent of very high dielectric constant. Of course, other considerations come into play as well.
For example, excessive solubility of the ionomer in the liquid may be undesirable.
Or, the liquid may be electrochemically unstable in the intended use.
One particularly preferred embodiment comprises the lithium ionomer combined with aprotic solvents, preferably organic carbonates, which are useful in lithium batteries.
15 The preferred electrode of the invention comprises a mixture of one or more electrode active materials in particulate form, the ionomer of the invention, at least one electron conductive additive, and at least one organic carbonate.
Examples of useful anode active materials include, but are not limited to, carbon (graphitic, coke-type, mesocarbons, polyacenes, and the like) and lithium-20 intercalated carbon, lithium metal nitrides such as Li2.6Cop.4N, tin oxide, based glasses, lithium metal, and lithium alloys, such as alloys of lithium with aluminum, tin, magnesium, silicon, tin, manganese, iron, and zinc. Lithium intercalation anodes employing carbon are preferred. Useful cathode active materials include, but are not limited to, transition metal oxides and sulfides, 25 lithiated transition metal oxides and sulfides, and organosulfur compounds.
Examples of such are cobalt oxides. manganese oxides, molybdenum oxides, vanadium oxides, sulfides of titanium, molybdenum and niobium, lithiated oxides such as spinet lithium manganese oxides Lii+XMn2-X04, chromium-doped spinet lithium manganese oxides LiXCryMnZ04, LiCo02, LiNi02, LiNiXCo 1 _X02 where 30 x is 0 < x < 1, with a preferred range of 0.5 < x < 0.95, LiCoV04, and mixtures thereof. LiNiXCo~-X02 is preferred. A highly preferred electron conductive aid is carbon black, preferably Super P carbon black, available from the MMM S.A.
Carbon, Brussels, Belgium, in the concentration range of 1-10%. Preferably, the volume fraction of the lithium ionomer in the finished electrode is between 4 and 35 40%.
The electrode of the invention may conveniently be made by dissolution of all polymeric components into a common solvent and mixing together with the carbon black particles and electrode active particles. For cathodes the preferred electrode active material is LiNi,;Co~_XO~ wherein 0 < x < 1, while for anodes the preferred electrode active material is graphitized mesocarbon microbeads. For example, a preferred lithium battery electrode of the invention can be fabricated by dissolving ionomer of the invention in a mixture of acetone and dimethyl formamide, followed by addition of particles of electrode active material and carbon black, followed by deposition of a film on a substrate and drying. The resultant preferred electrode will comprise electrode active material, conductive carbon black, and ionomer of the invention, where, preferably, the weight ratio of ionomer to electrode active material is between 0.05 and 0.8 and the weight ratio of carbon black to electrode active material is between 0.01 and 0.2. Most preferably the weight ratio of ionomer to electrode active material is between 0.1 and 0.25 and the weight ratio of carbon black to electrode active material is between 0.02 and 0.1. This electrode can then be cast from solution onto a suitable support such as a glass plate or current collector metal foil, and formed into a film using techniques well-known in the art. The electrode film thus IS produced can then be incorporated into a mufti-layer electrochemical cell structure by lamination, as hereinbelow described.
It may be desirable to incorporate into the separator composition of the invention such adjuvants as may be useful for such purposes as improving the binding of the components thereof, or providing improved structural integrity of an article fabricated therefrom. One particularly preferred additional material is Si02 which may be incorporated simply by dispersing the particles thereof into the same solution from which the separator is being formed, as hereinabove described. Preferred are silica particles of an average particle dimension of less than 1.0 micrometers, the silica being present in the admixture at up to 50%
by weight of the total.
In an alternative process, the dispersion of electrode-active material and optional carbon black and other adjuvants can first be cast onto a surface followed by addition of the ionomer of the invention in organic carbonate solution.
The invention is further described in the following specific embodiments.
EXAMPLES
Precursor non-ionic polymers I-XIV hereinbelow described, were formed by copolymerization of ethylene with a comonomer of the formula FS02-CF2CF2-O-(CF2)~(CH2)4CH=CHZ
where n = 2 or 4. The solvent employed was toluene, except in the case of the synthesis of Polymer XI wherein it was dichloromethane.
Referring to Table 1, polymers I-X and X1V were synthesized by combining in a Schlenk flask in a nitrogen purged drybox, the indicated amounts of the indicated catalyst, comonomer, and solvent. The structure of the designated catalyst is provided in Table 2. The mixture was then brought out of the dry box and placed under 1 atmosphere of ethylene. The mixture was purged with ethylene for 15 minutes while cooling by immersion in an ice water bath. 2.2 ml of a 7.1 % solution of polymethylalumoxane (PMAO) in toluene (4.4 mL for polymers VII and XIV) was then introduced to initiate the reaction, and the 5 mixture was agitated for the indicated time. At the end of the indicated time, 5 ml of methanol was slowly added to the reaction mixture, after which the mixture was decanted into 150 ml of methanol, followed by addition of 1.5 ml of concentrated aqueous HC1. The resulting mixture was stirred for ca. 30 minutes.
The resulting white solid polymer was filtered, washed with six 20 ml aliquots of methanol. and dried in vacuo.
Polymer XI was synthesized by combining the indicated amounts of the indicated catalyst, comonomer and dichloromethane solvent in a Schlenk flask.
Reaction was initiated by placing the mixture under 1 atmosphere of ethylene at room temperature; no PMAO was added. Reaction proceeded for 4,260 minutes 15 under agitation. The resulting polymer was an oily liquid. The reaction was filtered. To the filtrate was added 350 ml of methanol with agitation. An oil precipitate was isolated and redissolved in 100 ml of dichloromethane followed by addition of 350 ml of methanol. A light yellow oil product was isolated and dried in vacuo. The material so-produced exhibited a glass transition temperature of -66°C and no melting point.
Polymers XII and XIII were produced by combining in a Schlenk flask in a drybox the indicated amounts of the indicated catalyst, comonomer, and solvent.
The mixture was placed under 1 atmosphere of ethylene and purged with ethylene for 15 minutes. 10 ml of a 7.1 % solution of PMAO in toluene was added to 25 initiate the reaction which continued under agitation for the indicated time at the indicated temperature. 350 ml of methanol was slowly added to the reaction mixture followed by 5 ml conc. HCI. The white solid polymer was filtered, washed with methanol and dried in vacuo.
Molecular weight was determined by gel permeation chromatography using polyethylene standards. Melting points were determined by employing a DuPont model 912 Differential Scanning Calorimeter by cooling to -100°C, then heating at l OC°/min to 150°C. In the examples hereinbelow described, the polymers are designated according to Roman numerals I-XVII. The catalysts employed are designated in Table 1 by a letter designation corresponding to the catalysts listed in Table 2. The % of comonomer in the polymer was determined by a combination of proton and ~3C nuclear magnetic resonance.
O ~ N N N N ~ N O ~ OC f-~ O O
~ .-. ~
N
h ~
~ --N N O~ v W n ~ V O N ~ N
; h _ \ ~
. ~O N r ~ M ~ O vp 1 r Q N
0000 (Vv1 ~pN h V M ~ O M -\O
N - ~-N .-N M ~ N .-.-U
.0 O.. o0 C V'~ cYh O~M V'00 O~vJ V h C
~O
M M ~ V~ N O f~1f~ f1V~
O
U
> N
C U U f'J O~ v~ ~- fV V O 00 h 00 v~ M N
'_' N h O~ O pp n 4. O ...
a O O
_ 3i C
O y 00 00 O O O O O ~n O ~n O O O o0 h! M M fn M M O ~f C ~p M M N
~ N
2~ ~1' C
o n O O O O O O O O O O M M O O
E-~ N N
OG
T
C
.
C = 4-.
O ~ O ~ O O O O O O O O O ~n O v'1inO
~
- _ ~ " M f~1M M M M h N M M V1M M ~D
a U
_ _ O ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ 0 ~
_ ppv OD OWO
O O O O O O O O N Yl v1 ~ N ~ fn ~ O~
O
U ~~ N N N N N CV N N ~ ~ N N N
C
V
c N h h h h h c v h h h c ~ 0 0 0 0 0 0 0 0 0 0 - o °0 0 E ~ 0 0 0 0 0 0 0 0 0 0 0 o c o a~
Q cn U D u7 c~. D D m fn C7 ~ 2 m > > > > X x x X >C 7G
TABLE 2: Catalysts Employed in the Synthesis of Polymers I-XIV
CATALYST
DESIGNATION Catalyst A
~N
Ni r\
tar Br B
Br/ \ Br C H H
N~ /N
Ni Br Br D
N/ ~ N
Ni Br Br E i N~ ~N
\ /
Ni Br / Br F
N\ ~N
Ni Br/ \Br G Pd(CH2)3C(O)OCH3( {2,6-[CH(CH3)2]2C6fI3}2DAB(CH3)2)SbF6 H rac-ethylenebis(indenyl)zirconium (IV) dichloride Precursor non-ionic polymrs XV and XVI hereinbelow described, were formed by copolymerization of propylen with a comonomer of the formula FS02-CF2CF2-O-(CF~)2(CH2)4CH=CHI
The solvent employed was toluene.
