WO2003083973A1 - Polymer electrolyte for electrochemical cell - Google Patents
Polymer electrolyte for electrochemical cell Download PDFInfo
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- WO2003083973A1 WO2003083973A1 PCT/US2003/008779 US0308779W WO03083973A1 WO 2003083973 A1 WO2003083973 A1 WO 2003083973A1 US 0308779 W US0308779 W US 0308779W WO 03083973 A1 WO03083973 A1 WO 03083973A1
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- WO
- WIPO (PCT)
- Prior art keywords
- poly
- polymer electrolyte
- polymer
- ethylene oxide
- electrolyte
- Prior art date
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- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 38
- -1 cyclic siloxane Chemical class 0.000 claims abstract description 52
- 239000003792 electrolyte Substances 0.000 claims abstract description 30
- 229920000642 polymer Polymers 0.000 claims abstract description 28
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 26
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052796 boron Inorganic materials 0.000 claims abstract description 4
- 239000003990 capacitor Substances 0.000 claims abstract description 3
- 229910003002 lithium salt Inorganic materials 0.000 claims description 14
- 159000000002 lithium salts Chemical class 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000004122 cyclic group Chemical group 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 6
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 6
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 claims description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229910013884 LiPF3 Inorganic materials 0.000 claims description 4
- 229940093476 ethylene glycol Drugs 0.000 claims description 4
- 239000003039 volatile agent Substances 0.000 claims description 4
- 229910001560 Li(CF3SO2)2N Inorganic materials 0.000 claims description 3
- 229910007042 Li(CF3SO2)3 Inorganic materials 0.000 claims description 3
- 229910000552 LiCF3SO3 Inorganic materials 0.000 claims description 3
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001642 boronic acid derivatives Chemical class 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 3
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 3
- 239000011118 polyvinyl acetate Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 2
- 229920006037 cross link polymer Polymers 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229920000233 poly(alkylene oxides) Polymers 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 3
- 229920000361 Poly(styrene)-block-poly(ethylene glycol) Polymers 0.000 claims 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 229910021450 lithium metal oxide Inorganic materials 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 abstract description 13
- 239000007784 solid electrolyte Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000005977 Ethylene Substances 0.000 abstract 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 9
- 210000004027 cell Anatomy 0.000 description 9
- 229940021013 electrolyte solution Drugs 0.000 description 9
- 239000008151 electrolyte solution Substances 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000005587 bubbling Effects 0.000 description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229910018557 Si O Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000011244 liquid electrolyte Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910013385 LiN(SO2C2F5)2 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012230 colorless oil Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013394 LiN(SO2CF3) Inorganic materials 0.000 description 1
- 229910013406 LiN(SO2CF3)2 Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- WDOAICYFLKLOGD-UHFFFAOYSA-N dilithium 2-dioxidoboranyloxy-2-oxoacetic acid Chemical compound [Li+].[Li+].OC(=O)C(=O)OB([O-])[O-] WDOAICYFLKLOGD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002201 polymeric electrolyte material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 210000000352 storage cell Anatomy 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/64—Liquid electrolytes characterised by additives
-
- 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
- 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
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
-
- 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
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- 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
Definitions
- the present invention relates to electrolytes for rechargeable electrochemical cells, and, more particularly to cyclic siloxane polymer electrolytes with a poly(ethylene oxide) as a pendant group.
- Polymer electrolytes have a number of advantages over the materials currently used in high-performance batteries. Compared to conventional batteries using heavy metals such as lead, nickel, and cadmium, the lithium-based polymer electrolyte batteries would be many times lighter. The proposed designs of these batteries would also allow them to be formed into various shapes besides the traditional cylindrical or rectangular shapes typical in regular batteries. ( See, Gray, F. M. Solid Polymer Electrolytes; VCH Publishers: New York, 1991, at 1-4, 5-21). These advantages have fueled commercial interests and research interests into improving the conductive properties of polymer electrolytes. Poly(ethylene oxide) (PEO) has been known to dissolve alkali metal salts and exhibit conductivity since the early 1970's. (See, Fenton, D. E.
