# US 5,350,646 A · Ionically conductive polymeric materials

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- Number: US 5,350,646 A
- Document ID: US5350646A
- Status: Granted
- Kind: A
- Application number: 07/945,639
- Filed: 1992-11-06
- Granted: 1994-09-27
- Earliest claimed: 1991-03-07
- Assignees: Centre National De La Recherche Scientifique; Hydro-Quebec
- Inventors: Michel Armand; Jean-Yves Sanchez; Daniel Deroo
- Web page: https://patentgrep.com/patent/US5350646A

## CPC

- H01M 6/166: {by the solute}
- C08G 75/32: Polythiazoles; Polythiadiazoles
- C08G 79/025: Polyphosphazenes
- H01B 1/122: {Ionic conductors}
- H01M 6/181: {with polymeric electrolytes}
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- H01B: CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES (selection for magnetic properties H01F1/00; waveguides H01P {; printed circuits H05K})

## Abstract

The present invention relates to ionically conductive polymeric materials, to their preparation and to their use as a solid electrolyte. The materials comprise a solid solution of one or more salts in a polymer and are characterized in that the transport and the mobility of a metal cation M.sup.n+ which has the valency n, 1.ltoreq.n.ltoreq.5, are provided by at least one complex anion, corresponding to the general formula [MZ.sub.n Y.sub.p ].sup.p- formed between an anionic ligand Z.sup.-, an anionic ligand Y.sup.- and the cation M.sup.n+, with 1.ltoreq.p.ltoreq.3. Application to the formation of electrochemical generators and of electrochemical systems which make it possible to affect the transmission of light.

## Claims

### Claim 1

Ionically conductive material comprising a solid solution of one or more salts in a polymer, characterized in that the polymer has a framework wherein the solvating units contain at least one heteroatom selected from the group consisting of O, N, F, and S, and that the transport and the mobility of a metal cation M.sup.n+ which has the valency n are provided by at least one complex anion corresponding to the general formula (MZ.sub.n Y.sub.p).sup.p-, wherein M is the same metal in M.sup.n+, formed between an anionic ligand Z.sup.-, an anionic ligand Y.sup.- and the cation M.sup.n+, and wherein 1.ltoreq.n.ltoreq.5, and 1.ltoreq.p.ltoreq.3.

### Claim 2 (depends on 1)

Material according to claim 1, characterized in that the solid solution is a polymeric complex denoted by the overall formula
Poly(s.u.).sub.u A(M.sub.x Z.sub.z Y.sub.y)
in which
A is a cation of valency p, with p=1 or 2;
(s.u.) denotes the solvation unit of the polymer;
u denotes the number of solvation units carried by the macromolecular framework which are needed for solvating a cation A;
x, y and z are such that the relationship z+y-nx=p is satisfied and that they permit the coexistence, in finite quantities, of the complex anion (MZ.sub.n Y.sub.p).sup.p- and of a species chosen from the group consisting of the anion Z.sup.-, the anion Y.sup.-, the complex anion (MZ.sub.n Y.sub.p+1).sup.p+1 , the complex anion (MZ.sub.n+1 Y.sub.p).sup.p+1 and the neutral species MZ.sub.n.

### Claim 3 (depends on 2)

Material according to claim 2, characterized in that the cation A is chosen from alkali metals, alkaline-earth metals, quaternary ammonium radicals corresponding to the formula NH.sub.(4-j) R.sub.j.sup.+, amidinium radicals corresponding to the formula RC(NH.sub.2-j R.sub.j).sub.2.sup.+, guanidinium radicals corresponding to the formula C(NH.sub.2-j R.sub.j).sub.3.sup.+, with j=0, 1 or 2, R being chosen from hydrogen and an alkyl, oxaalkyl or aryl group.

### Claim 4 (depends on 1)

Material according to claim 1, characterized in that the cation M.sup.n+ is a cation derived from an element chosen from Li, Mg, Ca, St, Mn, Fe, Ni, Co, Cu(I), Cu(II), Ag, Zn, Cd, Al, Sn(II), Sn(IV), Bi, Hg, Pb, Y and the rare earths.

