WO2005027255A1 - High performance energy storage devices - Google Patents
High performance energy storage devices Download PDFInfo
- Publication number
- WO2005027255A1 WO2005027255A1 PCT/AU2004/001262 AU2004001262W WO2005027255A1 WO 2005027255 A1 WO2005027255 A1 WO 2005027255A1 AU 2004001262 W AU2004001262 W AU 2004001262W WO 2005027255 A1 WO2005027255 A1 WO 2005027255A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- lead
- capacitor
- electrode
- battery
- acid battery
- Prior art date
Links
- 238000004146 energy storage Methods 0.000 title description 3
- 239000003990 capacitor Substances 0.000 claims abstract description 205
- 239000002253 acid Substances 0.000 claims abstract description 113
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000003792 electrolyte Substances 0.000 claims abstract description 32
- 239000000654 additive Substances 0.000 claims description 80
- 230000000996 additive effect Effects 0.000 claims description 61
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 45
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 40
- 239000000463 material Substances 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 25
- 229910052799 carbon Inorganic materials 0.000 claims description 24
- 229910052725 zinc Inorganic materials 0.000 claims description 24
- 239000011701 zinc Substances 0.000 claims description 24
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 19
- 239000007772 electrode material Substances 0.000 claims description 19
- 239000011248 coating agent Substances 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 18
- 150000004679 hydroxides Chemical class 0.000 claims description 18
- 239000004020 conductor Substances 0.000 claims description 17
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 229910052787 antimony Inorganic materials 0.000 claims description 16
- 229910000464 lead oxide Inorganic materials 0.000 claims description 16
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 16
- 229910052742 iron Inorganic materials 0.000 claims description 15
- 229910052793 cadmium Inorganic materials 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 229910052709 silver Inorganic materials 0.000 claims description 14
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 12
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical group OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000011149 active material Substances 0.000 claims description 10
- 239000006229 carbon black Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 229910052745 lead Inorganic materials 0.000 claims description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 9
- 229910052797 bismuth Inorganic materials 0.000 claims description 9
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 9
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 9
- 239000004332 silver Substances 0.000 claims description 9
- -1 aluminium Chemical class 0.000 claims description 8
- 239000003575 carbonaceous material Substances 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- 229910001923 silver oxide Inorganic materials 0.000 claims description 6
- 239000007773 negative electrode material Substances 0.000 claims description 5
- 239000002861 polymer material Substances 0.000 claims description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 4
- 229920001940 conductive polymer Polymers 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- 229910001416 lithium ion Inorganic materials 0.000 claims description 4
- 235000011149 sulphuric acid Nutrition 0.000 claims description 4
- 239000001117 sulphuric acid Substances 0.000 claims description 4
- RLTFLELMPUMVEH-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[V+5] Chemical class [Li+].[O--].[O--].[O--].[V+5] RLTFLELMPUMVEH-UHFFFAOYSA-N 0.000 claims description 2
- IDSMHEZTLOUMLM-UHFFFAOYSA-N [Li].[O].[Co] Chemical class [Li].[O].[Co] IDSMHEZTLOUMLM-UHFFFAOYSA-N 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 239000002322 conducting polymer Substances 0.000 claims description 2
- 230000002687 intercalation Effects 0.000 claims description 2
- 238000009830 intercalation Methods 0.000 claims description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims description 2
- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical class [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 claims description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical class [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 2
- 229910000686 lithium vanadium oxide Inorganic materials 0.000 claims description 2
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical class [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052987 metal hydride Inorganic materials 0.000 claims description 2
- 150000004681 metal hydrides Chemical class 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 2
- 239000008199 coating composition Substances 0.000 claims 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 17
- 229910052739 hydrogen Inorganic materials 0.000 description 17
- 239000001257 hydrogen Substances 0.000 description 17
- 210000004027 cell Anatomy 0.000 description 15
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000013461 design Methods 0.000 description 7
- 239000011787 zinc oxide Substances 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 230000001172 regenerating effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 229920001410 Microfiber Polymers 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 230000001133 acceleration Effects 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000003658 microfiber Substances 0.000 description 3
- 229920001084 poly(chloroprene) Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910000978 Pb alloy Inorganic materials 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 150000001463 antimony compounds Chemical class 0.000 description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 description 2
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Inorganic materials [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940065285 cadmium compound Drugs 0.000 description 1
- 150000001662 cadmium compounds Chemical class 0.000 description 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000011262 electrochemically active material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003752 zinc compounds Chemical class 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
- H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
-
- 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
-
- 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/38—Carbon pastes or blends; Binders or additives therein
-
- 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- 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
-
- 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
- H01M10/06—Lead-acid accumulators
- H01M10/12—Construction or manufacture
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/52—Removing gases inside the secondary cell, e.g. by absorption
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
-
- 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
- H01M4/14—Electrodes for lead-acid accumulators
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/627—Expanders for lead-acid accumulators
-
- 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
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/531—Electrode connections inside a battery casing
- H01M50/54—Connection of several leads or tabs of plate-like electrode stacks, e.g. electrode pole straps or bridges
- H01M50/541—Connection of several leads or tabs of plate-like electrode stacks, e.g. electrode pole straps or bridges for lead-acid accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M16/00—Structural combinations of different types of electrochemical generators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- 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
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0005—Acid electrolytes
- H01M2300/0011—Sulfuric acid-based
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- 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
- Y02E60/13—Energy storage using capacitors
-
- 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
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to high performance energy storage devices, including batteries such as lead- acid batteries and other battery types, as well as capacitor electrodes and asymmetric capacitors.