Polymer XV was synthesized by combining in a Schlenk flask in a drybox 2.3 mg (0.0055 mmol) of the catalyst rac-ethylenebis(indenyl)zirconium (IV) dichloride, 2.72 g (7.11 mmol) CH2=CH(CH2)4(CF2)20(CF2)2S02F and 25 mL
toluene. This was placed under 3 psig of propylene in an ice-water bath and was 10 purged with propylene for 10 min. PMAO (7.2 mL 7.1 wt% toluene solution) was added to the mixture. After stirring under 3 psig of propylene at 0°C
for 1 hr, methanol (150 mL) was slowly added to the reaction mixture followed by 5 mL
conc. HCI. The white solid polymer was filtered, washed with methanol and dried in vacuo. Copolymer (1.35 g) was obtained. The polymer was isotactic based on ~ 3C NMR. ~ H NMR(TCE-d~) indicated a comonomer incorporation of 2.9 mole %. The copolymer exhibits a melting point of 133°C by differential scanning calorimetry. Gel permeation chromatography (TCB, 135°C, Polyethylene standard): Mw = 23,200; Mn = 11,000; Mw/Mn = 2.1.
Polymer XVI was synthesized by combining in a Schlenk flask in a drybox 2.3 mg (0.0055 mmol) of the catalyst rac-ethylenebis(indenyl)zirconium (IV) dichloride, 5.5 g (0.0144 mol) CH2=CH(CH2)4(CF2)20(CF2)~S02F, and 25 ml toluene. This was placed under 3 psig of propylene in an ice-water bath and was purged with propylene for 10 min. PMAO {4.0 mL 12.9 wt % toluene solution) was added to the mixture. After stirring under 3 psig of propylene at 0°C for 2 hr, methanol (5 rnL) was slowly added to the reaction mixture. The mixture was then poured into 150 mL methanol, followed by 5 mL of conc. HCI. After stirring at room temperature for 20 min, the white solid polymer was filtered, washed with methanol and dried in vacuo. Copolymer (4.6 g) was obtained. The polymer was isotactic based on ~--'C NMR. ~H NMR(TCE-d~) indicated a comonomer incorporation of 3.8 mole %. The copolymer exhibits a melting point of 124°C by differential scanning calorimetry. Gel permeation chromatography (TCB, 135°C, Polyethylene standard): Mw = 39,200; Mn = 20,900; Mw/Mn = 1.9.
10 Precursor non-ionic polymer XVII hereinbelow described was formed by grafting of CH2=CH(CF2)~O(CF~)~S02F on high density polyethylene.
Polymer XVII was synthesized by combining a solution of 13.03 g of high density polyethylene (Aldrich, Mw = 125,000) in 100 ml o-dichlorobenzene at 125°C, with 10.15 g CH2=CH(CF~)~O(CF~)~SO~F under nitrogen followed by 15 slow addition of a dichlorobenzene solution of tert-butyl peroxide(1.23 g tBu00tBu in 20 mL 0-dichlorobenzene). Addition was finished in 7 hr. The solution was then allowed to stir overnight. The solution was poured into 500 mL
methanol, and blended in a laboratory blender followed by filtration, the steps of methanol dissolution, blending, and filtration being performed a total of four 20 times. The solid polymer was then washed with methanol three times and dried in vacuo. White polymer (21.3 g) was obtained. Based on ~ H NMR, the mole percentage of comonomer incorporation was 5.4%. Based on NMR branching frequency was 7 Me/1000CI-h. GPC(TCB, i 35°C, PE standard): Mw =
65,700;
Mn = 4,820; P/D = 15.3. The copolymer has a melting point of 1 I 8°C
based on 25 DSC.
Films designated F 1-F 16, F I 9, F21-F23 of the invention were fabricated from the polymers of the invention.
Polymer VI was found to be excessively brittle to permit further handling, probably because of low molecular weight, and could not be fabricated into a free-30 standing film. Polymer XI was an oil which could not be fabricated into a free-standing film at room temperature.
All the other polymers hereinabove designated Polymer I-V and Polymer VII-X, and XII-XVII were fabricated into films. Melt-pressed films, designated in Table 3 as "MP", in the range of 3.75 cm x 3.75 cm to 7.5 cm 35 x7.5 cm were formed by placing ca. 0.25-5.0 g of the dried polymer between two sheets of Kapton~ Polyimide Film available from DuPont, Wilmington, DE, and inserted between the platens of a hydraulic press (model P218C, Pasadena Hydraulic Industries, City of Industry, CA) equipped with Omron Electronics lnc.
(Schaumburg, IL) ESCS temperature controllers. The polymer was preheated for two minutes, followed by compression for two minutes, followed by cooling under pressure. Resulting films ranged in thickness from ca. 63 to 127 micro-meters. Specific temperatures and pressures employed are provided in Table 3.
Solution cast films, designated in Table 3 as "soln", were prepared by dissolving 0.25-S.0 g of polymer into the indicated solvent by heating the solvent until the polymer dissolved, followed by casting onto a glass casting tray with 2.5 cm x 2.5 cm wells. The solvent was evaporated at room temperature leaving polymer films ranging in thickness from ca. 25-127 micrometers.
Table 3 - Formation of Polymer Films Polymer FILM SPECIMEN ~# Film Conditions IX F3 MP103 C/625psi/2min F4 MP103 C/625psi/2min VIII FS SOLN dichlorobenzene III F6 SOLN chlorobenzene F7 SOLN chlorobenzene II F10 MP240C/2500 Ibs/in' Fl 1 MP240C/2500 lbs/in2 V F12 MP240C/ 2500 lbs/in2 VII F13 MP240C/2500 lbs/in'-F14 MP240C/2500 Ibs/in2 XII F15 MP140C/2500 psi XIII F16 MP140C/2500 lbs/in2/2 Min XVI F22 MP 160C/2500 psi/2 min.
XVII F23 MP 250C/3000 psi/2 min.
Each of the film samples F I -F 16, F 19, F21-F23 described in Table 3, plus two oil aliquots of polymer XI, were hydrolyzed by treatment with a saturated t r solution of LiOH in 1:1 water methanol, followed by a rinse in I :1 water methanol at room temperature, and then heating in a fresh 1:1 water/methanol mixture.
Specimens were then dried, except where otherwise specified in a Model 1430 vacuum oven available from V WR Scientific, West Chester, PA, at a pressure of S ca. 220 torn. Table 4 provides the duration and temperature of film exposure to ' the LiOH solution, the duration of the room temperature rinse, the temperature and duration of the warm rinse, and the temperature and duration of drying of the ' hydrolyzed film.
c~
~' ~O M
,~ \ \
~
~ ~ ~
V_~M_ _V10_OI_~l_~ M_ O_0_ O O O O O O O ~ ~ O ~1 O
N
U U U U U o U o U U U
0 0 n o o o ~ ~n o o ... ~ ~ ~n o vovc ~ ~ ~t vo ~ ~O
~
ar a,ar ar ad~ w ar y x ~ .~ .~.~
,.,~ ~, ~, .~
~
~ ~, 3 -~
c O p N N
-.... ~ ~ ~ ~ ~ ~'N ~t z a ,~y x air ~.~r ~ o .b~ U U U U U U U U U U U
o o o O a O o o ~no ~n o ~n ~n o 0 o ~.
~
4 ~ ~ ~
a~
,3 a.u .~ ~ ~ an au ~ w.~ ~r ar ar ftS G~
CCS CV CC ~CCd CCSC~G~S CCi CC fC
~ ~ ~ ~ ~ .~~ ~ .~ C
N
N w0 ~O ~ . ~G N o0 ~D ~O .
eh ~O -r v0 ~-H
~r~ r.rv--y ~r O
w w w w w w r~,u~ w w W~
~.
z ..-rN M ~h'V7 ~O I~00 p~
C~ C~ C/~ C!~V7 C/~C/~C/7 i/1 ""a O
G ~
s.., E'r N O N .-~ N
U
~ ~
~ v ~ ~ C ~ v'~ ~D
C_ UU U U U U U U U
o o 0 o y.. ~ ~ 0 a c~ o G
N N 'd'~ ~h ~ -~ .x~
N
C
_ N
C
~ C
a. a.
