# US 12,009,485 B2 · Solid electrolyte membrane including cyan-based polymer electrolyte and battery including the same

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- Number: US 12,009,485 B2
- Document ID: US12009485B2
- Status: Granted
- Kind: B2
- Application number: 17/864,605
- Filed: 2022-07-14
- Published: 2022-11-03
- Granted: 2024-06-11
- Earliest claimed: 2020-05-04
- Assignees: Soelect Inc.
- Applicants: Soelect Inc.
- Inventors: Sungjin Cho; Jongsoo Cho
- Web page: https://patentgrep.com/patent/US12009485B2

## CPC

- H01M 4/13: Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M 10/4235: {Safety or regulating additives or arrangements in electrodes, separators or electrolyte (H01M10/4242 takes precedence)}
- 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 50/414: Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M 50/42: Acrylic resins
- H01M 50/426: Fluorocarbon polymers
- H01M 50/4295: {Natural cotton, cellulose or wood}
- H01M 50/44: Fibrous material
- H01M 50/446: Composite material consisting of a mixture of organic and inorganic materials
- H01M 50/449: having a layered structure
- H01M 50/46: Separators, membranes or diaphragms characterised by their combination with electrodes
- H01M 2300/0068: inorganic
- 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

This disclosure relates generally to solid electrolyte membranes made from the combination of a polymer, a lithium salt group comprising of inorganic and/or organic anion, cyano molecules, a plasticizer having such a high dielectric solvent, and, optionally, a filler having nano/micron size particles to prevent the crystallization of such a polymer matrix. The resultant structures are solid electrolyte membranes exhibiting high ionic conductivity, thermal and electrochemical stability capable of enhanced cycling performance as well as high mechanical strength able to permit improved battery manufacturing properties.

## Claims

### Claim 1

A solid electrolyte membrane comprising a reactive combination of constituents, said constituents comprising:
a) a polyacrylonitrile polymer or a co-polymer selected from the group of polyacrylonitrile, poly(styrene-co-acrylonitrile), poly(acrylonitrile-co-butadiene-co-styrene), acrylonitrile butadiene rubber (NBR), and any combination thereof;
b) at least one lithium salt having at least one of an inorganic anion and/or an organic anion;
c) at least one cyano-based molecule comprising a mono-cyano molecule, a di-cyano molecule, tetracyanoethylene, 2,5-cyclohexadiene-1,4-diylidene and any cyano-derivatives thereof, or any combination thereof;
d) at least one plasticizer present within at least one dielectric solvent selected from the group of propylene carbonate (PC), 1,3-dioxolan-2-one, and any combination thereof; and
e) at least one nano- and/or micron-sized particle filler comprising lithophilic inorganic compounds;
wherein the solid electrolyte membrane exhibits an ionic conductivity value between 2.0×10−4 S/cm and 1.3×10−3 S/cm at room temperature; and
wherein the solid electrolyte membrane exhibits a tensile strength of at least 0.5 megapascals (MPa).

### Claim 2 (depends on 1)

The solid electrolyte membrane of claim 1 wherein said membrane is a free-standing film.

### Claim 3 (depends on 1)

The solid electrolyte membrane of claim 1 wherein:
b) said lithium salt having an i) inorganic anion is selected from the group of lithium perchlorate (LiClO4), lithium tetrafluoroborate (LiBF4), lithium hexafluorophosphate (LiPF6), lithium hexafluoro-arsenate (LiAsF6), lithium hexafluoroantimonate (LiSbF6), lithium hexafluorotantalate (LiTaF6), and lithium hexafluoroniobate (LiNbF6),
ii) organic anion is selected from the group of lithium trifluoromethanesulfonate (LiCF3SO3), lithium perfluorobutylsulfonate (LiC4F9SO3), lithium bis(trifluoromethanesulfonyl)imide (LiC2F6NO4S2), lithium bis (perfluoro-ethane-sulfonyl)imide (Li(CF3CF2SO2)2N), lithium tris(trifluoromethanesulfonyl) methide (C4F9LiO6S3), lithium pentafluoroethyltrifluoroborate (LiBF3(C2F5)), lithium bis(oxalato)borate (LiB(C2O4)2), lithium tetra(pentafluorophenyl)borate (C24BF20Li), lithium fluoroalkylphosphate (LiPF3(CF3CF2)3), lithium difluorophosphate, and lithium(difluorooxalato)borate;
c) i) said mono-cyano group is selected from the group of butyl cyanide, 2-methylglutaronitrile, α-methyl-valerodinitrile, and percyanoethylene, and
ii) said di-cyano group is selected from the group of 1,4-dicyanobutane, 1,3-dicyanopropane, 1,2-dicyanoethane, 1,5-dicyanopetane, 1,6-dicyanohexane, trans-1,4-dicyano-2-butene, and trans-1,2-dicyanoethylene; and
e) v) said lithophilic inorganic compounds include cations selected from the group consisting of Al, Ag, Au, Zn, Mg, Si, Sn, Ge, In, Ba, Bi, B, Ca, Cd, Ir, Pd, Pt, Rh, Sb, Se, Sr, Te, Zn, AgO, MgO, MnO2, Co3O4, SnO2, SiO2, ZnO, CuO, and Cu2O.

