Electrochemical accumulator with bipolar architecture including a specific structure

Patent metadata

Field	Value
Publication number	US-12412899-B2
Application number	US-201917258855-A
Country	US
Kind code	B2
Filing date	Jul 10, 2019
Priority date	Jul 11, 2018
Publication date	Sep 9, 2025
Grant date	Sep 9, 2025

Abstract

An accumulator with a bipolar architecture that comprises two terminal current collectors, between which a stack of n electrochemical cells is disposed, with n being an integer at least equal to 2, wherein: —each electrochemical cell comprises a positive electrode, a negative electrode and an ion conducting membrane that is interposed between the positive electrode and the negative electrode and comprises a liquid electrolyte included in the electrodes and the ion conducting membrane; —the n electrochemical cells are separated from each other by n−1 bipolar current collectors; wherein the positive electrode and the negative electrode of each electrochemical cell are gel electrodes comprising a composite material comprising a polymeric matrix made of at least one gelling polymer (FF), an active electrode material and optionally one or more electronic conductive additives, the polymeric matrix trapping the liquid electrolyte.

First claim

What is claimed is:

1. An accumulator with bipolar architecture that comprises two end current collectors between which a stack of n electrochemical cells is disposed, n being an integer at least equal to 2, wherein:
each electrochemical cell comprises a positive electrode, a negative electrode, and an ion-conducting membrane that is interposed between the positive electrode and the negative electrode and comprises a liquid electrolyte included in the positive electrode, the negative electrode, and the ion-conducting membrane;
the n electrochemical cells are separated from each other by n−1 bipolar current collector(s);
and wherein the positive electrode and the negative electrode of each electrochemical cell are gelled electrodes each comprising a composite material comprising a polymer matrix made from at least one gelling polymer (FF), an active electrode material and optionally one or more electron-conducting additives, the polymer matrix trapping the liquid electrolyte, the at least one gelling polymer (FF) being chosen from fluorinated polymers comprising at least one repeating unit issuing from polymerization of a fluorinated monomer and at least one repeating unit issuing from polymerization of a monomer comprising at least one carboxylic acid group, optionally in the form of a salt,
wherein the bipolar current collector(s) and at least one of the end current collectors have at least one face, which accommodates the positive electrode or the negative electrode and which comprises, at a periphery thereof:
at least one free edge of the bipolar current collector(s) not occupied by the positive electrode or negative electrode, and
at least one tongue of the at least one end current collector, which is in contact with the at least one end current collector or extending the same,
the at least one free edge and/or the at least one tongue being metal parts each covered by a layer of insulating material positioned to avoid a direct contact between the metal parts of the bipolar current collector(s) and of the end current collector(s) situated opposite each other, the layer of insulating material not forming an impervious seal to the liquid electrolyte, and
wherein each electrochemical cell is devoid of a physical barrier to the flow of the liquid electrolyte.

2. The accumulator according to claim 1 , wherein the at least one repeating unit issuing from the polymerization of a fluorinated monomer issues from the polymerization of at least one ethylenic monomer comprising at least one fluorine atom, from the at least one ethylenic monomer being chosen from:
C 2 -C 8 perfluoroolefins;
C 2 -C 8 hydrogenated fluoroolefins;
perfluoroalkylethylenes of formula CH 2 =CHR 1 , wherein R 1 is a C 1 -C 6 perfluoroalkyl group;
C 2 -C 6 fluoroolefins including one or more other halogen atoms;
(per) fluoroalkylvinylethers of formula CF 2 =CFOR 2 , wherein R 2 is a C 1 -C 6 fluoro- or perfluoroalkyl group;
monomers of formula CF 2 =CFOR 3 , wherein R 3 is a C 1 -C 12 alkyl group, a C 1 -C 12 alkoxy group or a C 1 -C 12 (per) fluoroalkoxy group; and/or
monomers of formula CF 2 =CFOCF 2 OR 4 , wherein R 4 is a C 1 -C 6 fluoro- or perfluoroalkyl group, or a C 1 -C 6 fluoro- or perfluoroalkoxy group.

3. The accumulator according to claim 1 , wherein the at least one gelling polymer (FF) comprises, as repeating units issuing from the polymerisation of a fluorinated monomer, a repeating unit issuing from the polymerization of a monomer in the category of C 2 -C 8 perfluoroolefins, and a repeating unit issuing from the polymerization of a monomer in the category of C 2 -C 8 hydrogenated fluoroolefins.

