EP3931892A1 - Électrode pour dispositif de stockage de l'énergie rechargeable - Google Patents
Électrode pour dispositif de stockage de l'énergie rechargeableInfo
- Publication number
- EP3931892A1 EP3931892A1 EP20719687.4A EP20719687A EP3931892A1 EP 3931892 A1 EP3931892 A1 EP 3931892A1 EP 20719687 A EP20719687 A EP 20719687A EP 3931892 A1 EP3931892 A1 EP 3931892A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- electrode
- layers
- layer
- porous
- current collector
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004146 energy storage Methods 0.000 title claims abstract description 27
- 239000007772 electrode material Substances 0.000 claims abstract description 70
- 239000003792 electrolyte Substances 0.000 claims description 35
- 239000000463 material Substances 0.000 claims description 34
- 238000005470 impregnation Methods 0.000 claims description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 16
- 239000011148 porous material Substances 0.000 claims description 15
- 229910052725 zinc Inorganic materials 0.000 claims description 15
- 239000011701 zinc Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 229920005596 polymer binder Polymers 0.000 claims description 6
- 239000002491 polymer binding agent Substances 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 4
- 239000006260 foam Substances 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 238000012423 maintenance Methods 0.000 claims description 2
- 239000004020 conductor Substances 0.000 abstract description 9
- 239000010410 layer Substances 0.000 description 242
- 238000000576 coating method Methods 0.000 description 15
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 15
- 239000004810 polytetrafluoroethylene Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 239000011149 active material Substances 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- -1 polypropylene Polymers 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000007654 immersion Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 230000008602 contraction Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
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- 229910052744 lithium Inorganic materials 0.000 description 5
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- 238000007789 sealing Methods 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 238000003466 welding Methods 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 210000001787 dendrite Anatomy 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000000840 electrochemical analysis Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000011505 plaster Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 230000004584 weight gain Effects 0.000 description 2
- 235000019786 weight gain Nutrition 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910002640 NiOOH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000011532 electronic conductor Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
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- 230000008569 process Effects 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
Classifications
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/24—Electrodes for alkaline 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
- H01M10/24—Alkaline 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
- H01M10/24—Alkaline accumulators
- H01M10/30—Nickel accumulators
-
- 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
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
- H01M12/065—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode with plate-like electrodes or stacks of plate-like electrodes
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- H01M4/24—Electrodes for alkaline accumulators
- H01M4/244—Zinc electrodes
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- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/661—Metal or alloys, e.g. alloy coatings
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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
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
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- H01M4/74—Meshes or woven material; Expanded metal
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- 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
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
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- H01M4/74—Meshes or woven material; Expanded metal
- H01M4/742—Meshes or woven material; Expanded metal perforated material
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- 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
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
- H01M4/808—Foamed, spongy materials
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2300/0014—Alkaline electrolytes
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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
Definitions
- the present invention relates to the field of energy storage.
- the present invention relates to an electrode for a rechargeable energy storage device, such as a battery (electrochemical accumulator), comprising several layers of electrode material (“ME”) and several porous layers of current collector (“CC”) arranged in a specific manner, the electrode being characterized in that it has a relatively large total thickness (of the order of strictly greater than 4 mm up to 10 mm).
- a battery electrochemical accumulator
- ME electrode material
- CC current collector
- the present invention also relates to an energy storage device comprising said electrode, as well as to the uses of said electrode.
- Electrochemical batteries have become essential components in stationary and portable applications, such as portable electronic devices, electrical or mechanical devices. They are also widely studied for use in electric vehicles, as well as in the field of energy storage. The technologies and variants are numerous (Lead-Acid, Cadmium-Nickel, Metal-Hydride-Nickel, Lithium, Sodium-Sulfur, Zinc-Air, Zinc-Nickel, etc.).
- a metal-air rechargeable battery such as zinc-air
- a metal-air rechargeable battery is a system consisting (in discharge) of a metal anode, a cathode reacting with the oxygen in the air and a electrolyte.
- These batteries have a similar configuration to conventional batteries with respect to the negative electrode since the latter consists of the metal which serves as the negative active material.
- metal air batteries are similar to fuel cells since they are made of a porous structure containing a material allowing the oxygen in the air to be used as a positive active material by a electro catalytic reaction.
- capacity of the battery or of the accumulator is meant the quantity of electrical energy that he / she is able to restore after having received a full charge, for a given discharge current regime, a set stop voltage and temperature. It is usually expressed in ampere-hours (Ah).
- Ah ampere-hours
- the system is limited by geometric technological constraints, namely the two positive electrodes are arranged on either side of the single negative electrode. In this case, the only way to increase the capacity of the battery is to increase the quantity of active material present in the negative electrode and therefore its volume.
- Document US2017 / 0098856 is known from the state of the art.
- This document describes a method for forming a battery comprising at least: a positive electrode, a negative electrode, electrolytes and a porous separation layer.
- the purpose of this document is to provide a lithium battery having in particular a high electrode thickness.
- the electrode thickness can be up to 1 mm and is preferably between 10 and 1000 ⁇ m, in particular between 100 and 800 ⁇ m and typically between 200 and 600 ⁇ m.
- an electrode according to this invention may comprise layers of electrode material interposed with layers comprising a high content of conductive material. These layers with a high content of conductive material do not correspond to current collector layers.
- a stack of active material layer comprising in particular a layer based on carbon nanotubes.
- an object of the present invention is to provide a new electrode for a rechargeable energy storage device which meets, at least in part, the needs of the state of the art.