- the Si-O backbone of these polymers is highly flexible, yet retains its chemical and thermal integrity.
- Polysiloxanes also have low glass transition temperatures, T g , and solvate lithium salts, making the polysiloxanes good candidates for potentially useful polymer electrolytes.
- Carbonate solvents such as ethylene carbonate and propylene carbonate used for conventional lithium battery electrolytes, can easily bum with a source of ignition and generate flame, carbon dioxide, and hydrocarbons during thermal degradation.
- carbonate solvents are easily reduced or oxidized at the surface of either the positive or the negative electrode, leading to an increase in impedance and capacity fade of the cell.
- carbonate solvents used in lithium ion batteries react extremely exothermically with the charged electrode, potentially leading to thermal runaway of the battery.
- the reactivity between the carbonate solvent and the electrodes become significant, especially when the battery is large, such as in the case of hybrid and electric vehicles, satellites, submarines, and load leveling facilities, as well as medical devices and consumer electronics.
- Polymeric compounds however, have different combustion mechanisms than carbonates.
- the initial stage of a fire occurs when a source of ignition decomposes the polymeric materials into flammable volatile products.
- a source of ignition decomposes the polymeric materials into flammable volatile products.
- the application of heat must be sufficient to decompose the polymer
- the temperature must be sufficient to ignite the products of decomposition
- the amount of heat transferred from the flame back to the polymer must be sufficient to maintain the cycle.
- polymeric materials are more thermally stable than low molecular weight chemicals like carbonates because they are not volatile, and they vaporize at much higher temperatures.
- Electrolytes based on polymeric structure have fundamentally better heat resistance than conventional carbonate based electrolytes and can reduce many side chemical reactions occurring in a lithium secondary battery under abnormal operating conditions such as temperatures exceeding 60°C.
- the electrolytes with polymeric structure have advantages over carbonate solvent based electrolytes, their application in lithium secondary batteries as an ionic conducting medium has been limited due to low ionic conductivity, usually below 10 "5 S/cm at room temperature.
- a liquid polymer electrolyte that does not evaporate at temperatures up to 150°C, or a solid polymer electrolyte with high conductivity is needed.
- the new concept electrolytes described in this invention are ideal for lithium secondary batteries. They do not evaporate up to 150°C, offer high ionic conductivity of over 10 "4 S/cm around room temperature, and have a wide electrochemical stability window of over 4.5 V (vs. lithium).
- the present inventors have developed a new type of metal ionic conductive electrolyte based on liquid cyclic poly(siloxane-g-ethylene oxide)s to overcome the above mentioned problems such as volatility, flammability and chemically reactivity in lithium batteries that are usually observed when using conventional carbonate based liquid electrolytes.
- the proposed cyclic poly(siloxane-g--ethylene oxide) materials also have a good electrochemical stability window and high room temperature ionic conductivity.
- the present inventors have also incorporated the liquid polymer into solid electrolytes with the same benefits.
- the present inventors have considered the problems related to carbonate solvents in conventional lithium ion batteries and have concluded that to address these problems, new polymer materials that can readily dissolve metal salts to prepare electrolytes are needed for lithium storage cells and capacitors.
- the present inventors have developed new siloxane polymer structures with one or more poly(ethylene oxide) side chains.
- Siloxane is an inorganic material that is not readily decomposed by heat. When the material is thermally decomposed, only a few nonflammable by-products result from the decomposition process because the main chain is a Si-O linkage. This inhibits the combustion cycle.
- R is alkyl group.
- the present inventors have also carried out extensive research in this area. Previously, they invented another related liquid type siloxane polymer with one or more poly(ethylene oxide) as a side chain (see general formula II) that are directly bonded to Si atoms.
- R and R" are alkyl group and R' is hydrogen or alkyl group.
- the present inventors subsequently discovered a more effective structure of the poly(siloxane-g-ethylene oxide) which is relatively easy to synthesize and achieves high ionic conductivity (approaching to 10 " S/cm at around room temperature).
