# US 12,218,304 B2 · Solid composite electrolyte

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- Number: US 12,218,304 B2
- Document ID: US12218304B2
- Status: Granted
- Kind: B2
- Application number: 17/312,023
- Filed: 2019-12-11
- Published: 2022-01-27
- Granted: 2025-02-04
- Earliest claimed: 2018-12-21
- Assignees: Syensqo SA
- Applicants: Syensqo SA
- Inventors: Vincent Finsy; Luca Merlo; Marc-David Braida; Laure Bertry
- Web page: https://patentgrep.com/patent/US12218304B2

## CPC

- H01M 10/052: Li-accumulators
- H01M 10/0562: Solid materials
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 10/056: characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M 10/0563: Liquid materials, e.g. for Li-SOCl2 cells
- H01M 50/446: Composite material consisting of a mixture of organic and inorganic materials
- H01M 2300/0068: inorganic
- H01M 2300/0077: based on zirconium oxide
- H01M 2300/0082: Organic polymers
- H01M 2300/0091: in the form of mixtures
- Y02E 60/10: Energy storage using batteries
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

The invention relates to a solid composite electrolyte comprising: i) at least one solid inorganic particle, ii) at least one ionic liquid electrolyte, and iii) at least one ionically non-conductive polymer, wherein the at least one solid inorganic particle i) is ionic conductive and is blended with the at least one ionic liquid electrolyte ii). The invention also relates to a process for manufacturing the solid composite electrolyte, to a solid state battery comprising the solid composite electrolyte, and to the use of said solid composite electrolyte in a solid state battery for improving ionic conductivity and mechanical properties.

## Claims

### Claim 1

A solid composite electrolyte comprising:
i) at least one solid inorganic particle,
ii) at least one ionic liquid electrolyte, and
iii) at least one ionically non-conductive polymer,
wherein the at least one solid inorganic particle i) is ionic conductive and is blended with the at least one ionic liquid electrolyte ii) such that at least part of the at least one ionic liquid electrolyte covers at least part of the surface of the at least one solid inorganic particle, reducing grain-to-grain resistance between the at least one solid inorganic particle;
wherein an amount of the at least one solid inorganic particle i) is from 60.0 to 98.0% by weight (wt %), based on the total weight of the solid composite electrolyte; and
wherein the ionic liquid electrolyte comprises:
a positively charged cation selected from the group consisting of imidazolium, pyridinium, pyrrolidinium and piperidinium ions optionally containing one or more C1-C30 alkyl groups, and
a negatively charged anion selected from the group consisting of halides, fluorinated anions and borates,
wherein C1-C30 alkyl groups include methyl, ethyl, propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, isopentyl, 2,2-dimethyl-propyl, hexyl, 2,3-dimethyl-2-butyl, heptyl, 2,2-dimethyl-3-pently, 2-methyl-2-hexyl, octyl, 4-methyl-3-heptyl, nonyl, decyl, undecyl, and dodecyl groups.

### Claim 2 (depends on 1)

The solid composite electrolyte according to claim 1, wherein the at least one solid inorganic particle i) is a garnet-type inorganic particle having a general formula of M1aM2bM3cOd, wherein
M1 is a first cationic element selected from the group consisting of H, Li, Na, Mg, Al and Ga;
M2 is a second cationic element selected from the group consisting of La, Ba, Sr, Ca, In, Mg, Y, Sc, Cr, Al, K, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu;
M3 is a third cationic element selected from the group consisting of Zr, Ta, Nb, Sb, Sn, Hf, Bi, W, Si, Se, Ga, and Ge; and
a, b, c and d are positive numbers including various combinations of integers and decimals.

### Claim 3 (depends on 1)

The solid composite electrolyte according to claim 1, wherein the at least one solid inorganic particle i) is a garnet-type inorganic particle having a general formula of LixLayZrzAwO12, wherein:
A represents one or several dopants selected from the group consisting of Al, Ga, Nb, Fe, Nd, Pt, Ta, W, Mo, Hf, Si, Ca, Sr, Ba, Ge, and mixtures thereof;
w, x, y, and z are positive numbers, including various combinations of integers, zero and fractions or decimals;
0<y≤3;
0<z≤2;
0≤w≤0.5; and
x is derived from electroneutrality of the garnet structure.