- batteries such as lead- acid batteries and other battery types
- capacitor electrodes and asymmetric capacitors There is growing demand for the development and introduction of vehicles that do not rely almost entirely on fossil fuels, to combat air pollution in urban environments and to reduce the global consumption of limited supplies of the fossil fuels.
- Such vehicles fall into three main classes: electric vehicles (EVs) , hybrid electric vehicles (HEVs) and mild hybrid electric vehicles (also known as 42-volt powernet vehicles) .
- Electric vehicles and hybrid electric vehicles may use a variety of different battery types, including lead- acid batteries. Mild hybrid electric vehicles may use mainly lead-acid batteries because of reduced cost.
- Hybrid and mild hybrid electric vehicles rely on a combination of an internal combustion engine and a battery for power supply. Due to the increasing on-board power requirements in the present luxury cars (internal combustion engine cars), the capability of present 14-volt alternators is close to or beyond its limitation. Thus, mild hybrid electric vehicles have been developed. Such mild hybrid electric vehicles employ a 36-volt battery and a 42-volt alternator. The mild hybrid electric vehicles provide some advantages over the existing internal combustion engine cars, including higher use of the electrically generated power, resulting in lower emissions. Whilst there have been many significant advances in the development of new batteries and power networks for vehicles relying at least partly on electric power, the batteries used in these vehicles still suffer from a number of problems.
- the partial state-of-charge conditions (PSoC) under which these batteries generally operate is 20-100% for electric vehicles, 40-60% for hybrid electric vehicles, and 70-90% for mild hybrid electric vehicles.
- This is a high rate partial state-of- charge (HRPSoC) .
- HRPSoC high rate partial state-of- charge
- the lead-acid batteries fail prematurely mainly due to the progressive accumulation of lead sulphate on the surfaces of the negative plates. This occurs because the lead sulphate cannot be converted efficiently back to sponge lead during charging either from the regenerative braking or from the engine. Eventually, this layer of lead sulphate develops to such an extent that the effective surface area of the plate is reduced markedly, and the late can no longer deliver the higher current demanded from the automobile.
- a lead- acid battery comprising: - at least one lead-based negative electrode, at least one lead dioxide-based positive electrode, at least one capacitor negative electrode, and electrolyte in contact with the electrodes, wherein the positive electrode and the lead-based negative electrode define a battery part, and the positive electrode and the capacitor negative electrode define an asymmetric capacitor part, with the positive electrode shared by the battery part and the asymmetric capacitor part, and wherein the lead-based negative and capacitor negative electrodes are connected to a negative busbar, and the positive electrode or electrodes are connected to a positive busbar.
- the lead dioxide battery part and the asymmetric capacitor part of the lead-acid battery are connected in parallel in the one common unit.
- the asymmetric capacitor part preferentially takes or releases charge during high current charging or discharging. This occurs since the asymmetric capacitor part has a lower internal resistance than the battery-part, and will first absorb and release charge during high-rate charging (for instance during regenerative braking) or during high-rate discharging (for instance during vehicle acceleration and engine cranking) . Consequently, the asymmetric capacitor part will share the high-rate operation of the lead-acid battery part, and will provide the lead-acid battery with significantly longer life. All of this is achieved without any electronic control or switching between the battery and capacitor parts. According to one embodiment, the positive electrode shared by the two parts is disposed between the lead-based negative electrode and the capacitor negative electrode.
- a second aspect provides a lead-acid battery comprising: at least one lead-based negative electrode; at least one lead dioxide-based positive electrode; - at least one capacitor electrode; and electrolyte in contact with the electrodes; wherein a battery part is formed by the lead based negative electrode and the lead dioxide-based positive electrode; and an asymmetric capacitor part is formed by the capacitor electrode and one electrode selected from the lead based negative electrode and the lead dioxide based positive electrode; and wherein all negative electrodes are connected to a negative busbar, and all positive electrodes are connected to a positive busbar.