4. The accumulator according to claim 1 , wherein the at least one repeating unit issuing from the polymerization of a monomer comprising at least one carboxylic acid group, optionally in the form of a salt, issues from the polymerization of a monomer of the following formula (I):

wherein R 5 to R 7 represent, independently of each other, a hydrogen atom or a C 1 -C 3 alkyl group, and R 8 represents a hydrogen atom or a monovalent cation.

5. The accumulator according to claim 1 , wherein the at least one gelling polymer (FF) is a polymer comprising a repeating unit issuing from polymerization of vinylidene fluoride, a repeating unit issuing from polymerization of said monomer comprising at least one carboxylic acid group, and optionally a repeating unit issuing from the polymerization of a fluorinated monomer different from vinylidene fluoride.

6. The accumulator according to claim 1 , wherein the liquid electrolyte is trapped in the ion-conducting membrane and is an ion-conducting electrolyte comprising at least one organic solvent, at least one metal salt and optionally a compound in the family of vinyl compounds.

7. The accumulator according to claim 6 , wherein the at least one organic solvent is a carbonate solvent.

8. The accumulator according to claim 6 , wherein the at least one metal salt is chosen from the salts with the following formulae: Mel, Me (PF 6 ) n , Me(BF 4 ) n , Me(ClO 4 ) n , Me(bis(oxalato)borate) n , MeCF 3 SO 3 , Me[N(FSO 2 ) 2 ] n , Me[N(CF 3 SO 2 ) 2 ] n , Me[N(C 2 F 5 SO 2 ) 2 ] n , Me[N(CF 3 SO 2 )(RFSO 2 )] n , wherein R F is a —C 2 F 5 , —C 4 F 9 or —CF 3 OCF 2 CF 3 , Me(AsF 6 ) n , Me[C(CF 3 SO 2 ) 3 ] n , Me 2 Sn, Me(C 6 F 3 N 4 ) group, wherein Me is a metal element and n corresponds to the degree of valency of the metal element.

9. The accumulator according to claim 1 , wherein the ion-conducting membrane comprised in each electrochemical cell comprises an organic part comprising at least one fluorinated polymer (F) comprising at least one membrane repeating unit issuing from the polymerization of a fluorinated monomer and at least one membrane repeating unit issuing from the polymerization of a monomer comprising at least one hydroxyl group, optionally in the form of a salt, and comprises an inorganic part formed, at least partly, by one or more oxides of at least one element M chosen from Si, Ti and Zr and the combinations thereof.

10. The accumulator according to claim 9 , wherein the at least one membrane repeating unit issuing from the polymerization of a fluorinated monomer issues from the polymerization of one or more ethylenic monomers comprising at least one fluorine atom chosen from:
C 2 -C 8 perfluoroolefins;
C 2 -C 8 hydrogenated fluoroolefins;
perfluoroalkylethylenes of formula CH 2 =CHR 1 , wherein R 1 is a C 1 -C 6 perfluoroalkyl group;
C 2 -C 6 fluoroolefins including one or more other halogen atoms;
(per) fluoroalkylvinylethers of formula CF 2 =CFOR 2 , wherein R 2 is a C 1 -C 6 fluoro- or perfluoroalkyl group;
monomers of formula CF 2 =CFOR 3 , wherein R 3 is a C 1 -C 12 alkyl group, a C 1 -C 12 alkoxy group or a C 1 -C 12 (per) fluoroalkoxy group; and/or
monomers of formula CF 2 =CFOCF 2 OR 4 , wherein R 4 is a C 1 -C 6 fluoro- or perfluoroalkyl group, or a C 1 -C 6 fluoro- or perfluoroalkoxy group.

11. The accumulator according to claim 9 , wherein the fluorinated polymer (F) comprises, as membrane repeating units issuing from the polymerization of a fluorinated monomer:
a repeating unit issuing from the polymerization of a monomer in the category of C 2 -C 8 perfluoroolefins and a repeating unit issuing from the polymerization of a monomer in the category of C 2 -C 8 hydrogenated polyolefins.

12. The accumulator according to claim 9 , wherein the at least one membrane repeating unit issuing from the polymerisation of a monomer comprising at least one hydroxyl group, optionally in t

Assignees

• Commissariat Energie Atomique
• Solvay France

Inventors

• Mourzagh Djamel
• Abusleme Julio
• Besnard Gaëlle
• Braida Marc-David
• Gutel Elise
• Rouault Hélène
• Tomasi Daniel

Classifications

• Y02E60/10

  Energy storage using batteries · CPC title

• H01M2300/0091

  in the form of mixtures · CPC title

• H01M2300/0085

  Immobilising or gelification of electrolyte · CPC title

• H01M10/0585 Primary

  of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators · CPC title

• H01M10/0569

  characterised by the solvents · CPC title