- An object of the present invention is in fact to provide an electrode for a rechargeable energy storage device, such as a battery, making it possible to increase its capacity, and advantageously to obtain good mechanical strength, even a good cycle life, while taking into account the constraints inherent in the electrode (namely, its physicochemical properties, such as material transfer, porosity, conductivity, electronic percolation or even mechanical strength).
- the invention provides an electrode for a rechargeable energy storage device such as a battery whose negative electrode is zinc-based such as a zinc-air or zinc-nickel battery, comprising several interposed internal layers between two outer layers, said inner layers comprising several layers of ME electrode material composed of at least one electrode active material and several porous DC current collector layers composed of electroconductive material (s) whose conductivity electronics is greater than or equal to 10 2 S. cm -1 , preferably 10 4 S. cm 1 , said layers of ME electrode material and of DC current collector being alternated,
- said outer layers do not consist of said porous DC current collector layers
- said electrode has a total thickness ranging from strictly greater than 4 mm, preferably ranging from strictly greater than 4 mm up to 10 mm, in particular ranging from strictly greater than 4 mm up to 8 mm.
- a layer of ME electrode material is distinct from a porous layer of DC current collector.
- a porous layer of DC current collector exhibits higher electronic conductivity than that of a layer of ME electrode material.
- outer layer is meant a layer which does not constitute an internal layer of the electrode and which is the surface layer of the electrode (in contact with the electrolyte ).
- the outer layers do not consist of said porous layers of a DC current collector.
- the outer layers are intended to be in direct contact with the electrolyte of the rechargeable energy storage device and therefore, it is preferable that they are compatible with this electrolyte.
- this electrolyte contains, in solution, zinc ions.
- the electrolyte is incompatible with the electrically conductive materials composing the porous layers of the current collector.
- the latter are advantageously covered with active material (layer of ME electrode material) so as not to undergo preferential electrodeposition of zinc coming from the electrolyte and therefore, consequently, not to uncontrollably form a dendrite.
- the electrode has a total thickness ranging from strictly greater than 4 mm up to 6 mm.
- the present invention has the advantage of making it possible to achieve very large thicknesses of the electrode, while maintaining good physicochemical and electrochemical properties.
- a total thickness ranging from strictly greater than 4 mm up to 10 mm includes the following values or any interval between any one of these values: 4.5; 5; 5.5; 6; 6.5; 7; 7.5; 8; 8.5; 9; 9.5 and 10 mm.
- the porous layers of the DC current collector are identical or different and consist of layers of electroconductive material.
- the electrode is characterized in that at least part or each (all) of the porous layers of the DC current collector is in the form of a grid, a perforated sheet, of a felt, a mesh, a fabric, or a foam.
- the porous layers of the DC current collector are layers of metallic conductive material further comprising a metal M chosen from aluminum, copper, nickel, zinc, tin and a mixture of them.
- each of the layers of ME electrode material further comprises a polymer binder and optionally an agent conferring electronic conductivity or even additives.
- each of the layers of ME electrode material has a thickness ranging from 50 ⁇ m to 1 mm, preferably ranging from 100 ⁇ m to 500 ⁇ m.
- said electrode is in the form of an assembly of successive layers where each of the two outer layers of the electrode is a layer of ME electrode material, having the following structure: ME - [CC - ME] n or [ME - CC - ME] n
- ME is a layer of electrode material
- CC is a porous current collector layer
- "n" is a repeat pattern which is between 3 ⁇ n ⁇ 200, preferably between 3 ⁇ n ⁇ 100 and typically between 3 ⁇ n ⁇ 20.
- the characteristic "2 ⁇ n ⁇ 200" comprises the following values or any interval between any of these values: 2; 3; 4; 5; 6; 7; 8; 9; 10; 1 1; 12; 13; 14; 15; 16; 17; 18; 19; 20; 21; 25; 30 ; 35; 40; 45; 50; 55; 60; 65; 70; 75; 80; 85; 90; 95; 100; 105; 1 10; 1 15; 120; 125; 130; 135; 140; 145; 150; 155; 160; 165; 170; 175; 180; 185; 190; 195; 200.
- n is in particular a natural number.
- said electrode is in the form of an assembly of successive layers where at least one of said internal layers is an Ml impregnation layer comprising or consisting of an inert porous material (i.e. non-electrically conductive), with the proviso that when the electrode comprises two or more Ml impregnation layers, these are at least spaced 100 ⁇ m to 4 mm apart, preferably 300 ⁇ m to 3 mm, in particular from 500 ⁇ m to 2mm and ideally from 1 mm.
- each of the two outer layers of the electrode is a layer of ME electrode material and said electrode is in the form of an assembly of successive layers having the following structure:
- ME is a layer of electrode material
- CC is a porous current collector layer
- M1 is an impregnation layer
- n is such as defined above, namely a repeat unit which is between 2 ⁇ n ⁇ 200, preferably between 2 ⁇ n ⁇ 100, and typically between 2 ⁇ n ⁇ 20
- At least one of the two outer layers is / are a mechanical support and MMS separation layer comprising at least one inert material (ie: non-electrically conductive) suitable to or configured to allow circulation of the electrolyte and its ions.
- at least one inert material ie: non-electrically conductive
- the MMS layer can comprise or consist of at least one material which can be identical to the inert porous material of the Ml impregnation layer, namely comprise or consist of a polypropylene (PP) mesh, in polytetrafluoroethylene (PTFE) or any other equivalent porous material.
