# US 2022/0278366 A1 · Hybrid composite electrolyte comprising a fluoropolymer

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- Number: US 2022/0278366 A1
- Document ID: US20220278366A1
- Status: Published application
- Kind: A1
- Application number: 17/637,466
- Filed: 2020-08-31
- Published: 2022-09-01
- Earliest claimed: 2019-09-02
- Assignees: Solvay Specialty Polymers Italy S.P.A.
- Applicants: Solvay Specialty Polymers Italy S.P.A.
- Inventors: Maurizio BISO; Francesco LIBERALE; Vincent FINSY; Luca MERLO
- Web page: https://patentgrep.com/patent/US20220278366A1

## CPC

- H01M 10/0565: Polymeric materials, e.g. gel-type or solid-type
- H01M 4/0404: {by coating on electrode collectors}
- H01M 4/139: Processes of manufacture
- H01M 4/623: {fluorinated polymers}
- H01M 10/052: Li-accumulators
- H01M 10/0562: Solid materials
- H01M 2300/0068: inorganic
- H01M 2300/0082: Organic polymers
- H01M 2300/0088: Composites
- H01M 2300/0091: in the form of mixtures
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY

## Abstract

The present invention relates to a solid electrolyte film comprising sulfide-based solid electrolyte particles dispersed into an amorphous fluorinated binder, said solid electrolyte film being characterized by improved ionic conductivity, improved resistance to oxidation and good mechanical properties. The invention further relates to a process for the manufacture of said solid electrolyte film and to its use in solid state batteries.

## Claims

### Claim at position 1

1-14. (canceled)

### Claim 15

A composite solid electrolyte film for solid state batteries comprising:
i) at least one sulfide-based solid electrolyte; and
ii) at least one (per)fluorinated amorphous polymer [polymer (A)].

### Claim 16 (depends on 15)

The composite solid electrolyte film according to claim 15 wherein the at least one sulfide-based solid electrolyte is selected from the group consisting of:
lithium tin phosphorus sulfide (“LSPS”) materials;
lithium phosphorus sulfide (“LPS”) materials;
doped LPS;
lithium phosphorus sulfide oxygen (“LPSO”) materials of formula LixPySzO, where 0.33≤x≤0.67, 0.07≤y≤0.2, 0.4≤z≤0.55, 0≤w≤0.15;
lithium phosphorus sulfide materials including X (“LXPS”), wherein X is Si, Ge, Sn, As, Al;
lithium phosphorus sulfide oxygen including X (“LXPSO”), wherein X is Si, Ge, Sn, As, Al;
lithium silicon sulfide (“LSS”) materials;
lithium boron sulfide materials;
lithium tin sulfide materials and lithium arsenide materials; and
Argyrodite-type sulfide materials of formula Li6PS5Y, wherein Y is Cl, Br or I , the compounds optionally being deficient in sulfur, lithium or halogen or doped with a heteroatom.

### Claim 17 (depends on 15)

The composite solid electrolyte film according to claim 15 wherein the at least one (per)fluorinated amorphous polymer [polymer (A)] is selected from the group consisting of:
polymers (A-1) comprising recurring units derived from:
perfluorodioxoles of formula (I):
wherein R1, R2, R3 and R4, equal to or different from each other, are independently selected from the group consisting of —F, a C1-C6 fluoroalkyl group, optionally comprising one or more oxygen atoms;
at least one fluorinated monomer selected from the group consisting of:
C2-C8 perfluoroolefins;
C2-C8 hydrogenated fluoroolefins; and
chloro- and/or bromo- and/or iodo-C2-C6 fluoroolefins;
polymers (A-2) comprising recurring units derived from:
C2-C8 perfluoroolefins;
at least one fluorinated monomer selected from the group consisting of:
perfluoroalkylvinylethers of formula CF2=CFORf1′ wherein Rf1′ is a C1-C6 perfluoroalkyl group;
perfluoro-oxyalkylvinylethers of formula CF2=CFOX0 wherein X0 is a C1-C12 perfluorooxyalkyl group comprising one or more ether groups; and
optionally, recurring units derived from C2-C8 hydrogenated fluoroolefins;
polymers (A-3) comprising recurring units derived from at least one cyclopolymerizable monomer of formula
CR5R6=CR7OCR8R9(CRloR11)a(O)bCR12=CR13R14, wherein each R5 to R14, independently of one another, is selected from —F and a C1-C3 fluoroalkyl group, a is 0 or 1, b is 0 or 1 with the proviso that b is 0 when a is 1;
polymers (A-4) comprising:
recurring units derived from C2-C8 perfluoroolefins; and
recurring units derived from C2-C8 hydrogenated fluoroolefins.

### Claim 18 (depends on 17)

The composite solid electrolyte film according to claim 17 wherein polymer (A-1) comprises recurring units derived from at least one perfluorodioxole of formula (I) wherein R1=R3=R4=—F and R2=—OCF3 or wherein R1=R2=—F and R3=R4=—CF3 and recurring units derived from tetrafluoroethylene (TFE).

### Claim 19 (depends on 17)

The composite solid electrolyte film according to claim 17 wherein polymer (A-2) comprises recurring units derived from tetrafluoroethylene (TFE), recurring units derived from perfluoromethylvinylether of formula CF2=CFOCF3, and recurring units derived from vinylidene fluoride (VDF).

### Claim 20 (depends on 17)

The composite solid electrolyte film according to claim 17 wherein polymer (A-4) comprises recurring units derived from vinylidene fluoride (VDF) and recurring units derived from hexafluoropropene (HFP).

### Claim 21 (depends on 15)

A composition (C) suitable for preparing the composite solid electrolyte film according to claim 15, said composition comprising:
i) at least one sulfide-based solid electrolyte;
ii) at least one (per)fluorinated amorphous polymer [polymer (A)]; and
iii) at least one (per)fluorinated solvent (S).

### Claim 22 (depends on 21)

The composition (C) according to claim 21 wherein the at least one (per)fluorinated solvent (S) is selected from (per)fluoropolyethers, perfuoroalkanes, hydrofluoroethers, and mixtures thereof.

### Claim 23 (depends on 21)

A process for manufacturing a composite solid electrolyte film for solid state batteries comprising the steps of:
I) processing the composition (C) according to claim 21 to form a wet film of a solid composite electrolyte; and
II) drying the wet film provided in step (I).

### Claim 24 (depends on 23)

The process according to claim 23 which further includes a step (III) of subjecting the dry film provided in step (II) to a compression step.

### Claim 25 (depends on 21)

A process for manufacturing an electrode for solid state battery comprising the steps of:
A) providing an electrode-forming composition comprising:
a composition (C) according to claim 21;
at least one electrode active material (AM); and
- optionally, at least one electrical conductive additive;
B) providing a metal substrate having at least one surface;
C) applying the electrode-forming composition provided in step A) onto the at least one surface of the metal substrate provided in step B), thereby providing an assembly comprising a metal substrate coated with said composition (C) onto the at least one surface;
D) drying the assembly provided in step C).

### Claim 26 (depends on 25)

An electrode for a solid state battery obtainable by the process according to claim 25.

### Claim 27 (depends on 15)

A solid state battery comprising the composite solid electrolyte film according to claim 15.

### Claim 28 (depends on 26)

The solid state battery comprising:
a positive electrode and a negative electrode,
wherein at least one of the negative electrode or the positive electrode is an electrode according to claim 26.