# US 10,320,029 B2 · All-solid-state lithium-sulfur polymer electrochemical cells and production methods thereof

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 10,320,029 B2
- Document ID: US10320029B2
- Status: Granted
- Kind: B2
- Application number: 14/899,788
- Filed: 2014-06-20
- Published: 2016-05-26
- Granted: 2019-06-11
- Earliest claimed: 2013-06-21
- Assignees: Hydro-Quebec
- Applicants: Hydro-Quebec
- Inventors: Karim Zaghib; Chisu Kim; Abdelbast Guerfi; Francis Barray; Catherine Gagnon; Julie Trottier
- Web page: https://patentgrep.com/patent/US10320029B2

## CPC

- H01M 10/0565: Polymeric materials, e.g. gel-type or solid-type
- H01M 4/0404: {by coating on electrode collectors}
- H01M 4/134: Electrodes based on metals, Si or alloys
- H01M 4/136: Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
- H01M 4/1397: of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
- H01M 4/366: {as layered products}
- H01M 4/382: {Lithium (H01M4/405 takes precedence)}
- H01M 4/405: {Alloys based on lithium}
- H01M 4/58: of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M 4/5815: {Sulfides}
- H01M 4/5825: {Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines}
- H01M 4/587: for inserting or intercalating light metals
- H01M 4/622: {being polymers}
- H01M 4/625: {Carbon or graphite}
- H01M 4/661: {Metal or alloys, e.g. alloy coatings (H01M4/669 take precedence)}
- H01M 4/667: {in the form of layers, e.g. coatings}
- 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 10/0562: Solid materials
- H01M 10/058: Construction or manufacture
- H01M 10/0583: of accumulators with folded construction elements except wound ones, i.e. folded positive or negative electrodes or separators, e.g. with "Z"-shaped electrodes or separators
- H01M 10/0585: of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
- H01M 10/0587: of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
- H01M 50/403: Manufacturing processes of separators, membranes or diaphragms
- H01M 50/46: Separators, membranes or diaphragms characterised by their combination with electrodes
- H01M 2004/027: {Negative electrodes}
- H01M 2004/028: {Positive electrodes}
- H01M 2220/20: Batteries in motive systems, e.g. vehicle, ship, plane
- H01M 2220/30: Batteries in portable systems, e.g. mobile phone, laptop
- Y02E 60/10: Energy storage using batteries
- Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product
- 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
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

All-solid-state lithium-sulfur electrochemical cells and production methods thereof are described. The Li—S electrochemical cells comprise at least one multilayer component which comprises an ion-conductive solid electrolyte film, a positive electrode film containing a sulfur composite, and a negative electrode film containing lithium. Positive electrodes films, prefabricated electrolyte-positive electrode elements, their uses as well as methods of their production are also described.

## Claims

### Claim 1

An electrochemical cell comprising at least one multilayer component which comprises:
a positive electrode film comprising, on a current collector, elemental sulfur particles as an electrochemically active material, conductive carbon, and a polymer binder, the elemental sulfur particles being encapsulated in an inorganic coating material, said inorganic coating material comprising an inorganic material selected from:
LiaM1b(XO4), wherein 0≤a≤2, 0<b≤1; M1 is selected from Fe, Mn, Co, Ni, and Ti, or combinations thereof, and X is selected from P, Si and S;
LicM2dZe, wherein 0≤c≤4, 0<d≤5, 0<e≤12, M2 is selected from Mo, V, Ti, Al, and Si, and Z is O; and
LicM2dZe, wherein 1≤c≤4, 0<d≤5, 0<e≤12, M2 is selected from Mo, V, Ti, Al, and Si, and Z is selected from S and Se;
a negative electrode film comprising lithium as an electrochemically active material; and
a solid electrolyte film between the negative and positive electrode films, said solid electrolyte film comprising at least one lithium salt and at least one polymeric layer, wherein the solid electrolyte film is an ion-conductive film and further comprises at least one electrolyte inorganic compound in the polymeric layer or in a separate ion-conductive solid layer, the polymeric layer comprising a block copolymer composed of at least one lithium-ion solvating segment and at least one cross-linkable segment, the cross-linkable segment being a polymer segment comprising at least one functional group cross-linkable multi-dimensionally by irradiation or thermal treatment, and the lithium-ion solvating segment being selected from homo- and copolymers having repeating units of formula (I):
wherein,
R is selected from H, C1-C10 alkyl, or —(CH2—O—RaRb);
Ra is (CH2—CH2—O)y;
Rb is selected from H and a C1-C10 alkyl group;
x is an integer selected from the range of 10 to 200,000; and
y is an integer selected from the range of 0 to 10.