- PP polypropylene
- PTFE polytetrafluoroethylene
- said electrode is in the form of an assembly of successive layers having the following structure:
- ME is a layer of electrode material
- CC is a porous current collector layer
- Ml is an impregnation layer
- MMS is a mechanical maintenance and separation layer
- "n" is a repeating pattern which is between 2 ⁇ n ⁇ 200, preferably between 2 ⁇ n ⁇ 100 and typically between 2 ⁇ n ⁇ 20.
- said electrode is a positive or negative electrode.
- the electrode is a negative zinc-based electrode.
- the present invention also relates to an energy storage recharging device comprising at least: a positive electrode, a negative electrode and an electrolyte, said device being characterized in that at least the positive electrode or the negative electrode, preferably the negative electrode, is an electrode as defined above.
- the recharging device is an alkaline accumulator chosen from a battery whose negative electrode is zinc-based, such as a zinc-air battery and a zinc-nickel battery.
- the battery is a zinc-air battery.
- the present invention also relates to the use of an electrode as defined above, to improve the capacity of a rechargeable energy storage device.
- FIG. 1 is an electrode diagram according to an alternative embodiment, in which the electrode is in the form of an assembly of successive layers having the following structure: ME- [CC-ME] n where “ME” (hatched ) and “CC” (dotted) are as defined above and where “C n " corresponds to collector “n”, n corresponds to the number of repetitions of layer (s) of DC current collectors and layer (s ) of ME electrode material and E is the electrode;
- FIG. 2 is an electrode diagram according to another variant embodiment, in which the electrode is in the form of an assembly of successive layers having the following structure: ME - CC - [ME - Ml - ME - CC] n - ME where "ME” (hatched), “CC” (dotted), “E”, “Cn” and “n” are such that defined above and where “M1” corresponds to an impregnation layer;
- FIG. 3 is an electrode diagram according to another variant embodiment, in which the electrode is in the form of an assembly of successive layers having the following structure: MMS - ME - CC - [ME - Ml - ME - CC ] n - ME - MMS where "ME” (hatched), “CC” (dotted), “E”, “Ml”, “C n “ and “n” are as defined previously and where "MMS" corresponds to a mechanical support and separation layer,
- FIG. 4 is a graph showing the evolution of the mass of the electrode according to Example 1 in accordance with the invention (mass gain in%) as a function of its immersion time in deionized water (in minutes );
- FIG. 5 is a graph showing in "dotted line” the evolution of the mass of the electrode (weight gain in%) according to Example 2 (without layer of impregnation material M1) as a function of its dwell time. immersion in deionized water (in minutes); and in “continuous line” the evolution of the mass of the electrode (weight gain in%) according to Example 3 (with layer of impregnation material M1) in accordance with the invention as a function of the immersion time in deionized water (in minutes).
- the Applicant has focused on the development of a new electrode having an improved capacity compared to the electrodes of the prior art and this, while taking into account the technological constraints related in particular to the physicochemical properties of its materials forming the electrode and taking into account the internal resistance problems which may be present within it (difficulty in transferring the material) and which may lower its performance.
- the present invention relates to an electrode for a rechargeable energy storage device, comprising several internal layers interposed between two external layers, said internal layers comprising several layers of ME electrode material composed of 'at least one electrode active material and several porous DC current collector layers composed of electroconductive material (s) whose electronic conductivity is greater than or equal to 10 2 S. cm -1 , said layers of material d 'ME and DC current collector electrode being alternated, characterized in that said outer layers do not consist of said porous DC current collector layers, and in that said electrode has a total thickness ranging from strictly greater than 4 mm, preferably ranging from strictly greater than 4 mm up to 10 mm, in particular ranging from strictly greater than 4 mm up to 8 mm.
- the total thickness of the electrode ranges from strictly greater than 4 mm up to 6 mm.
- the Applicant has in fact developed a new electrode having a large storage capacity. By virtue of its characteristics and in particular its relatively large thickness, the electrode according to the invention indeed has excellent capacity.
- the electrode according to the invention is used for example as a negative electrode in a metal-air battery, such as zinc-air, in which the positive electrode has a fixed dimension (height x width), the relatively large thickness of the electrode according to the invention leads to better internal conductivity.
- the electrode according to the invention in fact has a large quantity of metal and a high number of conductors, making it possible to increase the collection and its energy density.
- the inventors of the present application have surprisingly discovered that the electrode structure as defined above is particularly suitable when the conductivity of the active material in the electrode material is low (ie ⁇ 10 1 S cnr 1 ) and / or that the thickness of the electrode within the device is not a limiting factor (eg stationary applications). It is also suitable for devices in which the transport of matter and charges in the electrolyte is not limiting (eg supercapacitors).
- the electrode according to the invention comprises in particular separate layers of ME electrode material and DC current collector which are alternated. These CC and ME layers will be described below.
- the porous layers of the DC current collector according to the invention are intended for or configured to ensure the electrical connection of the electrode with the external circuit. Their role is in fact to transport the electrons produced / received by the layers of electrode material ME to the outside of the system of the rechargeable energy storage device (battery).
- at least part or each of the porous layers of the DC current collector can be in the form of a grid, a perforated sheet, a felt, a mesh, d a fabric, foam, preferably open porosity foam.
- Each of the porous DC current collector layers of the electrode is preferably in the form of a grid. This allows an optimal active electrode volume to be obtained while ensuring minimum weight.
- the porous layers of the DC current collector are composed of or comprise materials whose electronic conductivity is good (ie.> 10 2 S. cm 1 ).