E
y ~O ~ U
;~ U U U U U U oU o 0o U U U
o 0 0 0 0 0 0 0 ~ ~ o o o ~' 0 0 0 ~n n 0 ~ o ~ o ~ o ~. ~ o o ~, . WD I~ I~~ \O00 ~ y, I~ I~ 00 L ..y.. y ~ "", c ~ N
C
. ~n N . ~n ~D ~O vD~D W O -~ vG ~ ~D w0 N -~ -~
v. _ ~_ ~_~_ ~
O
z~
C~ N M d'~ ~ t~ o0 O~ ~ N
r.r .--i .-r.-,...,.~..r .-~ .~ N N
~ w w w w w w w w w w ~.
z N M ~t~n ~Dt~ 00 Ov -.~ N
.--i .-~rr.--i..-r.~ .--n ~ N N
~
~
_ '.~
r-.
C~
C
_ N
C
~ C
a. a.
E
y ~O ~ U
;~ U U U U U U oU o 0o U U U
o 0 0 0 0 0 0 0 ~ ~ o o o ~' 0 0 0 ~n n 0 ~ o ~ o ~ o ~. ~ o o ~, . WD I~ I~~ \O00 ~ y, I~ I~ 00 L ..y.. y ~ "", c ~ N
C
. ~n N . ~n ~D ~O vD~D W O -~ vG ~ ~D w0 N -~ -~
v. _ ~_ ~_~_ ~
O
z~
C~ N M d'~ ~ t~ o0 O~ ~ N
r.r .--i .-r.-,...,.~..r .-~ .~ N N
~ w w w w w w w w w w ~.
z N M ~t~n ~Dt~ 00 Ov -.~ N
.--i .-~rr.--i..-r.~ .--n ~ N N
~
~
_ '.~
r-.
C~
ono '~
~ ~s ' o ~
~U
i~
.r a~
~.
E~
M
M II
y x ~ ~ ~ II
o .C D0~0~ C) ~ a x Nv ~, v 3 x ~~ o.~ 3 o Ha :~gx~
~
O o~ 3 o ~ 3 N N ~
w s ~
.a w. ~ ~ 'in i~ > c , >, O
X _ O
ar e~
~, .O
z ~y/ 'n N
_ CA t~ w N
~. w ~' ~ z c c .
~s i~ co i M ~
.
..
N
'~ V7 >, C
N
"~
r0~
C~
b dE
iF iF
A 4.43 g sample of Polymer XIV in the form of as-polymerized polymer crumb formed as described in Example XIV, was subject to hydrolysis by immersing for two hours into an excess of a saturated solution of LiOH in a 1:1 water/methanol mixture preheated to 70°C, followed by heating to 75°C and holding for an additional two hours, followed in turn by cooling to room temperature and holding for 12 hours, and followed by heating to 75°C
again, and holding for 4 hours. The resulting hydrolyzed polymer was then subject to a 12 hour rinse at room temperature in a 1:1 mixture of water/methanol, followed by a 4 hour rinse at 80°C in a fresh mixture of 1:1 water/methanol followed by a 12 hour rinse at room temperature in a 1:1 mixture of water/methanol.
The hydrolyzed polymer was then dissolved in THF and cast into a film by casting onto a glass plate, followed by evaporation of the THF, and separation of the film from the plate. The hydolyzed film so formed is designated hereinbelow as specimen 520.
0.2817 g of lithiated polymer sample S 19 prepared as hereinabove described was placed in 10 mL of THF and warmed gently until dissolved.
0.056 g of Cabot Cab-o-silk TS530 was added and stirred until dispersed. The dispersion was cast into a round petri dish of Teflon~ PFA, 50 mm in diameter, and the solvent was allowed to evaporate to form the hydrolyzed film designated hereinbelow as specimen S24.
The dried hydrolyzed films of Examples 1-24, S 1-524, were transferred to a sealed container while still warm and conveyed to a glove box having a positive pressure of dry nitrogen applied thereto, wherein the membrane was removed from the sealed container and allowed to come to room temperature. Still in the glove box, the membrane was then cut into several sections 1.0 cm by 1.5 cm in size. Typically, the specimens as prepared were then heated at 100°C
under vacuum for 24-48 hours.
A cooled 1.0 cm by 1.5 cm membrane sample was then soaked in an excess of one or more liquids in a sealed glass vial for 24 hours at room temperature. The liquids employed are all commercially available, and were used as received. Following immersion, the membrane sample was removed from the liquid bath, blotted with a paper towel to remove excess liquid, and tested.
Ionic conductivity was determined using the so-called four-point probe technique described in an article entitled "Proton Conductivity of Nafion~ 117 As Measured by a Four-Electrode AC Impendance Method" by Y. Sone et al., J. Electrochem. Soc., 143,1254 (1996). The method as described applies to aqueous electrolyte membranes. The method was modified for purposes of obtaining the measurements reported herein for non-aqueous solvents by placing the apparatus described in a sealed glove box purged with dry nitrogen in order to minimize any exposure to water. The method was also modified by substituting parallel linear probes traversing the full width of the test specimen for the point probes employed in the published method.
A 1.0 cm by 1.5 cm film was blotted dry and positioned into the conductivity cell. Cell impedance was determined over the range of 10 Hz to 100,000 Hz, and the value with zero phase angle in the higher frequency range (usually 500-5000 Hz) was ascribed to the bulk sample resistance in Ohms. The raw resistance value was then converted to conductivity, in S/cm, using the cell constant and liquid-swollen film thickness.
The following abbreviations have been used:
DEC diethyl carbonate DEE diethoxyethane DMC dimethyl carbonate DME 1,2-dimethoxyethane DMF N,N -dimethyl formamide DMSO dimethyl sulfoxide EC ethylene carbonate (1,3-dioxolan-2-one) GBL y-butyrolactone MA methyl acetate MeOH methanol MG methyl glycolate NMF N-methyl formamide NMP N-methyl pyrrolidone PC propylene carbonate PEG polyethylene glycol) THF tetrahydrofuran In the conductivity tests so performed, wherein hydrolyzed films of the invention, S1-S24, were combined with the liquids indicated to form conductive compositions of the invention, as described the compositions shown in Table 5 were found to exhibit room temperature ionic conductivity greater than 10-5 S/cm.
Table 5 Examples ~5-138' lonically Conductive Compositions Formed by Combining Liguid and Film Which Exhibited Conductivity Greater Than 10-SS/cm Hydrolyzed Film Specimen Liquids Imbibed S2 PC/DME; EC/DME
S4 PC/DME; EC/DME; PC; DMSO; DMF
S9 PC; PC/DMC; PC/DME; EC/PC; EC/DMC; EC/DME
S10 PC; EC/DME; DMSO; DMC; THF; PC/DME; PC/DMSO;
PC/DMC
S11 PC/DEC; EC/DMC; EC/PC; NMF; DME; PC; DME; EC/PC/DMC
S12 PC; DME; GBL; DEE; PC/DME; GBL/DMSO; PC/DEE
S13 PC; EC/DME; DMSO; DMF; GBL; PC/DMSO; PC/GBL
S14 PC/DEC; ECIDMC; EC/PC; NMF; DME; PC; DME; EC/PC/DMC
*S15 PC; DME; GBL; DMF; DMSO; EC/DME; PC/EC; PC/DME;
PC/GBL; PC/DMF; PC/DMSO; EC/PC/DME
S 16 PC; DME; DMSO; DMF; DEC; GBL; NMP; MG; PC/DME;
PEG/DME; PC/DMSO; PC/DMF; PC/GBL; THF/GBL; NMP/DMF;
MA/GBL; MG/DMSO; EC/DMC; EC/DME
S19 DMSO; DMF; GBL
S20 PC; EC/DMC; EC/PCIDMC
S21 DMSO; DMF; GBL
S22 DME; EC/DMC; DMSO; GBL; DMF
S23 PC; DMSO; PC/DME
S24 EC/DMC; GBL; DMSO; EC/PC/DMC; EC/DMC/GBL;
EC/DMC/DMSO
~ ~s ' o ~
~U
i~
.r a~
~.
E~
M
M II
y x ~ ~ ~ II
o .C D0~0~ C) ~ a x Nv ~, v 3 x ~~ o.~ 3 o Ha :~gx~
~
O o~ 3 o ~ 3 N N ~
w s ~
.a w. ~ ~ 'in i~ > c , >, O
X _ O
ar e~
~, .O
z ~y/ 'n N
_ CA t~ w N
~. w ~' ~ z c c .