### Claim 2 (depends on 1)

The electrochemical cell according to claim 1, wherein the electrolyte inorganic compound in the solid electrolyte film is selected from SiO2, Al2O3, TiO2, lithium ion-conductive glasses or ceramics, and other lithium ion-conductive solids, and combinations thereof.

### Claim 3 (depends on 2)

The electrochemical cell according to claim 2, wherein the lithium ion-conductive glasses or ceramics are selected from NASICON, LISICON, thio-LISICON, Garnet, either in crystalline or amorphous form, and combinations thereof.

### Claim 4 (depends on 1)

The electrochemical cell according to claim 1, wherein the solid electrolyte film has a thickness between 10 and 200 μm.

### Claim 5 (depends on 1)

The electrochemical cell according to claim 1, wherein the polymer binder is a block copolymer composed of at least one lithium ion-solvating segment and at least one cross-linkable segment.

### Claim 6 (depends on 5)

The electrochemical cell according to claim 5, wherein the lithium ion-solvating segment is selected from homo- or copolymers having repeating units of Formula (I):
wherein,
R is selected from H, C1-C10 alkyl, or —(CH2—O—RaRb);
Ra is (CH2—CH2—O)y;
Rb is selected from H and a C1-C10 alkyl group;
x is an integer selected from the range of 10 to 200,000; and
y is an integer selected from the range of 0 to 10.

### Claim 7 (depends on 1)

The electrochemical cell according to claim 1,
wherein the inorganic material is in the form of particles, optionally coated with carbon.

### Claim 8 (depends on 1)

The electrochemical cell according to claim 1, wherein the inorganic material is selected from LiFePO4, LiNiPO4, LiMnPO4, LiCoPO4, and LiFe1-xTixPO4, where 0<x<1.

### Claim 9 (depends on 1)

The electrochemical cell according to claim 1, wherein the inorganic material is selected from TiO2, V2O5, LiV3O8, Li4Ti5O12, MoO2, SiO2, and Al2O3.

### Claim 10 (depends on 1)

The electrochemical cell according to claim 1, wherein the positive electrode film comprises a composite material including sulfur encapsulated in a coating material and the composite material is prepared by mechanofusion.

### Claim 11 (depends on 1)

The electrochemical cell according to claim 1, wherein the conductive carbon is a carbon powder or fiber selected from carbon black, activated carbon, graphite, graphene, and mixtures thereof.

### Claim 12 (depends on 11)

The electrochemical cell according to claim 11, wherein the conductive carbon has a specific surface area of at least 5 m2/g.

### Claim 13 (depends on 1)

The electrochemical cell according to claim 1, wherein the electrochemically active material of the negative electrode film comprises a lithium metal foil or a lithium metal alloy comprising at least 90% by weight of lithium.

### Claim 14 (depends on 13)

The electrochemical cell according to claim 13, wherein a surface of the electrochemically active material of the negative electrode film further includes a passivation layer formed in situ.

### Claim 15 (depends on 13)

The electrochemical cell according to claim 13, wherein the negative electrode film further comprises a protective layer.

### Claim 16 (depends on 1)

A method for the manufacturing of an electrochemical cell as defined in claim 1, comprising the following steps:
a) providing the positive electrode film, the electrolyte film, and the negative electrode film; and
b) stacking and laminating together the positive electrode, electrolyte, and negative electrode films between at least two rollers;
wherein the step of providing the positive electrode film comprises the steps of mixing the electrochemically active material of the positive electrode together with a conductive carbon, polymer precursors, and optionally lithium salt(s), inorganic compound(s) and/or solvent(s), coating the mixture obtained on a current collector, evaporating the solvent (if present) and polymerizing, by UV irradiation or thermal treatment, to form the positive electrode film.

### Claim 17 (depends on 16)

The method according to claim 16, wherein the step of providing the electrolyte film comprises the steps of mixing polymer precursors, lithium salt(s), optionally inorganic compound(s) and/or solvent(s) to adjust viscosity, casting the mixture obtained on a substrate, evaporating the solvent (if present) and polymerizing, by UV irradiation or thermal treatment, to form the solid electrolyte film.