- the porous layers of a DC current collector which are identical or different, consist of layers of conductive material.
- the porous layers of the DC current collector can be chosen from non-metallic porous layers (conductive carbon felt type) or from metallic porous layers.
- the porous DC current collector layers are in particular layers of metallic conductive material such as a carbon fabric further comprising a metal M chosen from aluminum , copper, nickel, zinc, tin and one of their mixtures.
- the electrode may include porous DC current collector layers 1 comprising (or consisting of) a metal M 1 and porous collector layers of current CC 1 comprising (or consisting of) a metal M 1 ' , M 1 and M 1' being different and having the same definition as M.
- the thicknesses of the porous layers of the DC current collector can be identical or different.
- the entire surface of the porous layers of the DC current collector can be covered with a protective metallic layer.
- the metallic protective layers which may be identical or different, comprise (or consist of) a metal M 'chosen from lead, silver, tin, and a mixture thereof.
- the metallic protective layers make it possible to protect the porous layers of the DC current collector from possible corrosion, in particular when the electrolyte of the device is a basic aqueous electrolyte.
- each of the layers of ME electrode material comprises at least one active electrode material, and in general a polymer binder and optionally an agent conferring electronic conductivity.
- the active material is a positive electrode active material and when the electrode is intended to be a negative electrode, the active material is a negative electrode active material .
- the ME electrode material layers comprise the same electrode active material, in particular they are of identical compositions.
- the electrode is a zinc-based negative electrode.
- the active material of the layers of ME electrode material is preferably chosen from calcium zincate or a mixture of zinc oxide and calcium hydroxide or a mixture of zinc and sodium hydroxide. calcium.
- the polymeric binder of the layer of ME electrode material can be chosen from the polymeric binders known to those skilled in the art, in particular polyvinylidene fluoride (PVDF), carboxymethylcellulose (CMC), polytetrafluoroethylene (PTFE), polyvinyl alcohol (PVOH), poly (acrylic acid) (PAA), polyethylene glycol (PEO).
- PVDF polyvinylidene fluoride
- CMC carboxymethylcellulose
- PTFE polytetrafluoroethylene
- PVOH polyvinyl alcohol
- PAA poly (acrylic acid)
- PEO polyethylene glycol
- an agent conferring electronic conductivity can be chosen from electronic conductors known to those skilled in the art, in particular carbon compounds in all its forms (nanotubes, graphene oxides, submicron powders) , or else conductive ceramics such as titanium nitride and other metal oxides (silver oxide, bismuth oxide, etc.)).
- This agent conferring electronic conductivity has, in a known manner, the role of creating a percolating network of electronic conductivity, in particular by the transport of electrons within the layer of electrode material. Their use also has the effect of lowering the internal resistance of the layer of ME electrode material.
- the electronic conductivity of the agent conferring electronic conductivity is greater than or equal to 10 2 S cm 1 and preferably greater than or equal to 10 4 S. cm 1 .
- the polymer binder, the agent conferring electronic conductivity, are well known to those skilled in the art and will not be described in more detail below.
- each of the layers of ME electrode material has a thickness varying from about 50 ⁇ m to 1 mm, and preferably varying from about 100 ⁇ m to 500 ⁇ m.
- the Applicant has in fact discovered that the internal resistance of the electrode changes increasingly with the thickness of the layers of electrode material ME.
- the thinner this layer of ME the lower the internal resistance, which leads to better performance of the electrode.
- the thicknesses of the layers of ME electrode material can be identical or different, and are preferably identical.
- said electrode is in the form of an assembly of successive layers where each of the two outer layers of the electrode is a layer of ME electrode material, having the following structure:
- CC is a porous current collector layer
- "n" is a repeat pattern which is between 3 ⁇ n ⁇ 200, preferably between 3 ⁇ n ⁇ 100 and typically between 3 ⁇ n ⁇ 20.
- the "outer layers" of the electrode are each formed by a layer of ME electrode material and the DC current collector layer is interposed between two layers of electrode material.
- outer layer is meant a layer which does not constitute an internal layer of the electrode and which is the surface layer of the electrode.
- an “outer layer” does not constitute, according to this first variant embodiment, a layer of ME electrode material interposed between two porous layers of a DC current collector.
- the outer layer (s) may be formed from a layer of ME electrode material of an MMS mechanical support and separation layer.
- the outer layer / s of the electrode which is / are a layer / s of ME electrode material is / are preferably intended to be in contact with the electrolyte of the device .
- the number of DC current collector layers depends on the overall thickness of the electrode and the choice of the thickness of the layers of ME electrode material.
- the thickness of the electrode preferably varies from 4 to 10 mm, in particular from 4 to 8 mm and typically from 4 to 6 mm.
- each of the layers of ME electrode material has a thickness varying from approximately 50 ⁇ m to 1 mm, and preferably from approximately 100 ⁇ m to 500 ⁇ m.
- an electrode having a thickness ranging from 4 mm (not included) to 1 cm can have up to 200 layers of CC and 201 layers of ME, the layers of ME having a thickness ranging from 50 ⁇ m to 1 mm, preferably 100 ⁇ m at 500 ⁇ m; an electrode having a thickness ranging from 4 mm to 8 mm can have up to 160 layers of CC and 161 layers of ME, the layers of ME having a thickness ranging from 50 ⁇ m to 1 mm, preferably from 100 ⁇ m to 500 ⁇ m, and
- an electrode having a thickness ranging from 4 mm to 6 mm can have up to 120 layers of CC and 121 layers of ME, the layers of ME having a thickness ranging from 50 ⁇ m to 1 mm, preferably 100 ⁇ m to 500 ⁇ m.