~s i~ co i M ~
.
..
N
'~ V7 >, C
N
"~
r0~
C~
b dE
iF iF
A 4.43 g sample of Polymer XIV in the form of as-polymerized polymer crumb formed as described in Example XIV, was subject to hydrolysis by immersing for two hours into an excess of a saturated solution of LiOH in a 1:1 water/methanol mixture preheated to 70°C, followed by heating to 75°C and holding for an additional two hours, followed in turn by cooling to room temperature and holding for 12 hours, and followed by heating to 75°C
again, and holding for 4 hours. The resulting hydrolyzed polymer was then subject to a 12 hour rinse at room temperature in a 1:1 mixture of water/methanol, followed by a 4 hour rinse at 80°C in a fresh mixture of 1:1 water/methanol followed by a 12 hour rinse at room temperature in a 1:1 mixture of water/methanol.
The hydrolyzed polymer was then dissolved in THF and cast into a film by casting onto a glass plate, followed by evaporation of the THF, and separation of the film from the plate. The hydolyzed film so formed is designated hereinbelow as specimen 520.
0.2817 g of lithiated polymer sample S 19 prepared as hereinabove described was placed in 10 mL of THF and warmed gently until dissolved.
0.056 g of Cabot Cab-o-silk TS530 was added and stirred until dispersed. The dispersion was cast into a round petri dish of Teflon~ PFA, 50 mm in diameter, and the solvent was allowed to evaporate to form the hydrolyzed film designated hereinbelow as specimen S24.
The dried hydrolyzed films of Examples 1-24, S 1-524, were transferred to a sealed container while still warm and conveyed to a glove box having a positive pressure of dry nitrogen applied thereto, wherein the membrane was removed from the sealed container and allowed to come to room temperature. Still in the glove box, the membrane was then cut into several sections 1.0 cm by 1.5 cm in size. Typically, the specimens as prepared were then heated at 100°C
under vacuum for 24-48 hours.
A cooled 1.0 cm by 1.5 cm membrane sample was then soaked in an excess of one or more liquids in a sealed glass vial for 24 hours at room temperature. The liquids employed are all commercially available, and were used as received. Following immersion, the membrane sample was removed from the liquid bath, blotted with a paper towel to remove excess liquid, and tested.
Ionic conductivity was determined using the so-called four-point probe technique described in an article entitled "Proton Conductivity of Nafion~ 117 As Measured by a Four-Electrode AC Impendance Method" by Y. Sone et al., J. Electrochem. Soc., 143,1254 (1996). The method as described applies to aqueous electrolyte membranes. The method was modified for purposes of obtaining the measurements reported herein for non-aqueous solvents by placing the apparatus described in a sealed glove box purged with dry nitrogen in order to minimize any exposure to water. The method was also modified by substituting parallel linear probes traversing the full width of the test specimen for the point probes employed in the published method.
A 1.0 cm by 1.5 cm film was blotted dry and positioned into the conductivity cell. Cell impedance was determined over the range of 10 Hz to 100,000 Hz, and the value with zero phase angle in the higher frequency range (usually 500-5000 Hz) was ascribed to the bulk sample resistance in Ohms. The raw resistance value was then converted to conductivity, in S/cm, using the cell constant and liquid-swollen film thickness.
The following abbreviations have been used:
DEC diethyl carbonate DEE diethoxyethane DMC dimethyl carbonate DME 1,2-dimethoxyethane DMF N,N -dimethyl formamide DMSO dimethyl sulfoxide EC ethylene carbonate (1,3-dioxolan-2-one) GBL y-butyrolactone MA methyl acetate MeOH methanol MG methyl glycolate NMF N-methyl formamide NMP N-methyl pyrrolidone PC propylene carbonate PEG polyethylene glycol) THF tetrahydrofuran In the conductivity tests so performed, wherein hydrolyzed films of the invention, S1-S24, were combined with the liquids indicated to form conductive compositions of the invention, as described the compositions shown in Table 5 were found to exhibit room temperature ionic conductivity greater than 10-5 S/cm.
Table 5 Examples ~5-138' lonically Conductive Compositions Formed by Combining Liguid and Film Which Exhibited Conductivity Greater Than 10-SS/cm Hydrolyzed Film Specimen Liquids Imbibed S2 PC/DME; EC/DME
S4 PC/DME; EC/DME; PC; DMSO; DMF
S9 PC; PC/DMC; PC/DME; EC/PC; EC/DMC; EC/DME
S10 PC; EC/DME; DMSO; DMC; THF; PC/DME; PC/DMSO;
PC/DMC
S11 PC/DEC; EC/DMC; EC/PC; NMF; DME; PC; DME; EC/PC/DMC
S12 PC; DME; GBL; DEE; PC/DME; GBL/DMSO; PC/DEE
S13 PC; EC/DME; DMSO; DMF; GBL; PC/DMSO; PC/GBL
S14 PC/DEC; ECIDMC; EC/PC; NMF; DME; PC; DME; EC/PC/DMC
*S15 PC; DME; GBL; DMF; DMSO; EC/DME; PC/EC; PC/DME;
PC/GBL; PC/DMF; PC/DMSO; EC/PC/DME
S 16 PC; DME; DMSO; DMF; DEC; GBL; NMP; MG; PC/DME;
PEG/DME; PC/DMSO; PC/DMF; PC/GBL; THF/GBL; NMP/DMF;
MA/GBL; MG/DMSO; EC/DMC; EC/DME
S19 DMSO; DMF; GBL
S20 PC; EC/DMC; EC/PCIDMC
S21 DMSO; DMF; GBL
S22 DME; EC/DMC; DMSO; GBL; DMF
S23 PC; DMSO; PC/DME
S24 EC/DMC; GBL; DMSO; EC/PC/DMC; EC/DMC/GBL;
EC/DMC/DMSO
5 It was observed that the specimens of S 15 employed in the examples hereinabove described retained their physical integrity to a particularly high degree while immersed in the numerous solvents listed in Table 5.
Specimens of each of hydrolyzed film samples S2, S4, S5, Sb, and S7 were soaked in PC according to the method hereinabove described except that the period of exposure was either 2 hours or 54 hours, as indicated in Table 6.
Table 6 Ionic Conductivity of Hydrolyzed Films in PC at Room Temperature 6 hrs. 54 hrs S2 3.91x10-5 9.80x10-5 SS 2.06x10-4 1.89x10-4 SS mush '3 .4x 10-4 S6 2. 34x 10-4 2. 82x I 0-4 S7 1.61x10-4 2.2x10-4 S4 2.12x 10-4 2 . 86x 10-4 S The polymeric oil formed by hydrolysis of Polymer XI was mixed with the solvents indicated in Table 7 to form gels at the temperatures indicated.
Conductivity measurements were made using an Orien liquid immersion conductivity probe. Results are shown in Table 7.
Table 7 Ionic conductivities of gel solutions of Polymer XI
Temperature Ionic Conductivity Solvent Mixture Conc. M C) (S/cm PC 0.00375 55 2.42x 10-5 PC/DME 0.00375 55 6.12x10-5 PC/DME 0.0375 SS 2.93x 10-4 PC/DME/DMF 0.00341 55 3.60x10-5 PC/DME/DMF 0.01875 55 2.37x10-4 DMF ' 0.025 29 4.48x10-4 DMF 0.025 35 4.60x10-4 DMF 0.025 40 4.90x10-4 DMF 0.025 55 5 .70x 10-4 DMF 0.025 75 6.40x10-4 Specimens of the hydrolyzed films indicated in Table 8 were evaluated for conductivity in an aqueous medium both in the lithiated form prepared as hereinabove described, and in the acid form. The acid form membranes were prepared from the lithium-form membranes by immersing the membrane into an excess of I.0 M nitric acid (Reagent grade, EM Science, Gibbstown, NJ) for one hour, followed by rinsing at T=80°C in deionized water for one hour and then cooling in deionized water.
The films were then treated by immersion into deionized water and heating to T=80°C for two hours, followed by cooling at room temperature.
Conductivity was measured using the same procedures as above except all measurements were done outside of the glove box.
