# US 11,444,270 B2 · Treating sulfide glass surfaces and making solid state laminate electrode assemblies

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- Number: US 11,444,270 B2
- Document ID: US11444270B2
- Status: Granted
- Kind: B2
- Application number: 16/948,863
- Filed: 2020-10-02
- Published: 2021-04-29
- Granted: 2022-09-13
- Earliest claimed: 2017-07-07
- Assignees: PolyPlus Battery Company
- Applicants: PolyPlus Battery Company
- Inventors: Steven J. Visco; Vitaliy Nimon; Yevgeniy S. Nimon; Bruce D. Katz; Richard L. Swisher
- Web page: https://patentgrep.com/patent/US11444270B2

## CPC

- H01M 4/0423: {Physical vapour deposition}
- C03C 17/36: at least one coating being a metal
- C03C 17/3626: {one layer at least containing a nitride, oxynitride, boronitride or carbonitride}
- C03C 17/3649: {made of metals other than silver}
- C03C 17/3671: {specially adapted for use as electrodes}
- C23C 14/022: {by means of bombardment with energetic particles or radiation}
- C23C 14/024: {Deposition of sublayers, e.g. to promote adhesion of the coating (C23C14/027 takes precedence)}
- C23C 14/0641: {Nitrides (C23C14/0617 takes precedence)}
- C23C 14/24: Vacuum evaporation
- C23C 14/34: Sputtering
- C23C 14/48: Ion implantation
- C23C 14/541: {Heating or cooling of the substrates}
- H01M 4/0407: {by coating on an electrolyte layer}
- H01M 4/134: Electrodes based on metals, Si or alloys
- H01M 4/1395: of electrodes based on metals, Si or alloys
- H01M 4/382: {Lithium (H01M4/405 takes precedence)}
- H01M 4/628: {Inhibitors, e.g. gassing inhibitors, corrosion inhibitors}
- H01M 10/052: Li-accumulators
- H01M 10/0562: Solid materials
- H01M 10/058: Construction or manufacture
- C03C 2218/151: by vacuum evaporation
- H01M 2300/0068: inorganic
- Y02E 60/10: Energy storage using batteries
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- C03C: CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04)
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

Methods for making solid-state laminate electrode assemblies include methods of forming a solid electrolyte interphase (SEI) by ion implanting nitrogen and/or phosphorous into the glass surface by ion implantation.

## Claims

### Claim 1

A method for making a battery cell, the method comprising:
forming a solid-state laminate electrode assembly by,
providing a lithium ion conducting sulfide glass substrate, the substrate comprising a sulfide glass solid electrolyte sheet having room temperature Li ion conductivity of at least 10−5 S/cm, the sulfide glass substrate having first and second major surfaces;
injecting nitrogen and/or phosphorous into the first major surface of the sulfide glass substrate, wherein the nitrogen and/or phosphorous penetrates the glass surface forming an implanted zone;
evaporating lithium metal onto the implanted zone of the sulfide glass substrate; wherein at least a portion of the evaporated lithium reacts with the injected nitrogen and/or phosphorous to form a solid electrolyte interphase (SEI) layer comprising lithium and one or both of nitrogen and phosphorous; and
disposing a positive electrode adjacent to the second major surface of the sulfide glass substrate of the solid-state laminate electrode assembly.

### Claim 2 (depends on 1)

The method of claim 1, wherein the implanted zone is substantially uniform and the SEI layer is continuous.

### Claim 3 (depends on 1)

The method of claim 1, wherein the SEI comprises lithium nitride.

### Claim 4 (depends on 1)

The method of claim 1, wherein the SEI comprises lithium phosphide.

### Claim 5 (depends on 1)

The method of claim 1, wherein the SEI is a continuous layer of a lithium nitride and/or lithium phosphide compound.

### Claim 6 (depends on 1)

The method of claim 1, wherein the injecting is performed by ion implantation using a nitrogen and/or phosphorous ion gun.

### Claim 7 (depends on 1)

The method of claim 1, wherein the nitrogen and/or phosphorous ion implantation zone is not greater than 10 nm deep.

### Claim 8 (depends on 1)

The method of claim 1, wherein the nitrogen and/or phosphorous ion implantation zone is not greater than 10-100 nm deep.

### Claim 9 (depends on 1)

The method of claim 1, wherein the nitrogen and/or phosphorous ion implantation zone is not greater than 100-1000 nm deep.

### Claim 10 (depends on 1)

The method of claim 1, wherein the injecting and the lithium evaporation takes place simultaneously.

### Claim 11 (depends on 10)

The method of claim 10, comprising injecting nitrogen and/or phosphorous onto the glass surface prior to lithium evaporation; simultaneously injecting and evaporating lithium metal; and, stopping the nitrogen injection while continuing the evaporation.

### Claim 12 (depends on 1)

The method of claim 1, wherein the positive electrode is a lithium ion intercalating material electrode.

### Claim 13 (depends on 12)

The method of claim 12, wherein the lithium ion intercalating material electrode comprises an intercalating transition metal oxide.

### Claim 14 (depends on 13)

The method of claim 13, wherein the transition metal oxide is selected from the group consisting of lithium cobalt oxides, lithium manganese oxides, lithium nickel oxides, lithium nickel manganese cobalt oxides and lithium nickel cobalt aluminum oxides.

### Claim 15 (depends on 1)

The method of claim 1, wherein a battery electrolyte is disposed between the second major surface of the sulfide glass substrate of the solid-state laminate electrode assembly and the positive electrode.

### Claim 16 (depends on 15)

The method of claim 15, wherein the battery electrolyte is a liquid electrolyte impregnated in porous polymer membrane and/or a gel electrolyte layer.

### Claim 17 (depends on 1)

The method of claim 1, wherein the battery cell is fully solid-state and the positive electrode is disposed in direct contact with the second major surface of the sulfide glass substrate of the solid-state laminate electrode assembly.

### Claim 18

A battery cell, comprising:
a solid-state laminate electrode assembly comprising,
a lithium ion conducting sulfide glass substrate, the substrate comprising a sulfide glass solid electrolyte sheet having room temperature Li ion conductivity of at least 10−5 S/cm, the sulfide glass substrate having first and second major surfaces;
a solid electrolyte interphase (SEI) layer comprising lithium and one or both of nitrogen and phosphorous at the first major surface of the sulfide glass substrate; and
a lithium ion intercalating transition metal oxide positive electrode adjacent to the second major surface of the sulfide glass substrate of the solid-state laminate electrode assembly.

### Claim 19 (depends on 18)

The battery cell of claim 18, wherein a battery electrolyte is disposed between the second major surface of the sulfide glass substrate of the solid-state laminate electrode assembly and the positive electrode.

### Claim 20 (depends on 18)

The battery cell of claim 18, wherein the battery cell is fully solid-state and the positive electrode is disposed in direct contact with the second major surface of the sulfide glass substrate of the solid-state laminate electrode assembly.