- the new liquid poly(siloxane-g-ethylene oxide)s have cvclic structure (see general formula III) that can easily coordinate with lithium salt and dissociate the salt.
- solid polymer electrolytes can be used as ionic conductors of solid polymer electrolytes by entrapping them inside crosslinked polymer networks, or mixing with solid polymers such as polyacrylonitrile (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVdF), poly(vinylidene fluoride-co-hexafluoropropylene), poly(vinyl acetate), polystyrene, poly(ethylene oxide) (PEO), etc.
- PAN polyacrylonitrile
- PMMA poly(methyl methacrylate)
- PVdF poly(vinylidene fluoride)
- PVdF poly(vinylidene fluoride-co-hexafluoropropylene
- polystyrene poly(ethylene oxide) (PEO), etc.
- a primary object of the present invention is to provide a liquid polymer electrolyte solution having increased room temperature ionic conductivity and enhanced safety characteristics.
- Another object of the invention is to provide a liquid polymer electrolyte solution with a controlled viscosity for high-energy and long-life lithium secondary batteries, especially for biomedical devices, electric and hybrid vehicles, consumer electronics, submarines, and satellites.
- a further object of the invention is to provide an electrochemical cell with enhanced shelf life and safety by the use of the present polymeric electrolyte.
- the liquid polymer electrolyte solution in the present invention is prepared by using the composition which comprises liquid cyclic poly(siloxane- g-ethylene oxide) with proper viscosity and a lithium salt.
- Figure 1 is a summary of the synthesis of one species of the polysiloxane of present invention.
- Figure 2 is a plot of temperature vs. conductivity for poly(siloxane-g-3 ethylene oxide) electrolyte.
- the electrolyte solution of the present invention comprises cyclic siloxane polymers with poly(ethylene oxide) as a side chain (see general formula III).
- the cyclic type siloxane main body provides flame-retardant properties and chemical stability, and poly(ethylene oxide) side chains give ionic conducting phases.
- Poly(ethylene oxide) group is directly grafted to silicon atoms in the cyclic siloxane polymer.
- Cyclic poly(siloxane-g- ethylene oxide)s of the present invention are easily synthesized through simple dehydrogenation reaction using mild catalysts (e.g. aryl borate or potassium carbonate). These catalysts avoid problems arising from the use of metal catalysts such as platinum for the synthesis of poly(siloxane-g-ethylene oxide) with an alkylene spacer between the silicon atom and poly(ethylene oxide) (see general formula I above).
- the cyclic poly(siloxane-g-ethylene oxide) easily dissolves lithium salt and has enough flexibility to transport lithium ion.
- the viscosity of poly(siloxane-g-ethylene oxide) can be optimized by controlling the size of siloxane ring or the length of poly(ethylene oxide) side chain. By so optimizing the viscosity, the polymeric electrolyte solution provides high ionic conductivity of close to 10 "3 S/cm at around room temperature.
- the lithium salt to be used in the present invention is not particularly limited, as long as it serves as an electrolyte for a lithium secondary battery.
- specific lithium salts include LiClO 4 , LiBF 4 , LiAsF 6 , LiPF 6 , LiCF 3 SO 3 , Li(CF 3 SO 2 ) 2 N, Li(CF 3 SO 2 ) 3 C, LiN(SO 2 C 2 F 5 ) 2 ), lithium alkyl fluorophosphates, lithium oxalatoborate, as well as other lithium bis(chelato)borates having five to seven membered rings, LiPF 3 (C 2 F 5 ) 3 , LiPF 3 (CF 3 ) 3 , LiB(C 2 O ) 2j and mixtures thereof.
- the molar ratio of the side-chain oxygen of poly(siloxane-g-ethylene oxide), m in General Formula III, to the lithium salt is preferably about 5 to 50. If the proportion of side- chain oxygen is larger than 50, the ionic conductivity of the resulting polymeric electrolyte is undesirably decreased because of the inadequate numbers of carrier ions in the solid polymer electrolyte. If the molar ratio is smaller than 5, the lithium salt is not sufficiently dissociated in the resulting polymeric electrolyte and the aggregation of lithium ions can reduce the ionic conductivity.