- each of the capacitor electrodes may individually be positive or negative electrodes.
- the lead-acid battery comprises an alternating series of positive and negative electrodes.
- each of these may be a battery electrode, a capacitor electrode, or a combined battery/capacitor electrode.
- a lead-acid battery comprising an alternating series of positive and negative electrodes and an electrolyte in contact with the electrodes, wherein: - at least one pair of adjacent positive and negative electrode regions store energy capacitively, and at least one pair of adjacent lead dioxide positive and lead negative battery electrode regions store energy electrochemically, and wherein the positive electrodes are directly connected by a first conductor and the negative electrodes are directly connected by a second conductor.
- hydrogen gassing may occur. This particularly applies when the cell voltage is greater than the potential range of an electrode.
- At least one of the capacitor negative electrodes comprises a high surface area capacitor material and one or more additives selected from oxides, hydroxides or sulfates of lead, zinc, cadmium, silver and bismuth.
- the additives are preferably added in oxide form.
- the additives are preferably lead and/or zinc additives, most preferably lead and/or zinc oxide. Mismatching can also occur at the capacitor positive electrode.
- the capacitor positive electrode comprises: a high surface area capacitor material, Pb 2 0 3 , an oxide, hydroxide or sulfate of antimony, and optionally one or more additives selected from oxides, hydroxides and sulfates of iron and lead.
- a hybrid battery-capacitor comprising: at least one battery-type positive electrode, at least one battery-type negative electrode, at least one capacitor-type electrode selected from a capacitor negative electrode and a capacitor positive electrode, wherein the capacitor negative electrode comprises a high surface area capacitor material and one or more additives selected from oxides, hydroxides or sulfates of lead, zinc, cadmium, silver and bismuth, and wherein the capacitor positive electrode comprises: - a high surface area capacitor material, Pb 2 0 3 , an oxide, hydroxide or sulfate of antimony, and optionally one or more additives selected from oxides, hydroxides and sulfates of iron and lead, and an electrolyte in contact with the electrodes, wherein a battery part is formed between (i.e.
- the novel capacitor negative electrode comprises a current collector and a paste coating, the paste coating comprising a high surface area capacitor material, a binder and between 5-40wt%, based on the weight the paste coating, of an additive or additive mixture selected from oxides, hydroxides or sulfates of lead, zinc, cadmium, silver and bismuth, with the proviso that the additive includes at least one oxide, hydroxide or sulfate of lead or zinc.
- the novel capacitor positive electrode comprises a current collector and a paste coating, the paste coating comprising a high surface area capacitor material, a binder and between 10-40wt%, based on the weight the paste coating, of an additive mixture comprising: Pb 2 0 3 , an oxide, hydroxide or sulfate of antimony, and - optionally one or more oxides, hydroxides or sulfates of iron and lead.
- an additive mixture comprising: Pb 2 0 3 , an oxide, hydroxide or sulfate of antimony, and - optionally one or more oxides, hydroxides or sulfates of iron and lead.
- Figure 1 is a schematic side view of a lead-acid battery in accordance with one embodiment of the invention
- Figure 2 is a schematic plan view of the lead-acid battery of Figure 1
- Figure 3 is a graph representing a current profile of a single cycle of the test conducted on the battery of the embodiment of Figures 1 and 2
- Figure 4 is a graph representing the cycling performance of the battery of Figures 1 and 2 against a comparison battery
- Figure 5 is a schematic side view of a lead-acid battery in accordance with a second embodiment of the invention
- Figure 6 is a schematic side view of one of the negative electrodes of the lead-acid battery of Figure 5
- Figure 7 is a graph representing the hydrogen evolution rate of a negative capacitor electrode of a fourth embodiment of the invention, compared to a standard carbon electrode and a standard lead-based negative electrode
- Figure 8 is a schematic side view representing the electrode arrangement of a battery of a third embodiment of the invention.
- lead-acid battery is used in its broadest sense to encompass any unit containing one or more lead- acid battery cells.
- the lead-acid batteries described contain at least one lead-based negative electrode or region, at least one lead dioxide-based positive electrode or region and at least one capacitor negative electrode or region. In the following each of these electrode types are described, followed by the electrode region concept.
- Electrodes generally comprise a current collector (otherwise known as a grid or plate) , with the active electrode material applied thereto.
- the active electrode material is most commonly applied in a paste form to the current collector, and in the present specification the term paste applies to all such active-material containing compositions applied in any way to the current collector.