### Claim 5 (depends on 1)

Material according to claim 1, characterized in that Z.sup.- and Y.sup.-, which are identical or different, are chosen from:
F.sup.-, Cl.sup.-, Br.sup.-, I.sup.- ;
pseudohalogens corresponding to the formula Qs.sup.- ;
the radicals R.sub.F CO.sub.2.sup.-, (R.sub.F CO).sub.2 N.sup.-, (R.sub.F CO).sub.2 CQ.sup.-, R.sub.F COCQ.sub.2.sup.-, QCOC(CN).sub.2.sup.-, (R.sub.F CO).sub.2 CSO.sub.2 R.sub.F.sup.-, (R.sub.F CO).sub.2 CSO.sub.2 NR.sub.2.sup.-, R--(OCH.sub.2 CH.sub.2).sub.j --CH.sub.2 COC(CN).sub.2.sup.- ;
sulfonamides QN(SO.sub.2 R.sub.F).sup.- ;
Q denoting CN, R, RCO, R.sub.2 NCO, R.sub.2 NCS, R.sub.F, R.sub.F CO or a heterocyclic ring, R.sub.F denoting a perhaloalkyl or perhaloaryl radical, R denoting an alkyl, oxaalkyl or aryl radical.

### Claim 6 (depends on 1)

Materials according to claim 1, characterized in that Z and Y denote a multiradical, simultaneously or otherwise.

### Claim 7 (depends on 6)

Material according to claim 6, characterized in that the multiradical is a biradical denoted by the formula --(R.sub.F SO.sub.2)NQ'N(SO.sub.2 R.sub.F).sup.-, in which Q' denotes a bivalent radical carrying at least one functional group chosen from CN, R, RCO, R.sub.2 NCO, R.sub.2 NCS, R.sub.F, R.sub.F CO or a heterocyclic ring, R.sub.F denoting a perhaloalkyl or perhaloaryl radical, R denoting an alkyl, oxaalkyl or aryl radical.

### Claim 8 (depends on 1)

Material according to claim 1, characterized in that the solvation unit of the polymeric framework is an ether group or an amine group.

### Claim 9 (depends on 8)

Material according to claim 8, characterized in that the polymeric framework consists of a homopolymer, a block copolymer, a random copolymer, an alternating copolymer or an ethylene oxide copolymer with a comb structure.

### Claim 10 (depends on 1)

Material according to claim 1, characterized in that it contains additives chosen from salts of anions which cannot form a ligand for the ion M.sup.n+ and from plasticizing agents.

### Claim 11 (depends on 1)

Process for the preparation of a material according to claim 1, characterized in that a salt AY.sub.p and a salt MZ.sub.n are dissolved in a solvating polymer, in proportions such that the relationship z+y-nx=p is satisfied and that they permit the coexistence, in finite quantities, of the complex anion (MZ.sub.n Y.sub.p).sup.p- and of a species chosen from the group consisting of the anion Z.sup.-, the anion Y.sup.-, the complex anion (MZ.sub.n Y.sub.p+1).sup.(p+1 ) and the neutral species MZ.sub.n.

### Claim 12 (depends on 11)

Process according to claim 11, characterized in that the salts and the polymer are dissolved in a common liquid solvent which is then evaporated.

### Claim 13 (depends on 12)

Process according to claim 12, characterized in that the polymer is crosslinked in situ.

### Claim 14 (depends on 11)

Process according to claim 11, characterized in that the polymer is precrosslinked and impregnated with a solution of salt in an organic solvent, this solvent being removed after the impregnation.

### Claim 15 (depends on 11)

Process according to claim 11, characterized in that the salts are dissolved in the polymer in dry state by grinding.

### Claim 16 (depends on 1)

Electrochemical generator, characterized in that it comprises as electrolyte a material according to claim 1.

### Claim 17 (depends on 16)

Generator according to claim 16, characterized in that it comprises a "source" negative electrode of the metal M with a high chemical potential, a positive electrode or "well" establishing a low chemical potential of M, the two electrodes being in contact through the intermediacy of the electrolyte.

### Claim 18 (depends on 16)

Electrochemical generator according to claim 16, characterized in that at least one of the electrodes has a composite structure including an electrochemically active material, an electronically conductive material and the material forming the electrolyte.

### Claim 19 (depends on 1)

Electrochemical system which makes it possible to affect the transmission of light, comprising a counterelectrode, an electrolyte, and a transparent electrode used as substrate for the electrochemical deposition of the metal M, characterized in that the electrolyte is a material according to claim 1.

### Claim 20 (depends on 19)

Electrochemical system according to claim 19, characterized in that the counterelectrode consists of a grid of the metal M, optionally deposited on a transparent support.