5 ' Table 8 Ionic conductivities of copolymers of ethylene and fluorosulfonate monomers , in Li+ and H+-form equilibrated with l;rn~ir~ rlainni~PC~ water at room temperature Ionic Conductivity (S/cm) Sample H+ form Li+ Form Sg < 3.Ox10-~ 0.000435 S9 0.0336 0.00531 S2 0.00064 7.06x10-5 S4 0.0401 0.00746 S 13 0.0227 0.00490 S 10 0.0560 0.0112 S 15 0.0361 0.01002 S16 0.01455 0.00164 S 11 0.0420 0.00859 S 14 0.0348 0.00651 S24 0.0297 0.00757 S23 0.0648 0.01 i 6 Polymer IX synthesized as hereinabove disclosed is reacted with CF3CF2S02NNaSi(CH;)3 according to the method taught in Desmarteau, J.
Fluorine Chem. 52, pp 7ff ( I 991 ) which is herein incorporated by reference.
The 15 polymer thus formed is treated with H2S04 excess 30% at room temperature for 6 hours to form the proton (H+) form polymer. The proton form polymer thus formed is then readily ion-exchanged in a large excess of 0.1 M LiOH in a water methanol solution at room temperature for 5 hours. The resulting ionomer is a polymer having a substantially unsubstituted ethylene backbone and , 3.9 mol% of a pendant group comprising a radical of the formula:
-(CH2)q-0-CF2CF(CF3)-O-(CF2)2-S02-~--S02-CF2CF3 Li+
The Li imide ionomer is confirmed by NMR and elementary analysis.
(CF;CF2~S02)2C(BrMg)2 is synthesized from CH2(SO2CF~CF;)~ and CH3MgBr -according to the method of Seppelt, Inorg. Chem. 27, pp. 2135ff (1988). To a stirred THF solution of Polymer IX synthesized as hereinabove disclosed is added (CF3CF~~S02)~C(BrMg)2 at 0°C. After the addition is complete, the reaction mixture is stirred at R.T overnight. The THF is then pumped off, 3M HCL is added, the solution is stirred for several hours and filtered. The solid is washed with water to remove inorganic salts and then treated with 0.1 M LiCI in 50/50 water/MeOH at room temperature overnight.
Rf,S02C(Li)(SO~CF3)~ was obtained.
The resulting ionomer is a polymer having a substantially unsubstituted polyethylene backbone and 3.9 mol-% of a pendant group comprising a radical of the formula:
-(CH2)q-O-CF2CF(CF3)-0-(CF2)2-S02-~--(S02-CF2CF-~)2 Li+
The Li methide ionomer is confirmed by NMR and elementary analysis.
A dried 0.5 g sample of the hydrolyzed polymer of Example 23 was placed in a sealed flask with 12 g of tetrahydrofuran (THF) and stirred at 400 rpm and a temperature of 65°C for 4 hr. Fumed silica (0.125 g of TS530, Cabot Corp., Boston, MA) was added and the stirring continued for several minutes to disperse the silica. The suspension was filtered through a plug of glass wool to remove any gel particles, and cast on to Mylar~ polyester film, available from DuPont, with a doctor blade having a 0.050" gate height. The THF was allowed to evaporate at ambient temperature, yielding a film of 32 to 40 ~ thickness. The film so produced was employed as the separator film in the battery construction hereinbelow described.
A second sample of the hydrolyzed polymer of Example 23 was employed in the formation of the positive electrode employed in the battery hereinbelow described: 0.2 g of the dried ionomer was placed in a sealed flask with 7 g of tetrahydrofuran and stirred at 400 rpm at a temperature of 70°C for 2 hr. Carbon black (0.05 g, SP black, MMM S.A. Carbon, Brussels, Belgium) and graphite (0.75 g of mesophase carbon micro beads MCMB 25-28, Osaka Gas, Japan) were added and the mixture stirred for another 1 S minutes. The slurry was cast on to silanized Mylar~ available from DuPont and the THF allowed to evaporate at ambient temperature.
A round 12 mm dia. positive electrode was punched from the graphite film and dried under vacuum at 100°C, giving a mass of 1 I .6 mg (8.7 mg of graphite) and a thickness of 160 ~. A separator (11.5 mg mass, 43 p thick, and 19 mm dia.
round) was punched from the separator film ti-om above. These were soaked in excess anhydrous EC/DMC for 10 min, absorbing 21.8 mg of liquids. They were assembled with a lithium foil negative electrode into a size 232 coin cell.
The cell was discharged with constant current of 0.5 mA to a voltage of 0.01 V, at which point the voltage was held constant until the current dropped below 0.05 mA. The capacity on first discharge was 2.42 mAh, corresponding to ' 280 mAh per g of graphite positive electrode material. The cell was charged at a 0.~ mA rate to 1.2 V, and then the voltage was held constant at 1.2 V until the charging current dropped below 0.05 mA. The charge capacity was I .97 mAh, indicating an electrochemical efficiency of 81% in the first discharge/charge cycle. The cell was repeatedly discharged and charged in a manner similar to above, with the 14'x' discharge capacity being 1.8~ mAh.
Specimens of each of hydrolyzed film samples S2, S4, S5, Sb, and S7 were soaked in PC according to the method hereinabove described except that the period of exposure was either 2 hours or 54 hours, as indicated in Table 6.
Table 6 Ionic Conductivity of Hydrolyzed Films in PC at Room Temperature 6 hrs. 54 hrs S2 3.91x10-5 9.80x10-5 SS 2.06x10-4 1.89x10-4 SS mush '3 .4x 10-4 S6 2. 34x 10-4 2. 82x I 0-4 S7 1.61x10-4 2.2x10-4 S4 2.12x 10-4 2 . 86x 10-4 S The polymeric oil formed by hydrolysis of Polymer XI was mixed with the solvents indicated in Table 7 to form gels at the temperatures indicated.
Conductivity measurements were made using an Orien liquid immersion conductivity probe. Results are shown in Table 7.
Table 7 Ionic conductivities of gel solutions of Polymer XI
Temperature Ionic Conductivity Solvent Mixture Conc. M C) (S/cm PC 0.00375 55 2.42x 10-5 PC/DME 0.00375 55 6.12x10-5 PC/DME 0.0375 SS 2.93x 10-4 PC/DME/DMF 0.00341 55 3.60x10-5 PC/DME/DMF 0.01875 55 2.37x10-4 DMF ' 0.025 29 4.48x10-4 DMF 0.025 35 4.60x10-4 DMF 0.025 40 4.90x10-4 DMF 0.025 55 5 .70x 10-4 DMF 0.025 75 6.40x10-4 Specimens of the hydrolyzed films indicated in Table 8 were evaluated for conductivity in an aqueous medium both in the lithiated form prepared as hereinabove described, and in the acid form. The acid form membranes were prepared from the lithium-form membranes by immersing the membrane into an excess of I.0 M nitric acid (Reagent grade, EM Science, Gibbstown, NJ) for one hour, followed by rinsing at T=80°C in deionized water for one hour and then cooling in deionized water.
The films were then treated by immersion into deionized water and heating to T=80°C for two hours, followed by cooling at room temperature.
Conductivity was measured using the same procedures as above except all measurements were done outside of the glove box.
5 ' Table 8 Ionic conductivities of copolymers of ethylene and fluorosulfonate monomers , in Li+ and H+-form equilibrated with l;rn~ir~ rlainni~PC~ water at room temperature Ionic Conductivity (S/cm) Sample H+ form Li+ Form Sg < 3.Ox10-~ 0.000435 S9 0.0336 0.00531 S2 0.00064 7.06x10-5 S4 0.0401 0.00746 S 13 0.0227 0.00490 S 10 0.0560 0.0112 S 15 0.0361 0.01002 S16 0.01455 0.00164 S 11 0.0420 0.00859 S 14 0.0348 0.00651 S24 0.0297 0.00757 S23 0.0648 0.01 i 6 Polymer IX synthesized as hereinabove disclosed is reacted with CF3CF2S02NNaSi(CH;)3 according to the method taught in Desmarteau, J.
Fluorine Chem. 52, pp 7ff ( I 991 ) which is herein incorporated by reference.
The 15 polymer thus formed is treated with H2S04 excess 30% at room temperature for 6 hours to form the proton (H+) form polymer. The proton form polymer thus formed is then readily ion-exchanged in a large excess of 0.1 M LiOH in a water methanol solution at room temperature for 5 hours. The resulting ionomer is a polymer having a substantially unsubstituted ethylene backbone and , 3.9 mol% of a pendant group comprising a radical of the formula:
-(CH2)q-0-CF2CF(CF3)-O-(CF2)2-S02-~--S02-CF2CF3 Li+
The Li imide ionomer is confirmed by NMR and elementary analysis.