- the term "based" used in the context of electrodes is intended to refer to the active electrode material. This term is used to avoid suggesting that the electrode is formed entirely from the active material, as this is not the case. The term also is intended to indicate that the active material of the given electrode may contain additives or materials other than the active material specifically mentioned.
- the lead and lead dioxide electrodes may be of any arrangement or type suitable for use in a lead-acid battery. Generally, such electrodes are in the form of a metal grid (usually made from lead or lead alloy) that supports the electrochemically active material (lead or lead dioxide) which is pasted onto the grid. The operation of pasting is well known in the field. Although any suitable lead or lead dioxide known in the art may be used, it would be advantageous to use the lead compositions disclosed in co-pending application PCT/AU2003/001404 (claiming priority from Australian Patent Application AU 2002952234). It is to be noted that, prior to formation of the battery, the active material may not be in the active form (i.e. it may not be in the form of the metal, or in the dioxide form) . Thus, - li the terms encompass those other forms which are converted to lead metal or lead dioxide when the battery is formed.
- Capacitor electrodes similarly comprise a current collector and a coating of an active material. This is commonly applied as a paste.
- the term “capacitor” is used in the context of electrodes to refer to electrodes that store energy through the double layer capacitance of a particle/solution interface between high surface area materials and an electrolyte solution.
- capacitors There are two main classes of capacitors. One class is the “double-layer capacitors” (otherwise known as “symmetric capacitors”) containing two such electrodes, one as the positive and the other as the negative.
- the second class is the asymmetric capacitors, which are also referred to as hybrid capacitors, “ultracapacitors” and
- Asymmetric capacitors comprise one electrode that stores energy through double layer capacitance across a particle/solution interface, and a second electrode that is a faradaic or battery-type electrode which stores energy pseudo ⁇ apacitively.
- the prefixes "ultra” and “super” are sometimes used to refer generically to asmymmetric capacitors, and sometimes to refer to such capacitors having large storage capability. In the present application the prefix “ultra” is most usually used in this first sense, but on occasion it is used in the second sense, as the capacitance of the capacitor parts of the batteries of the present invention preferably have high capacitance.
- the asymmetric capacitor parts preferably have ultracapacitor capacitance, more preferably of supercapacitor capacitance.
- the capacitor electrode comprises a metal grid (usually made from a lead alloy) and a pasted coating containing the capacitor material, usually with a binder.
- the capacitor electrode suitably comprises a high surface area (or high-rate) materials suitable for use in capacitors. Such materials are well known in the art.
- high-rate capacitor materials include high surface area carbon, ruthenium oxide, silver oxide, cobalt oxide and conducting polymers.
- the capacitor negative electrode comprises a high surface area carbon material.
- high surface area carbon materials are activated carbon, carbon black, amorphous carbon, carbon nanoparticles, carbon nanotubes, carbon fibres and mixtures thereof. Often mixtures of materials are used to obtain an appropriate balance between surface area (and thus capacitance) and conductivity.
- activated carbon is the most appropriate source.
- One suitable activated carbon material is one with a surface area of between 1000 and 2500 m 2 /g, preferably 1000-2000 m/g. This material is suitably used in combination with a more conductive material, such as carbon black.
- One suitable carbon black material has a surface area of between 60-1000 m 2 /g.
- One suitable mixture of these materials comprises between 5-20% carbon black,
- the capacitor negative electrodes comprise an additive or additive mixture comprising an oxide, hydroxide or sulfate of lead, zinc, cadmium, silver and bismuth, or a mixture thereof.
- the additive includes at least one oxide, hydroxide or sulfate of lead or zinc.
- the additive is suitably one or more oxides selected from lead oxide, zinc oxide, cadmium oxide, silver oxide and bismuth oxide.
- each of the capacitor negative electrodes comprise the additive in addition to the high surface area capacitor material. Due to toxicity reasons, cadmium compounds are not preferred, and therefore the composition preferably comprises a lead compound and/or zinc compound, and optionally a silver compound. For cost reasons, silver oxide and bismuth oxide would usually be avoided. Irrespective of the form in which the additive is added, when conductor comes into contact with the electrolyte (for example, sulfuric acid), the additive may react with the electrolyte and thus be converted into another metal compound derived from the original metal oxide, sulfate or hydroxide.
- the electrolyte for example, sulfuric acid
- references to the oxides, sulfates and hydroxides of the subject additives are to be read as encompassing the products of the reactions between the additives and the electrolyte. Similarly, if during the charged or discharged state of the battery the additive is converted into another form through redox reactions, the references to the oxides, sulfates and hydroxides are to be read as encompassing the products of the redox reactions on these additives.
- the capacitor positive electrodes preferably comprises: a high surface area capacitor material (as described above) , Pb 2 0 3 ("red lead"), - an oxide, hydroxide or sulfate of antimony, and optionally one or more additives selected from oxides, hydroxides and sulfates of iron and lead.