### Claim 4 (depends on 1)

The solid electrolyte membrane of claim 1 wherein said membrane is a free-standing film or a substrate-assisted film present on at least one of cathodes or anodes.

### Claim 5 (depends on 4)

The solid electrolyte membrane of claim 4 wherein said membrane exhibiting a thickness between 0.1 to 200 μm.

### Claim 6 (depends on 4)

The solid electrolyte membrane of claim 4 wherein said membrane is a free-standing film or a substrate-assisted film present on at least one of cathodes or anodes.

### Claim 7 (depends on 6)

The solid electrolyte membrane of claim 6 wherein said membrane exhibiting a thickness between 0.1 to 200 μm.

### Claim 8 (depends on 4)

The solid electrolyte membrane of claim 4 wherein said membrane is a substrate-assisted film.

### Claim 9 (depends on 8)

The solid electrolyte membrane of claim 8 wherein said substrate-assisted film is present on a substrate selected from the group consisting of an anode, a cathode, an anode-free substrate, a copper foil, a stainless-steel foil, and a separator.

### Claim 10 (depends on 8)

The solid electrolyte membrane of claim 8 wherein the anode is selected from the group consisting of a-1) carbonaceous based materials including graphite(s), hard carbon, soft carbon, carbon nanotube, silicon-graphite, carbon composite, and lithium titanate (Li4Ti5O2);
a-2) lithium metal, lithium metal alloy, lithium metal composite, and any negative substrates in anode free cell configuration; and
a-3) a substrate without active materials including copper foil, copper mesh, stainless steel, nickel-plated copper, and any combination of anode active material free substrates.

### Claim 11 (depends on 9)

The solid electrolyte membrane of claim 9 wherein said substrate is the separator, which constitutes materials selected from the group consisting of polyolefin, polyester, ceramic-embedded polyester, polyvinylidene fluoride (PVDF), ceramic-filled PVDF, ceramic-coated PVDF, polytriphenylamine, porous cellulose, hemi-cellulose, lignin, and ceramic-filled porous fiber.

### Claim 12 (depends on 9)

The solid electrolyte membrane of claim 9 wherein the cathode is selected from the group consisting of a) lithium metal oxides, b) tavorite phosphate- and sulfate-based compounds, c) fluorophosphates, d) LiMSO4F, wherein M=Co, Ni, Mn, V, or Fe, e) polyanionic compounds, and/or f) sulfur (S8) for lithium sulfur batteries and porous carbon cathode for lithium air batteries.

### Claim 13 (depends on 12)

The solid electrolyte membrane of claim 12 wherein said: a) lithium metal oxide is selected from the group consisting of LiNiCoMnO2, LiNiCoAlO2, LiCoO2, LiMn2O4, LiFePO4, LiNi0.5Mn1.5O4, layer-spinel oxide, olivine LiMPO4, and monolithic Li3M2(PO4)3, wherein M=Co, Ni, Mn, V, or Fe;
b) tavorite phosphate- and sulfate-based compounds selected from the group consisting of LiyMXO4Z, wherein y=0, 1, 2; M=Co, Ni, Mn, V, Fe; X═P, S; and Z═F, O, OH;
c) fluorophosphates selected from the group consisting of Li2MPO4F, wherein M is Co or Ni; and
e) polyanionic compounds are selected from the group consisting of lithium pyrophosphates, lithium diphosphates, and lithium silicates.

### Claim 14 (depends on 1)

A rechargeable lithium-ion battery comprising the solid electrolyte membrane of claim 1.

### Claim 15 (depends on 1)

A rechargeable lithium-ion battery comprising the solid electrolyte membrane of claim 1, wherein the solid electrolyte membrane is a cathode-based solid electrolyte membrane that comprises reactants of a) the at least one mono and/or di-cyano molecule, and b) the at least one lithium salt with at least one organic anion functional group, wherein the thickness of said cathode-based solid electrolyte membrane ranges from about 0.1 μm to 200 μm.

### Claim 16 (depends on 1)

A rechargeable lithium-ion battery comprising the solid electrolyte membrane of claim 1, wherein the solid electrolyte membrane is an anode-based solid electrolyte membrane that comprises reactants of a) the at least one mono and/or di-cyano molecule, and b) the at least one lithium salt with at least one organic anion functional group, wherein the thickness of said anode-based solid electrolyte membrane ranges from about 0.1 μm to 200 μm.

### Claim 17 (depends on 1)

A rechargeable lithium-ion battery comprising the solid electrolyte membrane of claim 1, wherein the solid electrolyte membrane is an anode-free substrate-based solid electrolyte membrane that includes a copper foil and reactants of a) the at least one mono and/or di-cyano molecule, and b) the at least one lithium salt with at least one organic anion functional group, wherein the thickness of said anode-free substrate-based solid electrolyte membrane ranges from about 0.1 μm to 200 μm.

### Claim 18 (depends on 4)

A rechargeable lithium-ion battery comprising the solid electrolyte membrane of claim 4.

### Claim 19 (depends on 6)

A rechargeable lithium-ion battery comprising the solid electrolyte membrane of claim 6.

### Claim 20 (depends on 2)

A rechargeable lithium-ion battery comprising the solid electrolyte membrane of claim 2.