- said electrode is in the form of an assembly of successive layers where at least one of said internal layers of the electrode according to the invention is an impregnation layer M1 comprising an inert porous (i.e. non-electrically conductive) material, provided that when the electrode comprises two or more M1 impregnation layers, these are at least spaced 100 ⁇ m to 2 mm apart, preferably 200 ⁇ m to 2 mm apart. pm to 1 mm, in particular 300 pm to 800 pm and most preferably 500 pm.
- M1 comprising an inert porous (i.e. non-electrically conductive) material
- the electrode according to the invention can comprise within its internal layers, one or more impregnation layers M1 made of inert porous material (namely non-electrically conductive).
- M1 layers allow in particular or are configured to allow the free circulation of the electrolyte through a sufficient open porosity.
- this inert impregnation material is electrochemically inactive, it necessarily decreases the energy density of the electrode.
- Ml based on the total weight of active material.
- the inert porous material (s) which can form an M1 layer can be chosen from polymer materials having good resistance properties with respect to the electrolyte. Also, the inert porous material (s) capable of forming an M1 layer can be chosen from polymeric materials having good hydrophilic properties, or having received a surface treatment making them hydrophilic (namely, hydrophobic to hydrophilic).
- the inert porous material (s) which can form an M1 layer have an open porosity ranging from 40% to 70%, preferably from 50% to 60% and typically from 53% to 55% measured according to conventional methods which apply to the field of porous materials, separators and other thin films.
- a porosity situated between 40% and 70% comprises the following values or any interval between these values: 40; 41; 42; 43; 44; 45; 46; 47; 48; 49; 50; 51; 52; 53; 54; 55; 56; 57; 58; 59; 60; 61; 62; 63; 64; 65; 66; 67; 68;
- the material which can form the M1 layer can correspond to the porous products sold by the company Freudenberg.
- the inert porous material (s) capable of forming an M1 layer meet the standards of compliance with EN 29073-03 in terms of absorption of aqueous electrolyte consisting of 30% potassium hydroxide.
- each layer of M1 has a thickness measured according to standard ISO 9073-2 ranging from 0.070 mm to 0.0130 mm, in particular from 0.090 mm to 0.120 mm and typically from 0.100 mm to 0.110 mm.
- the M1 layer (s) can be formed from a mesh-type fabric made of polytetrafluoroethylene (PTFE), polypropylene (PP), polyolephine (PO) or any other equivalent material.
- PTFE polytetrafluoroethylene
- PP polypropylene
- PO polyolephine
- each of the two outer layers of the electrode is a layer of ME electrode material and said electrode is in the form of an assembly of successive layers having the following structure :
- ME is a layer of electrode material
- CC is a porous current collector layer
- M1 is an impregnation layer
- n is a repeat pattern which is between 2 ⁇ n ⁇ 200, preferably between 2 ⁇ n ⁇ 100 and typically between 2 ⁇ n ⁇ 20.
- the two “outer layers” of the electrode are each formed by a layer of electrode material ME, as is also the case. case for the first variant embodiment.
- the layer M1 is alternately distributed according to the pattern
- the number of layers of M1 depends on the total thickness of the electrode.
- an electrode having a thickness ranging from 4 mm (not included) to 1 cm can have 5 to 200 layers of CC and 6 to 201 layers of ME, and from 1 to 16 layers of Ml the layers of ME having a thickness ranging from 50 ⁇ m to 1 mm, preferably 100 ⁇ m to 500 ⁇ m ..;
- an electrode having a thickness ranging from 4 mm to 8 mm can have 5 to 160 layers of CC and 6 to 161 layers of ME, and from 1 to 80 layers of M1 the layers of ME having a thickness ranging from 50 ⁇ m to 1 mm, preferably 100 ⁇ m to 500 ⁇ m; and an electrode having a thickness ranging from 4 mm to 6 mm can have 5 to 120 layers of CC and 5 to 121 layers of ME, and from 1 to 60 layers of Ml the layers of ME having a thickness ranging from 50 ⁇ m to 1 mm, preferably 100 ⁇ m to 500 ⁇ m.
- the electrode can be characterized in that at least one of the two outer layers, preferably both, is / are a mechanical support layer and MMS separation comprising at least one inert material suitable for or configured to allow the circulation of the electrolyte and its ions.
- the MMS layer is adapted in order to circulate the electrolyte of the energy storage device and can therefore be considered as “ionic conductor” because it is capable of allowing the ions of the electrolyte to circulate, ie in a manner physical by its porosity, or by other mechanisms, of the diffusion / migration type, if the layer is uniform and non-porous.
- it is not electrically conductive because it does not conduct electrons.
- the MMS layer can comprise or consist of at least one material which can be identical or different to the inert porous material of the M1 impregnation layer, namely comprising or consisting of:
- porous materials such as a mesh made of PP, PTFE or any other equivalent porous material;
- non-porous materials such as polyvinyl alcohol (PVOH), Nafion®, ion exchange membranes or any other ionically conductive material.
- PVH polyvinyl alcohol
- Nafion® Nafion®
- ion exchange membranes any other ionically conductive material.
- the MMS layer has a porosity of less than or equal to 20%, preferably less than or equal to 10% and typically less than or equal to 5%.