- the compound of antimony is beneficial in suppressing (oxygen) gassing at the positive capacitor electrode. However, if it migrates to the negative capacitor electrode, it produces an adverse effect on hydrogen gassing at that electrode.
- the antimony compound In the absence of an agent to fix the antimony compound to the positive capacitor electrode, when the antimony compound comes into contact with the electrolyte, it may dissolve in the electrolyte, and be deposited on the negative electrode when a current is applied.
- the red lead is used to fix or prevent transfer of the antimony to the negative electrode.
- Compounds (i.e. oxides, sulfates or hydroxides) of lead and iron are also advantageous in this electrode, and may also be used in the additive mixture.
- the additive is used in amount to avoid hydrogen and oxygen gassing. This is generally an amount that increases the potential window of the capacitor negative and positive electrode from the typical +0.9V or ⁇ l.OV to at least ⁇ 1.2V, and preferably at least ⁇ 1.3V.
- the total oxide content may be between 5-40wt%, based on the total active material composition (including high surface active material, binder, and any other component in the dried paste composition) .
- the negative capacitor electrode additive comprises between l- 0wt% Pb compound (more preferably 1-20%), l-20wt% Zn compound (more preferably 1- 10%), 0-5wt% Cd compound and 0-5wt% Ag compound.
- the total is within the 5-40wt% range mentioned above.
- the use of ZnO additive alone provides good results, as does PbO alone, or a mixture of PbO and ZnO.
- the positive capacitor electrode additive comprises between 0-30wt% Pb (preferably l-30wt%) in oxide (any oxide) , sulfate or hydroxide form, l-10wt% Pb 2 0 3 , 0-2wt% Fe (preferably l-2wt%) in oxide, sulfate or hydroxide form and 0.05 to lwt% Sb in oxide, sulfate or hydroxide form.
- Pb preferably l-30wt% in oxide (any oxide) , sulfate or hydroxide form
- l-10wt% Pb 2 0 3 0-2wt% Fe (preferably l-2wt%) in oxide, sulfate or hydroxide form
- 0.05 to lwt% Sb in oxide, sulfate or hydroxide form.
- Sb is added as an oxide.
- the total is within 5-40wt% range mentioned above.
- the additive-containing capacitor electrodes may be used with a battery type electrode (lead or lead dioxide) and an electrolyte to form an asymmetric capacitor, without any battery positive and battery negative electrode pair defining a battery part.
- This asymmetric capacitor containing novel components can be externally connected to a battery in the conventional manner, but without any extra electronic device.
- the battery may include electrodes of other types in addition to or as a replacement of the electrodes described above.
- the battery may comprise one or more mixed capacitor-battery electrodes, such as a capacitor-battery positive electrode.
- the capacitor positive electrode (as described above) comprises lead oxide, this is converted into lead dioxide during charging of the battery.
- the capacitor electrode comprising a lead source which is converted into lead dioxide in operation of the battery may be considered to be a capacitor-battery electrode having some qualities of both a capacitor electrode and a battery electrode.
- the incorporation of high surface area material such as carbon into some positive electrodes may be undertaken to address the need to balance the surface area ratio of the positive to negative electrodes.
- the high surface area capacitor negative electrodes will add to a greater overall surface area for negative electrodes compared to positive electrodes.
- failure of the lower surface area electrodes By making the surface area of the positive electrode greater, by incorporating high surface area carbon into some positive electrodes, the balance is addressed.
- the battery may comprise an alternating series of positive and negative electrodes, with an electrolyte in contact with the electrodes, and a first conductor for directly connecting the positive electrodes and a second conductor for directly connecting the negative electrodes, wherein at least one pair of the adjacent positive and negative electrode regions form a capacitor (by storing capacitive energy), and at least one pair of adjacent positive and negative electrode regions form a battery (by storing energy as electrochemical potential between the two electrode pairs) .
- the electrodes of the present invention may be composite electrodes (i.e. they may be composites of battery electrode materials and capacitor electrode materials) .
- the references to "lead-based", “lead dioxide-based” and “capacitor” electrodes encompass the regions of an electrode that have the specified function, irrespective of whether or not the single electrode has other regions of a different type.
- electrodes having regions of different types are deliberately used.
- one or more of the negative electrodes has at least two regions, including a battery-electrode material region and a capacitor-electrode material region.
- the electrode having two regions comprises an electrode current collector, which may be of the type described above, having one face pasted with battery electrode material (such as lead) and the opposite face pasted with capacitor negative electrode material.
- a battery-type electrode containing battery electrode material on both sides may be coated on one face or any other region thereof by a capacitor electrode material.