- the polymeric electrolyte solution of the present invention can be applied in lithium secondary batteries in the same way as common carbonate-based electrolyte solutions.
- Lithium secondary batteries with the present invention's polymeric electrolyte solution as a conducting medium can be fabricated by injecting the polymeric electrolyte solution into a spiral wound cell or prismatic type cell (laminated, Z-fold, etc.). It can also be coated onto the surface of electrodes and assembled with a porous separator to fabricate a single or multi- stacked cell that is packaged in a plastic or plastic/foil laminated pouch.
- the electrolyte of the present invention can be mixed with the active material, the binder and the electronic additive (a conductor typically made from graphite, carbon black, acetyl black, or other carbonaceous material) to form a slurry and then cast the slurry with an embedded current collector to obtain a composite electrode after drying.
- Example 1 Eight-membered ring poly(siloxane-g-3 ethylene oxide) (see general formula IV) was synthesized (Sample W98) using a boron catalyst as follows:
- poly(siloxane-g-3 ethylene oxide) electrolyte shows high ionic conductivity of 1.13 x 10 S/cm at 25°C.
- Table 1 reports the results of conductivity testing of both 8 member and 10 member ring molecules.
- Example 3 and the 10 membered ring samples (see Example 2 below) showed favorable conductivity.
- Example 2 A 10- membered ring poly(siloxane-g-3 ethylene oxide) was synthesized (Sample W96) using a boron catalyst as follows:
- Example 3 Eight-membered ring poly(siloxane-g-3 ethylene oxide) (see general formula IV) was synthesized (Sample W92) using triethylamine (Et 3 N) as a catalyst as follows: [0033] Triethylamine (Aldrich, 73 ml, 52.50 g, 0.52 mol) was slowly added through a syringe to the cloudy mixture of Df (Gelest Inc., 31.25 g, 0.52 mol Si-H) and tri(ethyleneglycol) monomethyl ether (Aldrich, 85.30 g, 0.52 mol) at 0°C under nitrogen atmosphere. Vigorous bubbling was observed.
- Example 4 A freestanding solid polymer electrolyte was prepared using the interpenetrating polymerization technique. It was made up of an 8-membered ring poly(siloxane-g-3 ethylene oxide) electrolyte (see general formula IV), poly(ethylene oxide) dimethacrylate as a network forming agent, benzoyl peroxide as a radical initiator and LiN(SO 2 CF 3 ) 2 (LiTFSI) as a lithium salt. The reaction was cured at 70°C for 2hrs. The ionic conductivity of the polymeric electrolytes at 37°C was measured from the AC impedance curves of 2030 button cells assembled by interposing the polymeric electrolyte between two stainless steel discs. The measurement frequency range was from 1 MHz to 10 Hz.
- the preferred embodiment of the invention is poly(siloxane-g-ethylene oxide) with a molar ratio of the side-chain oxygen of poly(siloxane-g-ethylene oxide), m in General Formula III, to the lithium salt equal to about 5 to 50.
- Any commonly used lithium salt is acceptable including, without limitation, LiClO 4 , LiBF 4 , LiAsF 6 , LiPF 6 , LiCF 3 SO 3 , Li(CF 3 SO 2 ) 2 N, Li(CF 3 SO 2 ) 3 C, LiN(SO 2 C 2 F 5 ) 2 ), lithium alkyl fluorophosphates, lithium oxaloborate, and mixtures thereof.
- the average molecular weight of the liquid poly(siloxane- g-ethylene oxide) is optimally less than or equal to 20,000 g/mole.
- the optimal viscosity of the electrolyte of the present invention is about 10,000 cps or less.
- Tris(pentafluorophenyl)boron B(C 6 F 5 ) 3 is the preferred catalyst.