### Claim 18 (depends on 16)

The process according to claim 16, wherein the step of providing the electrolyte film comprises the steps of (i) mixing polymer precursors, lithium salt(s), inorganic compound(s), and optionally solvent(s) to adjust the viscosity, casting the mixture obtained on a substrate, evaporating the solvent (if present) and polymerizing, by UV irradiation or thermal treatment, to form the solid electrolyte film, thus obtaining a polymer-inorganic compound film; and (ii) mixing polymer precursors, lithium salt(s), and optionally solvent(s) to adjust the viscosity, casting the mixture obtained on the polymer-inorganic compound film, evaporating the solvent (if necessary) and polymerizing, by UV irradiation or thermal treatment, to form the solid electrolyte film.

### Claim 19 (depends on 16)

The method according to claim 16, wherein step (b) comprises laminating the positive electrode film together with the solid electrolyte film and subsequently laminating the negative electrode film thereon.

### Claim 20

A positive electrode film comprising, on a current collector, elemental sulfur particles as an electrochemically active material, a polymer binder and a conductive carbon, the elemental sulfur particles being encapsulated in an inorganic coating material, said inorganic coating material comprising an inorganic material selected from:
LiaM1b(XO4), wherein 0≤a≤2, 0<b≤1; M1 is selected from Fe, Mn, Co, Ni, and Ti, or combinations thereof, and X is selected from P, Si and S;
LicM2dZe, wherein 0≤c≤4, 0<d≤5, 0<e≤12, M2 is selected from Mo, V, Ti, Al, and Si, and Z is O; and
LicM2dZe, wherein 1≤c≤4, 0<d≤5, 0<e≤12, M2 is selected from Mo, V, Ti, Al, and Si, and Z is selected from S and Se;
wherein the polymer binder is a block copolymer composed of at least one lithium ion-solvating segment and at least one cross-linkable segment,
wherein the lithium ion-solvating segment is selected from homo- or copolymers having repeating units of Formula (I):
wherein,
R is selected from H, C1-C10 alkyl, or —(CH2—O—RaRb);
Ra is (CH2—CH2—O)y;
Rb is selected from H and a C1-C10 alkyl group;
x is an integer selected from the range of 10 to 200,000; and
y is an integer selected from the range of 0 to 10.

### Claim 21 (depends on 20)

A prefabricated electrolyte-positive electrode element comprising:
a positive electrode film as defined in claim 20; and
a solid electrolyte film at least one lithium salt and at least one polymeric layer, wherein the solid electrolyte film is an ion-conductive film and further comprises at least one electrolyte inorganic compound in the polymeric layer or in a separate ion-conductive solid layer;
wherein the positive electrode and solid electrolyte films are stacked and laminated.

### Claim 22 (depends on 21)

A method for the preparation of a prefabricated electrolyte-positive electrode element as defined in claim 21, comprising the steps of:
a) mixing sulfur together with conductive carbon, polymer precursors, and optionally lithium salt(s), inorganic compound(s), and/or solvent(s);
b) coating the mixture obtained in step (a) on a current collector, evaporating the solvent (if present) and polymerizing to form the positive electrode film;
c) mixing polymer precursors, lithium salt(s) and inorganic compound(s) in a solvent or solvents and coating on a substrate to form an electrolyte film precursor;
d) irradiating or heating the electrolyte film precursor of step (c) to form the solid electrolyte film; and
e) stacking and laminating the positive electrode film of step (b) together with the solid electrolyte film of step (d) to produce the prefabricated electrolyte-positive electrode element.

### Claim 23 (depends on 21)

A method for the preparation of a prefabricated electrolyte-positive electrode element as defined in claim 21, comprising the steps of:
a) mixing sulfur together with conductive carbon, polymer precursors, and optionally lithium salt(s), inorganic compound(s), and/or solvent(s);
b) coating the mixture obtained in step (a) on a current collector and evaporating the solvent (if present) to form a positive electrode film precursor;
c) mixing polymer precursors, lithium salt(s), inorganic compound(s) and optionally solvent(s), and coating on a surface of the positive electrode film precursor of step (b) to produce an electrolyte film/positive electrode film precursor;
d) irradiating or heating the electrolyte film/positive electrode film precursor obtained in step (c) to form the prefabricated electrolyte-positive electrode element.