- a porosity less than or equal to 20% includes the following values or any interval between these values: 0; 1; 2; 3; 4; 5; 6; 7; 8; 9; 10; 1 1; 1 2; 13; 14; 15; 16; 17; 18; 19; 20.
- the MMS layer can be prepared by a physical deposition of the immersion, spray, brush application or any other technique making it possible to apply the material constituting the MMS layer in its dissolved form in a suitable or pure solvent.
- this variant embodiment can be combined with the first or the second variant embodiment, namely the MMS layers can coat the layers of electrode material ME forming the outer layers of these embodiments and be combined or not with one or more layers Ml.
- said electrode is in the form of an assembly of successive layers having the following structure:
- ME is a layer of electrode material
- CC is a porous current collector layer
- M1 is an impregnation layer
- MMS is a mechanical holding and separation layer
- "n" is a repeating unit which is between 2 ⁇ n ⁇ 200, preferably between 2 ⁇ n ⁇ 100 and typically between 2 ⁇ n ⁇ 20.
- the MMS layers encompass the entire electrode, therefore making it possible to separate the electrode (for example the negative electrode) from the second electrode of the energy storage device (for example positive electrode). These two outer MMS layers also function to improve the overall mechanical hold of the electrode.
- each layer of MMS has a thickness ranging from 20 ⁇ m to 150 ⁇ m, in particular from 20 to 70 ⁇ m and typically from 25 to 60 ⁇ m.
- the electrode can be a positive or negative electrode.
- the electrode is a negative electrode, preferably zinc-based.
- the electrode in accordance with the present invention can be easily manufactured by any type of method making it possible to apply a layer of electrode material in the form of an ink or a paste comprising at least one active material of positive or negative electrode, at least one solvent, optionally at least one polymer binder and optionally an agent conferring electronic conduction, on a porous layer of a DC current collector.
- a layer of electrode material in the form of an ink or a paste comprising at least one active material of positive or negative electrode, at least one solvent, optionally at least one polymer binder and optionally an agent conferring electronic conduction, on a porous layer of a DC current collector.
- coating dipping, spraying ("spray"), printing, calendering etc.
- the invention also relates to an energy storage recharging device comprising at least: a positive electrode, a negative electrode, and an electrolyte, said device being characterized in that at least the positive electrode or the negative electrode, preferably the negative electrode, is an electrode as defined above.
- an “electrolyte” is any liquid or solid substance allowing the passage of electric current by ionic displacement.
- the electrolyte is in direct contact with the electrode as defined above via the external layer which can be a layer of ME electrode material. or an MMS layer of said electrode.
- the electrolyte of the device is not in direct contact with the porous layers of the DC current collector of the electrode as described above. This thus makes it possible to avoid, or at least reduce, the formation of dendrites, and to avoid a short circuit within the device.
- the porous layers of the DC current collector being very conductive, their direct contact with the electrolyte can lead, from the first charge, to an unsaturation of the electrolyte and an increase in the thickness of the electrode, inducing the formation of dendrites, perforation of the separator and possibly a short circuit after 1 or 2 cycles.
- the device may further comprise at least one glassy carbon element in direct contact with the other of the two outer layers of the electrode, and in particular with the outer layer intended to ensure the electrical connection of the electrode with the electrode. outdoor circuit. Therefore, the electrical connection of the electrode with the external circuit is made through said element. This thus avoids any contact between said other of the two outer layers of the electrode and the electrolyte within the device.
- the device may in particular be chosen from an alkaline accumulator, a lithium-ion battery, a lead-acid battery, a metal hydride-nickel or Ni-MH battery (standing for “nickel-metal hydride”) and a supercapacitor .
- the electrolyte can be liquid, gelled or solid.
- the device is an alkaline accumulator chosen from a battery whose negative electrode is zinc-based, such as a zinc-air battery and a zinc-nickel battery
- the alkaline accumulator is defined as a rechargeable energy storage device comprising: at least one positive electrode, at least one negative electrode, a liquid electrolyte, and one or more porous separators.
- the negative electrode of the device is a zinc-based electrode as defined above.
- the positive electrode may be a nickel-based electrode, in particular comprising, as active material, nickel (III) oxide (NiOOH), nickel (II) hydroxide. ) (Ni (OH) 2, or a mixture thereof.
- the porous separator can be a porous material which is not electronically conductive, generally a polymer material based on polyolefin (e.g. polyethylene) or made of fibers (e.g. glass fibers or wood fibers, cellulosic fibers).
- polyolefin e.g. polyethylene
- fibers e.g. glass fibers or wood fibers, cellulosic fibers
- the electrode according to the first object of the invention can include edges (upper, lower or circular) intended to ensure the electrical connection with the external circuit. These edges can then be covered with an insulating material, such as polytetrafluoroethylene (PTFE). This thus makes it possible to isolate, within the device, the parts of the electrode which are not intended to be in contact with the electrolyte.
- PTFE polytetrafluoroethylene
- the device according to the invention can easily be assembled by any technique known to those skilled in the art.
- Another subject of the present invention is the use of an electrode as defined above, to improve the capacity of a rechargeable energy storage device.
- Table 1 illustrates the various tests carried out by the Applicant.
- a preliminary step is carried out. This step involves preparing an aqueous ink to form the different layers of ME electrode material.
- This aqueous ink represents the mixture of the ME electrode material.
- the homogeneous mixture is applied as a uniform layer deposited on the surface of a non-stick support using a coating scraper whose height is adjustable to 50 ⁇ m precision.
- the height of the first coating is determined at 1500 ⁇ m of ink.