- the battery electrodes may be of types other than lead lead-acid battery electrodes.
- the battery types of this embodiment are nickel rechargeable batteries, lithium metal or lithium ion rechargeable batteries, and so forth.
- Suitable battery-type positive electrode materials in this case include nickel oxide, silver oxide, manganese oxide, lithium polymer materials, mixed lithium oxides including lithium nickel oxides, lithium cobalt oxides, lithium manganese oxides and lithium vanadium oxides, and lithium conductive polymer cathode materials.
- Suitable battery-type negative electrode materials in this class include zinc, cadium, metal hydrides, lithium in metal or alloy form with other metals such as aluminium, and lithium ion intercalation materials.
- the details of, and alternatives for, these electrode materials used in various battery types can be gathered from various publications in the art of the invention.
- the electrodes may be of any suitable shape, and therefore may be in flat-plate form or in the form of a spirally-wound plate for the formation of either prismatic or spirally-wound cells. For simplicity of design, flat plates are preferred.
- any suitable acid electrolyte may be used.
- the electrolyte may, for instance, be in the form of a liquid or a gel. Sulphuric acid electrolyte is preferred.
- the electrolyte may be an aqueous or organic electrolyte, including alkalis such as potassium and other hydroxides, lithium- ion containing organic solvents, polymer electrolytes, ionic liquid electrolytes in liquid or solid state and so forth.
- Suitable electrolytes for the chosen battery positive and negative electrode materials can be routinely selected by a person skilled in the art.
- busbars or Conductors The busbar of the lead-acid battery may be of any suitable construction, and may be made from any suitable conductive material known in the art .
- the term "connected to" used in the context of the busbars refers to electrical connection, although direct physical contact is preferred. In the case where the battery is not of a typical lead-acid battery configuration with busbars, any conductor may be used that does not involve circuitry external to the battery.
- the components of the battery will be contained within a battery case with further features appropriate to the type of battery employed.
- the lead-acid battery may be either of a flooded-electrolyte design or of a valve-regulated design.
- the battery may be of any suitable design, and may for instance contain gel electrolyte. Specific features of the battery unit appropriate to such designs are well known in the art of the invention.
- the pressure that may be applied to the lead-acid battery may lie in the range of 5-20 kPa for flooded electrolyte design, and from 20-80 kPa for valve regulated lead-acid battery design.
- each of the positive and negative electrodes is separated from adjacent electrodes by porous separators.
- the separators maintain an appropriate separation distance between adjacent electrodes.
- Separators located between immediately adjacent lead-based negative electrodes and lead dioxide-based positive electrodes may be made from any suitable porous material commonly used in the art, such as porous polymer materials or absorptive glass microfibre (“AGM”) .
- AGM absorptive glass microfibre
- separator thickness is generally from 1-2.5 millimetres for these separators.
- Suitable polymer materials useful for forming the separators between the positive and negative electrodes forming the battery part are polyethylene and AGM.
- Polyethylene separators are suitably between 1 and 1.5 millimetres thick, whereas AGM separators are appropriately between 1.2 and 2.5 millimetres thick.
- separators located between the positive electrode and the capacitor negative electrode these are suitably much thinner than the separators of the battery part of the lead-acid battery.
- the separators are between 0.01 and 0.1 millimetres thick, and most preferably between 0.03 and 0.07 millimetres thick.
- separators are suitably made from microporous polymer material such as microporous polypropylene.
- Other separators are AGM and the thickness of this type of separators is between 0.1 and 1 millimetres, and preferably between 0.1 and 0.5 millimetres.
- the lead-acid battery After assembling of the appropriate components together in a battery case, the lead-acid battery generally needs to be formed.
- the formation operation is well known in the field. It is to be understood that the references to "lead-based” and “lead dioxide-based” materials are used to refer to lead or lead dioxide itself, materials containing the metal/metal dioxide or to materials that are converted into lead or lead dioxide, as the case may be, at the given electrode.
- the lead- acid battery contains at least one of each type of electrode. The number of individual cells (made up of a negative and positive plate) in the battery depends on the desired voltage of each battery.
- Electrode Arrangement For best operation according to one embodiment, the positive and negative electrodes are interleaved, so that each positive electrode has one lead-based negative electrode to one side of it, and one capacitor negative electrode to the opposite side. Accordingly, the arrangement of one embodiment has alternating positive and negative electrodes, with the negative electrodes being alternately a lead-based electrode and a capacitor negative electrode. All of the negative electrodes (lead and carbon) are connected to the negative busbar, and the positive electrodes are connected to the positive busbar, so that each battery cell and ultracapacitor cell is connected in parallel in the common lead-acid battery.