- the preferred network forming polymer comprises poly(alkylene oxide) dialkyl alkyl acrylates represented by General Formula (V):
- R represents a group selected from an alkyl group having 1 to 10 carbon atoms; and each of R' and R" represents hydrogen or a group selected from an alkyl group having 1 to 10 carbon atoms and or an alkenyl group having 2 to 12 carbon atoms; and X being hydrogen or a methyl group; and n represents numeral of 1 to 15.
Abstract
Description
Claims
Priority Applications (2)
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AU2003223327A AU2003223327A1 (en) | 2002-03-22 | 2003-03-20 | Polymer electrolyte for electrochemical cell |
US10/491,071 US20040214090A1 (en) | 2002-03-22 | 2003-03-20 | Polymer electrolyte for electrochemical cell |
Applications Claiming Priority (14)
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US10/104,352 | 2002-03-22 | ||
US10/104,352 US20030180624A1 (en) | 2002-03-22 | 2002-03-22 | Solid polymer electrolyte and method of preparation |
US10/167,940 US7498102B2 (en) | 2002-03-22 | 2002-06-12 | Nonaqueous liquid electrolyte |
US10/167,940 | 2002-06-12 | ||
PCT/US2003/002127 WO2003083970A1 (en) | 2002-03-22 | 2003-01-22 | Nonaqueous liquid electrolyte |
USPCT/US03/02128 | 2003-01-22 | ||
USPCT/US03/02127 | 2003-01-22 | ||
PCT/US2003/002128 WO2003083971A1 (en) | 2002-03-22 | 2003-01-22 | Solid polymer electrolyte and method of preparation |
US44389203P | 2003-01-30 | 2003-01-30 | |
US60/443,892 | 2003-01-30 | ||
US44684803P | 2003-02-11 | 2003-02-11 | |
US60/446,848 | 2003-02-11 | ||
US45106503P | 2003-02-26 | 2003-02-26 | |
US60/451,065 | 2003-02-26 |
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PCT/US2003/008783 WO2003083974A1 (en) | 2002-03-22 | 2003-03-20 | Method for fabricating composite electrodes |
PCT/US2003/008740 WO2003083972A1 (en) | 2002-03-22 | 2003-03-20 | Nonaqueous liquid electrolyte |
PCT/US2003/008779 WO2003083973A1 (en) | 2002-03-22 | 2003-03-20 | Polymer electrolyte for electrochemical cell |
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PCT/US2003/008783 WO2003083974A1 (en) | 2002-03-22 | 2003-03-20 | Method for fabricating composite electrodes |
PCT/US2003/008740 WO2003083972A1 (en) | 2002-03-22 | 2003-03-20 | Nonaqueous liquid electrolyte |
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Cited By (15)
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US6887619B2 (en) | 2002-04-22 | 2005-05-03 | Quallion Llc | Cross-linked polysiloxanes |
US7241822B2 (en) | 2001-08-30 | 2007-07-10 | Clariant Produkte (Deutschland) Gmbh | Dye composition for dyeing powder coatings |
US7528572B2 (en) | 2004-03-10 | 2009-05-05 | Quallion Llc | Power system for managing power from multiple power sources |
US7695860B2 (en) | 2002-03-22 | 2010-04-13 | Quallion Llc | Nonaqueous liquid electrolyte |
US7718321B2 (en) | 2004-02-04 | 2010-05-18 | Quallion Llc | Battery having electrolyte including organoborate salt |
US8076032B1 (en) | 2004-02-04 | 2011-12-13 | West Robert C | Electrolyte including silane for use in electrochemical devices |
US8076031B1 (en) | 2003-09-10 | 2011-12-13 | West Robert C | Electrochemical device having electrolyte including disiloxane |
US8153307B1 (en) | 2004-02-11 | 2012-04-10 | Quallion Llc | Battery including electrolyte with mixed solvent |
US8715863B2 (en) | 2004-05-20 | 2014-05-06 | Quallion Llc | Battery having electrolyte with mixed solvent |
US8765295B2 (en) | 2004-02-04 | 2014-07-01 | Robert C. West | Electrolyte including silane for use in electrochemical devices |
