# US 12,191,501 B2 · Anodes for lithium-based energy storage devices

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- Number: US 12,191,501 B2
- Document ID: US12191501B2
- Status: Granted
- Kind: B2
- Application number: 18/170,080
- Filed: 2023-02-16
- Published: 2023-07-06
- Granted: 2025-01-07
- Earliest claimed: 2019-08-21
- Assignees: Graphenix Development, Inc.
- Applicants: Graphenix Development, Inc.
- Inventors: John C. Brewer; Paul D. Garman; Kevin Tanzil
- Web page: https://patentgrep.com/patent/US12191501B2

## CPC

- H01M 4/667: {in the form of layers, e.g. coatings}
- H01M 4/0428: {Chemical vapour deposition}
- H01M 4/134: Electrodes based on metals, Si or alloys
- H01M 4/366: {as layered products}
- H01M 4/38: of elements or alloys
- H01M 4/386: {Silicon or alloys based on silicon}
- H01M 4/48: of inorganic oxides or hydroxides
- H01M 4/5815: {Sulfides}
- H01M 4/62: Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M 4/625: {Carbon or graphite}
- H01M 4/661: {Metal or alloys, e.g. alloy coatings (H01M4/669 take precedence)}
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 10/0565: Polymeric materials, e.g. gel-type or solid-type
- H01M 10/0568: characterised by the solutes
- H01M 10/0569: characterised by the solvents
- H01M 2004/027: {Negative electrodes}
- H01M 2004/028: {Positive electrodes}
- H01M 2300/0028: characterised by the solvent
- H01M 2300/0082: Organic polymers
- H01M 2300/0085: Immobilising or gelification of electrolyte
- 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

Methods of making an anode for a lithium-based energy storage device such as a lithium-ion battery are disclosed. Methods may include providing a current collector. The current collector may include an electrically conductive layer and a surface layer overlaying over the electrically conductive layer. The surface layer may have an average thickness of at least 0.002 μm. The surface layer may include a metal chalcogenide including at least one of sulfur or selenium. Methods may include depositing a continuous porous lithium storage layer onto the surface layer by a PECVD process. The continuous porous lithium storage layer may have an average thickness in a range of 4 μm to 30 μm and comprises at least 85 atomic % amorphous silicon.

## Claims

### Claim 1

A method of making an anode for use in an energy storage device, the method comprising:
providing a current collector comprising an electrically conductive layer and a surface layer overlaying over the electrically conductive layer, wherein the surface layer has an average thickness of at least 0.002 μm and comprises a metal chalcogenide comprising at least one of sulfur or selenium; and
depositing a continuous porous lithium storage layer onto the surface layer by a PECVD process, wherein the continuous porous lithium storage layer:
has an average thickness in a range of 4 μm to 30 μm,
comprises at least 85 atomic % amorphous silicon, and
is substantially free of high aspect ratio nanostructures.

### Claim 2 (depends on 1)

The method of claim 1, wherein the continuous porous lithium storage layer has a density in a range of 1.1 g/cm3 to 2.2 g/cm3.

### Claim 3 (depends on 2)

The method of claim 2, wherein the continuous porous lithium storage layer comprises less than 2 atomic % carbon.

### Claim 4 (depends on 1)

The method of claim 1, wherein the metal chalcogenide comprises a transition metal sulfide or transition metal polysulfide.

### Claim 5 (depends on 4)

The method of claim 4, wherein the transition metal is copper.

### Claim 6 (depends on 1)

The method of claim 1, wherein the electrically conductive layer comprises stainless steel, nickel, copper, titanium, or conductive carbon.

### Claim 7 (depends on 1)

The method of claim 1, further comprising forming the surface layer by treating the electrically conductive layer with a solution comprising at least one of a polysulfide salt, a thiosulfate salt, or a polyselenide salt.

### Claim 8 (depends on 7)

The method of claim 7, further comprising heating the electrically conductive layer to a temperature in a range of 100° C. to 350° C. after treating the electrically conductive layer with the solution.

### Claim 9 (depends on 1)

The method of claim 1, further comprising forming the surface layer by depositing a metal sulfide, a metal polysulfide, a metal selenide, or a metal polyselenide onto the electrically conductive layer by a PVD process, a CVD process, or an ALD process.

### Claim 10 (depends on 1)

The method of claim 1, wherein the surface layer further comprises a metal oxide.

### Claim 11 (depends on 10)

The method of claim 10, further comprising forming a first surface sublayer comprising the metal chalcogenide and depositing the metal oxide as a second surface sublayer disposed over the first surface sublayer.

### Claim 12 (depends on 11)

The method of claim 11, wherein the metal oxide is deposited by a PVD process, a CVD process, or an ALD process.

### Claim 13 (depends on 1)

The method of claim 1, further comprising depositing a supplemental layer over the continuous porous lithium storage layer, wherein the supplemental layer comprises a metal compound deposited by a process comprising ALD, CVD, sputtering, thermal evaporation, electrochemical deposition, or electroless deposition.

### Claim 14 (depends on 13)

The method of claim 13, wherein the supplemental layer comprises a lithium-containing material, a metal oxide, a metal nitride, or a metalcone.

### Claim 15 (depends on 1)

The method of claim 1, further comprising, after depositing the continuous porous lithium storage layer, thermally treating the anode at a temperature in a range of 100° C. to 450° C. for a thermal treatment time in a range of 0.1 to 60 minutes.

### Claim 16 (depends on 1)

The method of claim 1, wherein the surface layer has an average thickness in a range of 0.01 μm to 1.0 μm.

### Claim 17 (depends on 1)

A lithium-ion battery comprising the anode made according to claim 1, a liquid electrolyte, a cathode, and a current separator disposed between the anode and the cathode.

### Claim 18 (depends on 17)

The lithium-ion battery of claim 17, wherein the cathode comprises sulfur, selenium, or both sulfur and selenium.