(CF;CF2~S02)2C(BrMg)2 is synthesized from CH2(SO2CF~CF;)~ and CH3MgBr -according to the method of Seppelt, Inorg. Chem. 27, pp. 2135ff (1988). To a stirred THF solution of Polymer IX synthesized as hereinabove disclosed is added (CF3CF~~S02)~C(BrMg)2 at 0°C. After the addition is complete, the reaction mixture is stirred at R.T overnight. The THF is then pumped off, 3M HCL is added, the solution is stirred for several hours and filtered. The solid is washed with water to remove inorganic salts and then treated with 0.1 M LiCI in 50/50 water/MeOH at room temperature overnight.
Rf,S02C(Li)(SO~CF3)~ was obtained.
The resulting ionomer is a polymer having a substantially unsubstituted polyethylene backbone and 3.9 mol-% of a pendant group comprising a radical of the formula:
-(CH2)q-O-CF2CF(CF3)-0-(CF2)2-S02-~--(S02-CF2CF-~)2 Li+
The Li methide ionomer is confirmed by NMR and elementary analysis.
A dried 0.5 g sample of the hydrolyzed polymer of Example 23 was placed in a sealed flask with 12 g of tetrahydrofuran (THF) and stirred at 400 rpm and a temperature of 65°C for 4 hr. Fumed silica (0.125 g of TS530, Cabot Corp., Boston, MA) was added and the stirring continued for several minutes to disperse the silica. The suspension was filtered through a plug of glass wool to remove any gel particles, and cast on to Mylar~ polyester film, available from DuPont, with a doctor blade having a 0.050" gate height. The THF was allowed to evaporate at ambient temperature, yielding a film of 32 to 40 ~ thickness. The film so produced was employed as the separator film in the battery construction hereinbelow described.
A second sample of the hydrolyzed polymer of Example 23 was employed in the formation of the positive electrode employed in the battery hereinbelow described: 0.2 g of the dried ionomer was placed in a sealed flask with 7 g of tetrahydrofuran and stirred at 400 rpm at a temperature of 70°C for 2 hr. Carbon black (0.05 g, SP black, MMM S.A. Carbon, Brussels, Belgium) and graphite (0.75 g of mesophase carbon micro beads MCMB 25-28, Osaka Gas, Japan) were added and the mixture stirred for another 1 S minutes. The slurry was cast on to silanized Mylar~ available from DuPont and the THF allowed to evaporate at ambient temperature.
A round 12 mm dia. positive electrode was punched from the graphite film and dried under vacuum at 100°C, giving a mass of 1 I .6 mg (8.7 mg of graphite) and a thickness of 160 ~. A separator (11.5 mg mass, 43 p thick, and 19 mm dia.
round) was punched from the separator film ti-om above. These were soaked in excess anhydrous EC/DMC for 10 min, absorbing 21.8 mg of liquids. They were assembled with a lithium foil negative electrode into a size 232 coin cell.
The cell was discharged with constant current of 0.5 mA to a voltage of 0.01 V, at which point the voltage was held constant until the current dropped below 0.05 mA. The capacity on first discharge was 2.42 mAh, corresponding to ' 280 mAh per g of graphite positive electrode material. The cell was charged at a 0.~ mA rate to 1.2 V, and then the voltage was held constant at 1.2 V until the charging current dropped below 0.05 mA. The charge capacity was I .97 mAh, indicating an electrochemical efficiency of 81% in the first discharge/charge cycle. The cell was repeatedly discharged and charged in a manner similar to above, with the 14'x' discharge capacity being 1.8~ mAh.
Claims (28)
1. An ionomer comprising a backbone and pendant groups, the backbone consisting essentially of methylene and methine units and the pendant groups comprising ionic radicals of the formula -R n-R f-CF2CF2-SO2-X-(SO2R f)a- M+
where M+ is a univalent metal cation; the R f groups are independently selected from the group consisting of linear or branched perfluoroalkylene radicals, perfluoroalkylene radicals containing O or Cl, and perfluoroaryl radicals; R
is hydrocarbyl and n = 0 or 1; a = 0-2; and X = O, N or C; said ionic radicals being further limited in that a = 0 when X = O, a = 1 when X = N, and a = 2 when X =
C.
where M+ is a univalent metal cation; the R f groups are independently selected from the group consisting of linear or branched perfluoroalkylene radicals, perfluoroalkylene radicals containing O or Cl, and perfluoroaryl radicals; R
is hydrocarbyl and n = 0 or 1; a = 0-2; and X = O, N or C; said ionic radicals being further limited in that a = 0 when X = O, a = 1 when X = N, and a = 2 when X =
C.
2. The ionomer of Claim 1 wherein a = 0; X = O; R f is represented by the formula -O-[(CFR f'-CF2)x-O y]m-where Rf' is perfluoroalkyl or fluorine, x = 0, 1, 2, or 3, y = 0 or 1. and m = 0, 1, 2.
or 3; and R n is represented by the formula -(CH2)z-where z is an integer in the range of 2 to 6.
or 3; and R n is represented by the formula -(CH2)z-where z is an integer in the range of 2 to 6.
3. The ionomer of Claim 2 wherein M+ is an alkali metal cation, R f' is fluorine, x = 1 or 2, y = 0, m = 1 or 2, z = 4, and R is ethyl, propyl, or butyl.
4. The ionomer of Claim 3 wherein M+ is a lithium cation.
5. The ionomer of Claim 1 wherein the concentration of said ionic radicals is 1-20 mol%.
6. The ionomer of Claim 1 wherein the concentration of said ionic radicals is 2-10 mol-%.
7. The ionomer of Claim 1 further comprising up to 150 short chain branches per 1000 methylene groups in the backbone.
8. The ionomer of Claim 1 wherein there are 5-90 short chain branches per 1000 methylene groups in the backbone.
9. The ionomer of Claim 1 in the form of a film or sheet.
10. The ionomer of Claim 1 further comprising inorganic particles admixed therewith.
11. The ionomer of Claim 10 wherein the inorganic particles are silica particles of an average particle dimension of less than 1.0 micrometers, the silica being present in the admixture at up to 50% by weight of the total.
12. An ionically conductive composition comprising the ionomer of Claim 1 and a liquid imbibed therewithin.
13. The ionically conductive composition of Claim 12 wherein the liquid is water or methanol.
14. The ionically conductive composition of Claim 12 wherein the liquid is aprotic.
15. The ionically conductive composition of Claim 14 wherein the liquid is selected from the group consisting of organic carbonates and mixtures thereof.
16. The ionically conductive composition of Claim 13 wherein the liquid is a mixture of ethylene carbonate and at least one liquid selected from the group consisting of dimethyl carbonate, methyl ethyl carbonate and diethyl carbonate.
17. The ionically conductive composition of Claim 12 wherein M+ is a lithium cation, R n=(CH2)4, R f(CF2)x, X=O, a=0, the concentration of said ionic radicals is 2-10 mol-%, further comprising up to 150 short chain branches per 1000 methylene units in the backbone, and the liquid is selected from the group consisting of organic carbonates and mixtures thereof.
18. The ionically conductive composition of Claim 12 in a form selected from the group consisting of a film, sheet and gel.
19. The ionically conductive composition of Claim 17 in a form selected from the group consisting of a film. sheet and gel.
20. The ionically conductive composition of Claim 18 further comprising a microporous electrically insulating polymer film or sheet within the micropores of which the gel is imbibed.
21. The ionically conductive composition of Claim 19 further comprising a microporous electrically insulating polymer film or sheet within the micropores of which the gel is imbibed.
22. A process for forming an ionomer, the process comprising contacting a polyolefin comprising a backbone and pendant groups, the backbone consisting essentially of methylene and methine units and the pendant groups comprising ionic radicals of the formula XSO2-CF2CF2-R f-R n-where X is F or C1, R f is a linear or branched perfluoroalkylene, perfluoroalkylene containing O or Cl, or perfluoroaryl radical, and R is hydrocarbyl where n = 0 or 1, with a solution of an alkali metal base.
23. A process for forming a conductive composition the process comprising contacting the ionomer of Claim 1 with a liquid.
24. An electrode comprising at least one electrode active material, the ionomer of Claim 1 mixed therewith, and a liquid imbibed therewithin.
25. The electrode of Claim 24 wherein M+ is a lithium canon, R n=(CH2)4, R f(CF2)x, X=O, a=0, the concentration of said ionic radicals is 2-10 mol%, further comprising up to 150 short chain branches per 1000 methylene units in the backbone, and the liquid is selected from the group consisting of organic carbonates and mixtures thereof.
26. The electrode of Claim 25 further comprising carbon black.
27. The electrode of Claim 26 wherein the weight ratio of ionomer to electrode active material is between 0.05 and 0.8 and the weight ratio of carbon black to electrode active material is between 0.01 and 0.2.