US9192772B1 (en) | 2004-06-29 | 2015-11-24 | Quallion Llc | Portable medical power system |
US9590269B2 (en) | 2013-12-31 | 2017-03-07 | Industrial Technology Research Institute | Polyelectrolyte and energy storage device |
US9786954B2 (en) | 2004-02-04 | 2017-10-10 | Robert C. West | Electrolyte including silane for use in electrochemical devices |
US10122049B2 (en) | 2014-02-06 | 2018-11-06 | Gelion Technologies Pty Ltd | Gelated ionic liquid film-coated surfaces and uses thereof |
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US7883801B2 (en) | 2005-11-15 | 2011-02-08 | Samsung Sdi Co., Ltd. | Electrolyte for rechargeable lithium battery, and rechargeable lithium battery including the same |
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WO2020194438A1 (en) * | 2019-03-25 | 2020-10-01 | 日清紡ホールディングス株式会社 | Electrolyte additive |
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- 2003-03-20 AU AU2003224731A patent/AU2003224731A1/en not_active Abandoned
- 2003-03-20 WO PCT/US2003/008783 patent/WO2003083974A1/en not_active Application Discontinuation
- 2003-03-20 WO PCT/US2003/008740 patent/WO2003083972A1/en not_active Application Discontinuation
- 2003-03-20 WO PCT/US2003/008779 patent/WO2003083973A1/en not_active Application Discontinuation
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US7241822B2 (en) | 2001-08-30 | 2007-07-10 | Clariant Produkte (Deutschland) Gmbh | Dye composition for dyeing powder coatings |
US7695860B2 (en) | 2002-03-22 | 2010-04-13 | Quallion Llc | Nonaqueous liquid electrolyte |
US6887619B2 (en) | 2002-04-22 | 2005-05-03 | Quallion Llc | Cross-linked polysiloxanes |
US8076031B1 (en) | 2003-09-10 | 2011-12-13 | West Robert C | Electrochemical device having electrolyte including disiloxane |
US9786954B2 (en) | 2004-02-04 | 2017-10-10 | Robert C. West | Electrolyte including silane for use in electrochemical devices |
US8076032B1 (en) | 2004-02-04 | 2011-12-13 | West Robert C | Electrolyte including silane for use in electrochemical devices |
US7718321B2 (en) | 2004-02-04 | 2010-05-18 | Quallion Llc | Battery having electrolyte including organoborate salt |
US8765295B2 (en) | 2004-02-04 | 2014-07-01 | Robert C. West | Electrolyte including silane for use in electrochemical devices |
US8153307B1 (en) | 2004-02-11 | 2012-04-10 | Quallion Llc | Battery including electrolyte with mixed solvent |
US7528572B2 (en) | 2004-03-10 | 2009-05-05 | Quallion Llc | Power system for managing power from multiple power sources |
US8715863B2 (en) | 2004-05-20 | 2014-05-06 | Quallion Llc | Battery having electrolyte with mixed solvent |
US9192772B1 (en) | 2004-06-29 | 2015-11-24 | Quallion Llc | Portable medical power system |
US9590269B2 (en) | 2013-12-31 | 2017-03-07 | Industrial Technology Research Institute | Polyelectrolyte and energy storage device |
US10122049B2 (en) | 2014-02-06 | 2018-11-06 | Gelion Technologies Pty Ltd | Gelated ionic liquid film-coated surfaces and uses thereof |
CN109476838A (en) * | 2016-07-13 | 2019-03-15 | 三星Sdi株式会社 | Polymer, the electrolyte including polymer and the lithium battery including polymer |
US11183709B2 (en) | 2016-07-13 | 2021-11-23 | Samsung Sdi Co., Ltd. | Polymer, electrolyte including the same, and lithium battery including the polymer |
Also Published As
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AU2003223327A1 (en) | 2003-10-13 |
WO2003083972A1 (en) | 2003-10-09 |
AU2003218329A1 (en) | 2003-10-13 |
AU2003224731A1 (en) | 2003-10-13 |
WO2003083974A1 (en) | 2003-10-09 |
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