- the ultracapacitor cell in the lead-acid battery arrangement described has a lower internal resistance than the lead-acid battery cell, and therefore it will first absorb a release charge during high-rate charging (for generative braking) or during high-rate discharge (vehicle acceleration and engine cranking) . Consequently, the asymmetric capacitor cell will share the high-rate operation of the lead-acid battery cell and will provide the lead-acid battery with significantly longer life. More specifically, lead sulphate formation on the battery cell electrodes which generally occurs during high-current charging and discharging of the battery is minimised because the high- current charging and discharging is generally taken up by the asymmetric capacitor.
- Each battery cell of one embodiment of the invention provides a voltage of 2-volts.
- a lead-acid battery of one embodiment suitable for use in the broad range of electric vehicle battery applications will contain 8 negative electrodes and 9 positive electrodes, with 4 of the negative electrodes being lead-based negative electrodes, and the other 4 being capacitor electrodes, in an alternating arrangement. Variations in this arrangement and relative numbers of electrodes are also suitable, provided that there is a minimum of one of each electrode.
- a lead-acid battery of one embodiment of the invention suitable for testing purposes was made in the arrangement as illustrated schematically in Figures 1 and 2.
- Two sponge lead (negative plate) electrodes (1), two lead dioxide positive plate electrodes (2) and one high surface-area negative carbon electrode plate (3) were positioned in an alternating arrangement as illustrated in Figure 1 in a battery case (4) .
- the positive lead dioxide electrodes (2) and negative lead electrodes (1) were 40 millimetres wide by 68 millimetres high by 3.3 millimetres thick.
- the carbon electrode (3) was 40 millimetres wide by 68 millimetres high by 1.4 millimetres thick.
- the battery electrodes were of a standard configuration and composition for lead-acid batteries, and were made by the methods described in the detailed description above.
- the paste composition for the lead negative electrode comprised lead oxide (1kg), fibre 0.6g, BaS0 4 4.93g, Carbon black 0.26g, H 2 S0 4 (1.400 rel.dens.) 57 cm 3 , water 110 cm 3 , acid to oxide ratio 4% and paste density 4.7 g/cm 3 .
- the paste composition for the lead dioxide positive electrode comprised lead oxide 1kg, fibre 0.3g, H 2 S0 4 (1.400 rel.dens.) 57 cm 3 , water 130 cm 3 , acid to oxide ratio 4% and paste density 4.5 g/cm 3 .
- the lead oxide was converted into lead dioxide and lead by the formation techniques described in our co-pending application.
- the capacitor electrode (3) was made from 20wt% carbon black with specific surface area of 60 m 2 g (Denki Kagaku, Japan), 7.5wt% carboxymethyl cellulose, 7.5wt% neoprene, and 65wt% activated carbon with specific surface area of 2000 m 2 g "1 (Kurarekemikaru Co. Ltd. Japan) . Separators (5, 6) were located between the adjacent electrodes.
- Absorptive glass microfibre (AGM) separators (5) of 2 millimetres in thickness were positioned between the lead-dioxide (2) and lead (1) electrodes, and microporous polypropylene separators (6) of 0.05 millimetres thickness were sandwiched between the positive electrodes (2) and carbon electrode (3) .
- the battery case (4) was filled with sulfuric acid solution (7) .
- the positive electrodes were connected to a positive busbar (8), and the negative electrodes connected to a negative busbar (9) .
- the capacitor negative plate could be disconnected from the negative busbar.
- a charging and discharging profile was developed to simulate typical charge and discharge demands on a 42-volt mild HEV battery typically used in mild HEV applications.
- the profile has short duration (2.35 minutes) and is composed of several current steps that simulate the power requirements of the battery during vehicle operation.
- line 10 is the comparison battery internal resistance profile
- line 11 is the Example 1 battery internal resistance profile
- line 12 is the comparison battery minimum discharge voltage profile
- line 13 is the Example 1 battery minimum discharge voltage profile.
- the comparison battery performs about 2150 cycles, while the battery of Example 1 performs 8940 cycles before the minimum discharge voltages of each battery reaches the cut-off value of 1.6-volts (represented by line 15. Thus, the cycling performance of the battery of Example 1 is at least four times better than that of the comparison battery.
- Example 2 A variation on the battery of Example 1 is illustrated in Figures 5 and 6. For ease of comparison, the same numerals are used to refer to common features of the two batteries.
- the embodiment of this Example comprises three lead dioxide positive plate electrodes (2) and two composite negative electrodes (16) .