28. An electrochemical cell comprising a positive electrode, a negative electrode, a separator disposed between the positive and negative electrodes, and a means for connecting the cell to an outside load or source wherein at least one of the group consisting of the separator, the positive electrode, and the negative electrode, comprises the ionomer of Claim 1.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/061,132 US6100324A (en) | 1998-04-16 | 1998-04-16 | Ionomers and ionically conductive compositions |
US09/061,132 | 1998-04-16 | ||
PCT/US1999/008255 WO1999052954A1 (en) | 1998-04-16 | 1999-04-15 | Ionomers and ionically conductive compositions |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2326845A1 true CA2326845A1 (en) | 1999-10-21 |
Family
ID=22033801
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002326845A Abandoned CA2326845A1 (en) | 1998-04-16 | 1999-04-15 | Ionomers and ionically conductive compositions |
Country Status (9)
Country | Link |
---|---|
US (2) | US6100324A (en) |
EP (1) | EP1082358B1 (en) |
JP (1) | JP2002511502A (en) |
KR (1) | KR100541312B1 (en) |
CN (1) | CN1297457A (en) |
AU (1) | AU3645599A (en) |
CA (1) | CA2326845A1 (en) |
DE (1) | DE69918107T2 (en) |
WO (1) | WO1999052954A1 (en) |
Families Citing this family (68)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6100324A (en) * | 1998-04-16 | 2000-08-08 | E. I. Du Pont De Nemours And Company | Ionomers and ionically conductive compositions |
JP2003520872A (en) * | 2000-01-19 | 2003-07-08 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Method for producing graft copolymer |
BR0113004A (en) | 2000-07-28 | 2003-06-24 | Du Pont | Free radical graft process |
EP1220344B2 (en) * | 2000-12-26 | 2012-08-01 | Asahi Glass Company, Limited | Solid polymer electrolyte membrane, solid polymer fuel cell and fluorpolymer |
US6727019B2 (en) * | 2001-03-22 | 2004-04-27 | Ilion Technology | Electrochemical cell having an ionomer binder of Li-AMPS and associated fabrication |
CA2459357A1 (en) | 2001-10-15 | 2003-04-24 | E. I. Du Pont De Nemours And Company | Solid polymer membrane for fuel cell prepared by in situ polymerization |
US7094851B2 (en) | 2001-12-06 | 2006-08-22 | Gore Enterprise Holdings, Inc. | Low equivalent weight ionomer |
US6861489B2 (en) | 2001-12-06 | 2005-03-01 | Gore Enterprise Holdings, Inc. | Low equivalent weight ionomer |
US6679979B2 (en) * | 2001-12-12 | 2004-01-20 | Ballard Power Systems Inc. | Aqueous ionomeric gels and products and methods related thereto |
EP1474839B1 (en) * | 2002-02-06 | 2010-04-07 | Battelle Memorial Institute | Polymer electrolyte membranes for use in fuel cells |
AU2003210939A1 (en) * | 2002-02-06 | 2003-09-02 | Battelle Memorial Institute | Polymer electrolyte membrane fuel cell system |
US20050053818A1 (en) * | 2002-03-28 | 2005-03-10 | Marc St-Arnaud | Ion exchange composite material based on proton conductive functionalized inorganic support compounds in a polymer matrix |
WO2004051782A1 (en) * | 2002-06-28 | 2004-06-17 | Dubitsky Yuri A | Fuel cell incorporating a polymer electrolyte membrane grafted by irradiation |
US7317047B2 (en) | 2002-09-24 | 2008-01-08 | E.I. Du Pont De Nemours And Company | Electrically conducting organic polymer/nanoparticle composites and methods for use thereof |
EP1546283B1 (en) | 2002-09-24 | 2012-06-20 | E.I. Du Pont De Nemours And Company | Electrically conducting organic polymer/nanoparticle composites and methods for use thereof |
ATE404609T1 (en) | 2002-09-24 | 2008-08-15 | Du Pont | WATER DISPERSIBLE POLYTHIOPHENES PRODUCED USING COLLOIDS BASED ON POLYMERIC ACIDS |
JP2006500461A (en) | 2002-09-24 | 2006-01-05 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Water-dispersible polyaniline produced using polymer acid colloids for electronics applications |
US7390438B2 (en) | 2003-04-22 | 2008-06-24 | E.I. Du Pont De Nemours And Company | Water dispersible substituted polydioxythiophenes made with fluorinated polymeric sulfonic acid colloids |
US7537682B2 (en) | 2004-03-17 | 2009-05-26 | California Institute Of Technology | Methods for purifying carbon materials |
US7351358B2 (en) | 2004-03-17 | 2008-04-01 | E.I. Du Pont De Nemours And Company | Water dispersible polypyrroles made with polymeric acid colloids for electronics applications |
US8147962B2 (en) | 2004-04-13 | 2012-04-03 | E. I. Du Pont De Nemours And Company | Conductive polymer composites |
JP4978191B2 (en) * | 2004-06-30 | 2012-07-18 | Tdk株式会社 | Direct alcohol fuel cell and method for manufacturing the same |
JP4506403B2 (en) * | 2004-10-15 | 2010-07-21 | ダイキン工業株式会社 | Ionic conductor |
US7722785B2 (en) | 2005-06-27 | 2010-05-25 | E.I. Du Pont De Nemours And Company | Electrically conductive polymer compositions |
US7727421B2 (en) | 2005-06-27 | 2010-06-01 | E. I. Du Pont De Nemours And Company Dupont Displays Inc | Electrically conductive polymer compositions |
WO2007002740A2 (en) | 2005-06-28 | 2007-01-04 | E. I. Du Pont De Nemours And Company | Buffer compositions |
KR101356296B1 (en) | 2005-06-28 | 2014-02-06 | 이 아이 듀폰 디 네모아 앤드 캄파니 | High Work Function Transparent Conductors |
WO2007041415A2 (en) | 2005-09-30 | 2007-04-12 | Battelle Memorial Institute | Polymers for use in fuel cell components |
US20100221603A1 (en) * | 2006-03-03 | 2010-09-02 | Rachid Yazami | Lithium ion fluoride battery |
US7563542B2 (en) * | 2005-10-05 | 2009-07-21 | California Institute Of Technology | Subfluorinated graphite fluorides as electrode materials |
US8232007B2 (en) | 2005-10-05 | 2012-07-31 | California Institute Of Technology | Electrochemistry of carbon subfluorides |
US8377586B2 (en) | 2005-10-05 | 2013-02-19 | California Institute Of Technology | Fluoride ion electrochemical cell |
US7794880B2 (en) | 2005-11-16 | 2010-09-14 | California Institute Of Technology | Fluorination of multi-layered carbon nanomaterials |
US20070218364A1 (en) * | 2005-10-05 | 2007-09-20 | Whitacre Jay F | Low temperature electrochemical cell |
US7560497B2 (en) * | 2005-10-24 | 2009-07-14 | Yuan Ze University | Perfluorocarbon ionomer membrane with high proton conductivity and preparation thereof |
US8216680B2 (en) | 2006-02-03 | 2012-07-10 | E I Du Pont De Nemours And Company | Transparent composite conductors having high work function |
KR101398780B1 (en) | 2006-06-01 | 2014-06-18 | 이 아이 듀폰 디 네모아 앤드 캄파니 | Conductive polymer compositions |
WO2007145975A2 (en) | 2006-06-05 | 2007-12-21 | E. I. Du Pont De Nemours And Company | Process for forming an organic light-emitting diode and devices made by the process |
KR101387894B1 (en) | 2006-06-30 | 2014-04-25 | 이 아이 듀폰 디 네모아 앤드 캄파니 | Stabilized compositions of conductive polymers and partially-fluorinated acid polymers |
US8658309B2 (en) * | 2006-08-11 | 2014-02-25 | California Institute Of Technology | Dissociating agents, formulations and methods providing enhanced solubility of fluorides |
US7718319B2 (en) | 2006-09-25 | 2010-05-18 | Board Of Regents, The University Of Texas System | Cation-substituted spinel oxide and oxyfluoride cathodes for lithium ion batteries |
US7456314B2 (en) * | 2006-12-21 | 2008-11-25 | E.I. Du Pont De Nemours And Company | Partially fluorinated ionic compounds |
US20080191172A1 (en) | 2006-12-29 | 2008-08-14 | Che-Hsiung Hsu | High work-function and high conductivity compositions of electrically conducting polymers |
CA2679635A1 (en) * | 2007-03-14 | 2008-09-18 | California Institute Of Technology | High discharge rate batteries |