### Claim 4 (depends on 3)

The solid composite electrolyte according to claim 3, wherein A represents one or several dopants selected from the group consisting of Al, W, Ga or combinations thereof.

### Claim 5 (depends on 1)

The solid composite electrolyte according to claim 1, wherein the at least one ionic liquid electrolyte ii) comprises at least one ionic liquid and at least one Li salt.

### Claim 6 (depends on 5)

The solid composite electrolyte according to claim 5, wherein the lithium salt comprises at least one selected from the group consisting of lithium hexafluorophosphate (LiPF6), lithium bis(fluorosulfonyl)imide Li (FSO2)2N (LiFSI), lithium 2-trifluoromethyl-4,5-dicyanoimidazole (LiTDI), LiBF4, LiB (C2O4)2, LiAsF6, LiCIO4, LiNO3, lithium bis(osalato) borate, LiCF3SO3, LiN (SO2CF3)2 (LiTFSI), LIN (SO2C2F5)2, LiC(SO2CF3)3, LiN (SO3CF3)2, LiC4F9SO3, LiCF93SO3, LiAlCl4, LiSbF6, LiF, LiBr, LiCI, LiOH, LiPFSi, and lithium trifluoromethanesulfonate.

### Claim 7 (depends on 1)

The solid composite electrolyte according to claim 1, wherein the at least one ionically non-conductive polymer iii) comprises a polymer selected from the group consisting of vinylidene fluoride (VDF) (co) polymers, styrene-butadiene rubber (SBR), styrene-ethylene-butylene-styrene (SEBS), carboxymethylcellulose (CMC), polyamideimide (PAI), perfluoroalkoxy alkane (PFA), poly(tetrafluoroethylene) (PTFE), poly(acrylonitrile) (PAN) (co) polymers, and polyalkylene oxide (PAO) (co) polymers.

### Claim 8 (depends on 1)

The solid composite electrolyte according to claim 1, wherein an amount of the at least one ionic liquid electrolyte ii) is from 1.0 to 30.0 wt %, based on the total weight of the solid composite electrolyte.

### Claim 9 (depends on 1)

The solid composite electrolyte according to claim 1, wherein an amount of the at least one ionically non-conductive polymer iii) is from 1.0 to 10.0 wt %, based on the total weight of the solid composite electrolyte.

### Claim 10 (depends on 1)

A process for manufacturing the solid composite electrolyte according to claim 1, comprising the steps of
blending the at least one solid inorganic particle i) with the at least one ionic liquid electrolyte ii);
preparing a polymer solution of the at least one ionically non-conductive polymer iii);
mixing said blended solid inorganic particles with the polymer solution;
casting the resulting solid composite electrolyte on a substrate to form a wet film;
drying the wet film; and
calendaring the film.

### Claim 11 (depends on 1)

A process for manufacturing the solid composite electrolyte according to claim 1, comprising the steps of
blending the at least one solid inorganic particle i) with the at least one ionic liquid electrolyte ii);
mixing said blended solid inorganic particles with the at least one ionically non-conductive polymer iii) to obtain a viscous paste; and
calendaring or extruding the viscous paste in successive steps to obtain a solid uniform film,
wherein the at least one ionically non-conductive polymer iii) is in dry state.

### Claim 12 (depends on 1)

A solid state battery comprising the solid composite electrolyte according to claim 1.

### Claim 13 (depends on 1)

The solid composite electrolyte of claim 1, wherein the solid composite electrolyte has an ionic conductivity of at least 1×10−5 S/cm and the solid composite electrolyte is self-standing and flexible.

### Claim 14 (depends on 3)

The solid composite electrolyte according to claim 3, wherein in the general formula of LixLayZrzAwO12, A represents one or several dopants selected from the group consisting of Al, Ga, Nb, Fe, Nd, Pt, Ta, W, and mixtures thereof.