- a current collector in the form of a DC copper grid is applied to the surface of this first layer, a current collector in the form of a DC copper grid, previously cut with respect to the desired dimensions for the final surface of the electrode (100 cm 2 ).
- a second layer of ink is applied on which is deposited a second current collector in the form of a copper grid, positioned strictly parallel to the previous DC current collector.
- the process is repeated until the thickness and number of layers is reached. desired. For this example 1, this action is repeated 7 times.
- the coating heights namely the height of ink deposited per layer and the cumulative height of ink, are listed in the following table 4:
- Example 1 has the particularity of having the 1st and last layers of 1500 ⁇ m plaster and internal 700 ⁇ m plaster layers. This example 1 thus takes the form of an assembly of successive layers having the following structure:
- the wet assembly of electrode material namely ink
- DC current collectors is dried in an enclosure thermostatically controlled at 35 ° C. for 24 to 48 hours. Once dry, the raw electrode is recovered and then immersed for 2 h in deionized water at room temperature. As PVA and PTFE maintain their binding properties, the raw electrode does not disintegrate and remains in the form of the same block. Once hydrated, the electrode of Example 1 is carefully cut to the desired dimensions (100 cm 2 ) so that there is no DC current collector protruding from the edges of the electrode. An 8 ton press is applied to the wet electrode. The electrode is then dried under stress, in order to avoid detachment of the layers by contraction of the polymer material. To proceed with the drying, a vacuum chamber is used for this example 1.
- the electrode of Example 1 is an electrode 4.5 mm thick and with a capacity of 20.0 Ah for an area of 100 cm 2 .
- a nickel or nickel-plated steel BUS is applied to the electrode head by spot welding in order to group together all the current collectors in a single electrode head.
- the electrode head is then covered with a PTFE sealing tape.
- the electrode of this example 1 is subjected to an impregnation test in order to determine the time it takes for the latter to be able to start a possible electrochemical test in the context of the use of this type of electrode in a system. real.
- the electrode according to Example 1 exhibits a high impregnation rate and therefore an excellent capacity for assimilating aqueous electrolyte.
- aqueous ink containing 45% of solid matter, is prepared according to the proportions summarized in Table 3 above (Example 1).
- This aqueous ink represents the mixture of the ME electrode material.
- the homogeneous mixture is applied as a uniform layer deposited on the surface of a non-stick support using a coating scraper whose height is adjustable to 50 ⁇ m precision.
- a single coating of 2000 ⁇ m is applied until the ink is completely exhausted so as to obtain several wet coatings.
- These wet plasters are then dried in a thermostatically controlled chamber at 35 ° C. for 24 h.
- the dry raw plasters thus obtained are then re-impregnated with deionized water, then cut to the desired dimensions so as to obtain wet plasters.
- the coatings are cut according to the dimensions 60 x 40 mm.
- the wet plasters are assembled with layers of DC current collectors, then subjected to a 2 T press.
- the electrode is then dried under stress, in order to prevent the layers from detaching by contraction of the polymer material.
- a vacuum chamber is used for Example 2.
- the electrode of Example 2 is an electrode 8.0 mm thick and with a capacity of 12 Ah for a surface area of 27 cm 2 .
- a nickel or nickel-plated steel BUS is applied at the electrode head by spot welding in order to group together all the current collectors in a single electrode head.
- the electrode head is then covered with a PTFE sealing tape.
- Example 2 The electrode of Example 2 is subjected to an impregnation test in order to determine the time that the latter takes before being able to start a possible electrochemical test within the framework of the use of this type of electrode in real system. Impregnation is carried out by complete immersion of the electrode in deionized water and the result obtained for this electrode is shown in Fig. 5.
- aqueous ink containing 45% of solid matter, is prepared according to the proportions summarized in Table 3 above (Example 1).
- This aqueous ink represents the mixture of the ME electrode material.
- the homogeneous mixture is applied as a uniform layer deposited on the surface of a non-stick support using a coating scraper whose height is adjustable to 50 ⁇ m precision. For example, a single coating of 2000 ⁇ m is applied until the ink is completely exhausted.
- the wet plasters are dried in an enclosure thermostatically controlled at 35 ° C. for 24 hours.
- the raw, dry plasters are then re-impregnated with deionized water and then cut to the desired dimensions. For this example 3, the coatings are cut according to the dimensions 60 x 40 mm.
- the wet plasters are assembled with layers of current collectors as well as layers of impregnation material before being subjected to a 2 T press.
- the electrode of Example 3 is an electrode 8.0 mm thick and with a capacity of 12 Ah for an area of 27 cm 2 .
- a nickel or nickel-plated steel BUS is applied at the electrode head by spot welding in order to group together all the current collectors in a single electrode head. The electrode head is then covered with a PTFE sealing tape.
- the electrode of example 3 is subjected to an impregnation test in order to determine the time that the latter takes before being able to start a possible electrochemical test in the context of the use of this type of electrode in real system. Impregnation is carried out by complete immersion of the electrode in deionized water and the result obtained for this electrode is shown in Fig. 5.
- This Fig.5 thus shows that the electrodes according to Examples 2 and 3 exhibit excellent capacity (high impregnation speed), but that this is improved when the electrode comprises Ml impregnation layers (example 3).
- aqueous ink containing 45% of solid matter, is prepared according to the proportions summarized in Table 3 above (Example 1).
- This aqueous ink represents the mixture of the ME electrode material.