US20080232032A1 (en) * | 2007-03-20 | 2008-09-25 | Avx Corporation | Anode for use in electrolytic capacitors |
US7649730B2 (en) | 2007-03-20 | 2010-01-19 | Avx Corporation | Wet electrolytic capacitor containing a plurality of thin powder-formed anodes |
US20080251768A1 (en) | 2007-04-13 | 2008-10-16 | Che-Hsiung Hsu | Electrically conductive polymer compositions |
US8241526B2 (en) | 2007-05-18 | 2012-08-14 | E I Du Pont De Nemours And Company | Aqueous dispersions of electrically conducting polymers containing high boiling solvent and additives |
KR20100094475A (en) | 2007-10-26 | 2010-08-26 | 이 아이 듀폰 디 네모아 앤드 캄파니 | Process and materials for making contained layers and devices made with same |
US8216685B2 (en) | 2008-05-16 | 2012-07-10 | E I Du Pont De Nemours And Company | Buffer bilayers for electronic devices |
CN102203984A (en) * | 2008-11-04 | 2011-09-28 | 加州理工学院 | Hybrid electrochemical generator with a soluble anode |
TW201030086A (en) | 2008-12-09 | 2010-08-16 | Du Pont | Electrically conductive polymer compositions |
WO2010077710A2 (en) | 2008-12-09 | 2010-07-08 | E. I. Du Pont De Nemours And Company | Electrically conductive polymer compositions |
US8461758B2 (en) | 2008-12-19 | 2013-06-11 | E I Du Pont De Nemours And Company | Buffer bilayers for electronic devices |
US8785913B2 (en) | 2008-12-27 | 2014-07-22 | E I Du Pont De Nemours And Company | Buffer bilayers for electronic devices |
US8766239B2 (en) | 2008-12-27 | 2014-07-01 | E I Du Pont De Nemours And Company | Buffer bilayers for electronic devices |
TW201100480A (en) | 2009-03-12 | 2011-01-01 | Du Pont | Electrically conductive polymer compositions for coating applications |
US8223473B2 (en) | 2009-03-23 | 2012-07-17 | Avx Corporation | Electrolytic capacitor containing a liquid electrolyte |
JP5587980B2 (en) | 2009-04-21 | 2014-09-10 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Conductive polymer composition and film made therefrom |
CN102395627B (en) | 2009-04-24 | 2015-04-01 | E.I.内穆尔杜邦公司 | Electrically conductive polymer compositions and films made therefrom |
WO2010142772A1 (en) * | 2009-06-12 | 2010-12-16 | Solvay Solexis S.P.A. | Fluoroionomers dispersions having low surface tension, low liquid viscosity and high solid content |
EP2459379A4 (en) | 2009-07-27 | 2015-05-06 | Du Pont | Process and materials for making contained layers and devices made with same |
CN104136417A (en) * | 2011-12-06 | 2014-11-05 | 3M创新有限公司 | Fluorinated oligomers having pendant functional groups |
CN104798244B (en) | 2013-10-31 | 2017-07-28 | 株式会社Lg化学 | Lithium secondary battery |
KR102217106B1 (en) | 2016-05-09 | 2021-02-22 | 주식회사 엘지화학 | Composition for polymer electrolyte and lithium secondary battery comprising the same |
WO2017196012A1 (en) | 2016-05-09 | 2017-11-16 | 주식회사 엘지화학 | Composition for polymer electrolyte and lithium secondary battery comprising same |
JP6843889B2 (en) | 2016-05-27 | 2021-03-17 | エルジー・ケム・リミテッド | Diheteroamine in electrically conductive polymer composition |
WO2021066544A1 (en) * | 2019-09-30 | 2021-04-08 | 코오롱인더스트리 주식회사 | Ionomer dispersion having high dispersion stability, method for producing same, and polymer electrolyte membrane produced using same |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3282875A (en) * | 1964-07-22 | 1966-11-01 | Du Pont | Fluorocarbon vinyl ether polymers |
GB1034197A (en) * | 1963-09-13 | 1966-06-29 | Du Pont | Sulphonic acid derivatives of fluorocarbon vinyl ethers, and polymers thereof |
JPS568047B2 (en) * | 1972-07-14 | 1981-02-21 | ||
US4358545A (en) * | 1980-06-11 | 1982-11-09 | The Dow Chemical Company | Sulfonic acid electrolytic cell having flourinated polymer membrane with hydration product less than 22,000 |
JPS5785826A (en) * | 1980-11-17 | 1982-05-28 | Japan Atom Energy Res Inst | Cation exchange membrane |
JPS57131376A (en) * | 1981-02-06 | 1982-08-14 | Japan Atom Energy Res Inst | Electrolyzing method for water |
US5627292A (en) * | 1992-02-21 | 1997-05-06 | Centre National De La Recherche Scientifique | Monomers derived from perhalogenated sultones and polymers obtained from these monomers |
US5548055A (en) * | 1995-01-13 | 1996-08-20 | Sri International | Single-ion conducting solid polymer electrolytes |
EP0805826B1 (en) * | 1995-01-24 | 2003-04-23 | E.I. Du Pont De Nemours And Company | Olefin polymers |
US5798417A (en) * | 1996-10-15 | 1998-08-25 | E. I. Du Pont De Nemours And Company | (Fluorovinyl ether)-grafted high-surface-area polyolefins and preparation thereof |
US6100324A (en) * | 1998-04-16 | 2000-08-08 | E. I. Du Pont De Nemours And Company | Ionomers and ionically conductive compositions |
-
1998
- 1998-04-16 US US09/061,132 patent/US6100324A/en not_active Expired - Lifetime
-
1999
- 1999-04-15 CA CA002326845A patent/CA2326845A1/en not_active Abandoned
- 1999-04-15 CN CN99805082A patent/CN1297457A/en active Pending
- 1999-04-15 EP EP99918576A patent/EP1082358B1/en not_active Expired - Lifetime
- 1999-04-15 KR KR1020007011363A patent/KR100541312B1/en not_active IP Right Cessation
- 1999-04-15 JP JP2000543510A patent/JP2002511502A/en not_active Withdrawn
- 1999-04-15 AU AU36455/99A patent/AU3645599A/en not_active Abandoned
- 1999-04-15 DE DE69918107T patent/DE69918107T2/en not_active Expired - Fee Related
- 1999-04-15 WO PCT/US1999/008255 patent/WO1999052954A1/en active IP Right Grant
-
2000
- 2000-06-07 US US09/588,885 patent/US6268430B1/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JP2002511502A (en) | 2002-04-16 |
DE69918107T2 (en) | 2005-01-27 |
WO1999052954A1 (en) | 1999-10-21 |
US6268430B1 (en) | 2001-07-31 |
US6100324A (en) | 2000-08-08 |
EP1082358A1 (en) | 2001-03-14 |
CN1297457A (en) | 2001-05-30 |
EP1082358B1 (en) | 2004-06-16 |
AU3645599A (en) | 1999-11-01 |
DE69918107D1 (en) | 2004-07-22 |
KR20010042662A (en) | 2001-05-25 |
KR100541312B1 (en) | 2006-01-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1082358B1 (en) | Ionomers and ionically conductive compositions | |
EP1124796B1 (en) | Ionomers and polymers for electrochemical uses | |
US6033804A (en) | Highly conductive ion exchange polymer and process | |
US6025092A (en) | Fluorinated ionomers and their uses | |
EP1060200B1 (en) | Substantially fluorinated ionomers | |
EP1095071B1 (en) | Aromatic polymers with pendant fluorinated ionic groups | |
CA2342886A1 (en) | Polymers, containing a fluorocyclobutyl ring and their preparation | |
US7094501B2 (en) | Graft oligomeric electrolytes | |
CN112038693B (en) | Solid electrolyte and preparation method and application thereof | |
JP3348513B2 (en) | Polymer solid electrolyte battery | |
Ryoo et al. | Thermal and electrochemical characteristics of plasticized polymer electrolytes based on poly (acrylonitrile-co-methyl methacrylate) | |
MXPA00010034A (en) | Ionomers and ionically conductive compositions | |
CN116903850A (en) | Ionic polymer electrolyte LiPSBI, preparation method and application thereof | |
Monconduit et al. | Two Routes for N-Rich Solid Polymer Electrolyte for All-Solid-State Lithium-Ion Batteries | |
Alamgir et al. | Polyphosphazene-based Solid-state Secondary Lithium batteries | |
MXPA01004122A (en) | Monomers, ionomers and polymers for electrochemical uses | |
MXPA00007297A (en) | Fluorinated ionomers and their uses |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FZDE | Discontinued | ||
FZDE | Discontinued |
Effective date: 20040415 |