- the composite negative electrodes comprise a current collector or grid (17) with the lead-containing paste composition described above applied to one region (the face) thereof (18) and capacitor high surface-area carbon electrode material- containing paste applied to the opposite face (19) . Formation of the electrode is conducted in the manner known in the art. In a variation on this embodiment that is simpler to manufacture, a lead based negative electrode is prepared with lead pasted by conventional dipping techniques to the main body section in lead paste material, followed by formation, and then the capacitor material is pasted to a region or regions of this lead based negative electrode, such as one face thereof.
- the positive (2) and negative composite electrodes (16) are positioned in an alternating arrangement as illustrated in Figure 5 in a battery case (4) .
- the positive lead dioxide electrodes (2) and negative composite electrodes (16) of the embodiment illustrated in Figure 5 are 40 millimetres wide by 68 millimetres high by 3.3 millimetres thick.
- the carbon electrode region (19) of the negative electrode takes up 1.4 millimetres of the thickness of the negative electrode.
- Separators (5, 6) are located between the adjacent electrodes. Absorptive glass microfibre (AGM) separators (5) of 2 millimetres in thickness are positioned between the lead-dioxide (2) and lead face (18) of the negative electrode, and microporous polypropylene separators (6) of 0.05 millimetres thickness are sandwiched between the positive electrodes (2) and carbon face of the negative electrode (19).
- the battery case (4) is filled with sulfuric acid solution (7) .
- the positive electrodes are connected to a positive busbar (8), and the negative electrodes connected to a negative busbar (9) .
- Example 3 Further testing on the battery of Example 1 showed that improvements in electrolyte dry-out could be achieved by matching the hydrogen evolution rate of the carbon electrode (3) during battery charging to be similar to that of the lead negative electrode (1) .
- the hydrogen evolution rates for this electrode were tested and compared to the electrode used in Example 1, as well as the hydrogen evolution rates of the lead negative electrode of example 1.
- curve 20 represents the carbon electrode hydrogen evolution rate
- curve 21 represents the lead-acid negative plate hydrogen evolution rate
- the curve 22 represents the carbon plus additives electrode hydrogen evolution rate.
- the higher current density levels recorded for the carbon electrode with no oxide additive rise considerably at potentials falling below -1.2V, and even more so by -1.3V.
- the battery can be operated at higher potentials without earlier failure due to electrolyte dry-out.
- Inclusion of the oxide CdO would have a similar effect to ZnO and PbO, but for toxicity reasons was not used in the testing.
- AgO has a similar effect, but is an expensive additive and not as effective on its own.
- the levels of ZnO and PbO were varied within the range 1-10% and 1-20% respectively, and the AgO between 1-5%.
- the other oxides mentioned in the detailed description above have a similar impact to AgO.
- Example 4 A further variation on the battery of Example 1 is illustrated in Figure 8. For ease of comparison, the same numerals are used to refer to common features of the two batteries. In addition, for simplicity, only the battery electrodes are illustrated. It will be understood that the battery further includes the separators, case, electrolyte, busbars, terminals and other features of batteries common in the art.
- the battery of this Example comprises an alternating series of positive and negative electrodes.
- the electrodes are, in order from left to right, a lead dioxide battery positive electrode (2), a lead-based battery negative electrode (3), a second lead dioxide battery positive electrode (2), a capacitor carbon and additive negative electrode of the type described in Example 3 (103), a capacitor-battery positive electrode as described further below (23), a second capacitor carbon and additive negative electrode of the type described in Example 3
- the capacitor-battery electrode (23) comprises a metal current collector, with a mixture of activated carbon (60 wt%) , carbon black (20 wt%) and 10 wt% of lead oxide pasted thereon.
- the paste composition is formed with 10 wt%[5 wt% carboxymethyl cellulose and 5 wt% neoprene] binder and sintered onto the current collector.
- the electrode is about 0.8 mm thick.
- the battery of this Example can contain further alternating positive and negative electrodes of any type. Generally it is desirable to ensure that there is some level of matching the surface areas and hydrogen gassing rates of the sum of the positive and negative electrodes, and to include the requisite number of positive and negative electrodes to provide a battery of the desired voltage.
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Abstract
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Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL04761297T PL1665446T3 (en) | 2003-09-18 | 2004-09-16 | High performance energy storage devices |
US10/571,255 US7923151B2 (en) | 2003-09-18 | 2004-09-16 | High performance energy storage devices |
EP04761297A EP1665446B1 (en) | 2003-09-18 | 2004-09-16 | High performance energy storage devices |
AU2004273104A AU2004273104B2 (en) | 2003-09-18 | 2004-09-16 | High performance energy storage devices |
AT04761297T ATE550804T1 (en) | 2003-09-18 | 2004-09-16 | HIGH PERFORMANCE ENERGY STORAGE DEVICES |
KR1020067005440A KR101227779B1 (en) | 2003-09-18 | 2004-09-16 | High performance energy storage devices |
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