- the homogeneous mixture is applied as a uniform layer deposited on the surface of a non-stick support using a coating scraper whose height is adjustable to 50 ⁇ m precision. For this example 4, a single coating of 2000 ⁇ m is applied until the ink has run out.
- the wet plasters are dried in an enclosure thermostatically controlled at 35 ° C. for 24 hours.
- the raw, dry plasters are then re-impregnated with deionized water, then cut to the desired dimensions.
- the plasters are cut according to the dimensions 60 x 40 mm.
- the wet plasters are assembled with layers of current collectors and then subjected to a 2 T press. The assembly is then dried under stress, in order to prevent the layers from detaching by contraction of the polymeric material. To proceed with the drying, a vacuum chamber is used for this example 4.
- the electrode of Example 4 is an electrode 8.0 mm thick and with a capacity of 12 Ah for a surface area of 27 cm 2 .
- the assembly is then immersed in a PVA solution before being left to dry in a vertical position and at room temperature for 1 night.
- the PVA solution is at a concentration of 10% by mass.
- a nickel or nickel-plated steel BUS is applied at the electrode head by spot welding in order to group together all the current collectors in a single electrode head.
- the electrode head is then covered with a PTFE sealing tape.
- aqueous ink containing 45% of solid matter, is prepared according to the proportions summarized in Table 3 above (Example 1).
- This aqueous ink represents the mixture of the ME electrode material.
- the homogeneous mixture is applied in the form of a uniform layer deposited on the surface of a non-stick support using a coating doctor whose height is adjustable to 50 ⁇ m with precision. For this example 5, a single coating of 2000 ⁇ m was applied until the ink was completely exhausted.
- the wet plasters are dried in an enclosure thermostatically controlled at 35 ° C. for 24 hours. The raw dry plasters are then re-impregnated with deionized water and then cut to the desired dimensions. For this example 5, the plasters are cut according to the dimensions 60 x 40 mm.
- the wet plasters are assembled with layers of current collectors as well as layers of impregnation material before being subjected to a 2 T press.
- the assembly is then dried under stress, in order to avoid detachment of the layers by contraction of the polymer material.
- a vacuum chamber is used for this example 5.
- a measurement of the weight of the assembly makes it possible to determine, by subtracting the copper and other inactive materials, the capacity of the electrode.
- the electrode of this example 5 is an electrode 8.0 mm thick and with a capacity of 12 Ah for a surface of 27 cm 2 .
- the assembly is then immersed in a PVA solution before being left to dry in a vertical position and at room temperature for 1 night.
- a nickel or nickel-plated steel BUS is applied at the electrode head by spot welding in order to group together all the current collectors in a single electrode head.
- the electrode head is then covered with a PTFE sealing tape.
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Abstract
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Application Number | Priority Date | Filing Date | Title |
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FR1902150A FR3093380B1 (fr) | 2019-03-01 | 2019-03-01 | Électrode pour dispositif de stockage de l’énergie rechargeable |
PCT/FR2020/050395 WO2020178509A1 (fr) | 2019-03-01 | 2020-02-27 | Électrode pour dispositif de stockage de l'énergie rechargeable |
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US (1) | US20220149356A1 (fr) |
EP (1) | EP3931892A1 (fr) |
JP (1) | JP2022525730A (fr) |
KR (1) | KR20210133969A (fr) |
CN (1) | CN113474920B (fr) |
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JP5051988B2 (ja) * | 2005-07-29 | 2012-10-17 | 三洋電機株式会社 | 電極の製造方法、その製造方法に用いる電極の製造装置、及び当該電極の製造方法により製造された電極を用いた電池 |
CN101960653B (zh) * | 2008-10-08 | 2013-03-13 | 松下电器产业株式会社 | 负极及其制造方法和非水电解质二次电池 |
EP2474037A2 (fr) * | 2009-09-03 | 2012-07-11 | Molecular Nanosystems Inc. | Procédés et systèmes de fabrication d'électrodes possédant au moins un gradient fonctionnel, et dispositifs en résultant |
EP2709770A4 (fr) * | 2011-05-19 | 2014-12-03 | Univ Northeastern | Électrode à base de nanotubes de carbone et batterie rechargeable |
JP5942549B2 (ja) * | 2012-04-02 | 2016-06-29 | ソニー株式会社 | 空気電池、空気電池の使用方法および電子機器 |
US9692056B1 (en) * | 2012-04-13 | 2017-06-27 | Amprius, Inc. | Dual current collectors for battery electrodes |
CN106469825B (zh) * | 2015-08-21 | 2019-03-29 | 北京好风光储能技术有限公司 | 一种高功率大容量锂离子电池及其制备方法 |
US10361460B2 (en) * | 2015-10-02 | 2019-07-23 | Nanotek Instruments, Inc. | Process for producing lithium batteries having an ultra-high energy density |
JP6573682B2 (ja) * | 2015-12-24 | 2019-09-11 | 日本碍子株式会社 | 電極積層体及びそれを用いたニッケル亜鉛電池 |
JP6686789B2 (ja) * | 2016-08-16 | 2020-04-22 | トヨタ自動車株式会社 | 積層型アルカリ二次電池 |
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FR3093380B1 (fr) | 2021-03-12 |
CN113474920A (zh) | 2021-10-01 |
WO2020178509A1 (fr) | 2020-09-10 |
JP2022525730A (ja) | 2022-05-19 |
KR20210133969A (ko) | 2021-11-08 |
US20220149356A1 (en) | 2022-05-12 |
CN113474920B (zh) | 2023-12-29 |
FR3093380A1 (fr) | 2020-09-04 |
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