# US 2021/0242456 A1 · Patterned anodes for lithium-based energy storage devices

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- Number: US 2021/0242456 A1
- Document ID: US20210242456A1
- Status: Published application
- Kind: A1
- Application number: 17/237,217
- Filed: 2021-04-22
- Published: 2021-08-05
- Earliest claimed: 2019-06-27
- Assignees: Graphenix Development, Inc.
- Applicants: Graphenix Development, Inc.
- Inventors: Terrence R. O'Toole; John C. Brewer; Paul D. Garman; Robert G. Anstey
- Web page: https://patentgrep.com/patent/US20210242456A1

## CPC

- H01G 11/28: arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
- H01M 4/366: {as layered products}
- H01G 11/24: characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
- H01G 11/26: characterised by their structure, e.g. multi-layered, porosity or surface features
- H01G 11/36: Nanostructures, e.g. nanofibres, nanotubes or fullerenes
- H01G 11/46: Metal oxides
- H01G 11/50: specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
- H01G 11/68: characterised by their material
- H01G 11/70: characterised by their structure
- H01M 4/0404: {by coating on electrode collectors}
- H01M 4/0428: {Chemical vapour deposition}
- H01M 4/134: Electrodes based on metals, Si or alloys
- H01M 4/1395: of electrodes based on metals, Si or alloys
- H01M 4/386: {Silicon or alloys based on silicon}
- 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 4/661: {Metal or alloys, e.g. alloy coatings (H01M4/669 take precedence)}
- H01M 4/664: {Ceramic materials}
- 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
- H01G 11/06: with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
- H01M 4/70: characterised by shape or form
- H01M 2004/025: {with shapes other than plane or cylindrical}
- H01M 2004/027: {Negative electrodes}
- Y02E 60/10: Energy storage using batteries
- H01G: CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE (selection of specified materials as dielectric H01B3/00; capacitors having potential barriers H10D1/62, H10K10/10)
- 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

An anode for an energy storage device includes a current collector having a metal layer; and a metal oxide layer provided in a first pattern overlaying the metal layer. The anode further includes a patterned lithium storage structure having a continuous porous lithium storage layer selectively overlaying at least a portion of the first pattern of metal oxide. A method of making an anode for use in an energy storage device includes providing a current collector having a metal layer and a metal oxide layer provided in a first pattern overlaying the metal layer. A continuous porous lithium storage layer is selectively formed by chemical vapor deposition by exposing the current collector to at least one lithium storage material precursor gas.

## Claims

### Claim 1

A method of making an anode for use in an energy storage device, the method comprising:
providing a current collector comprising a metal layer and a metal oxide layer provided in a first pattern overlaying the metal layer; and
selectively forming by chemical vapor deposition, a continuous porous lithium storage layer overlaying the first pattern of metal oxide, wherein the chemical vapor deposition includes exposing the current collector to at least one lithium storage material precursor gas.

### Claim 2 (depends on 1)

The method of claim 1 wherein the lithium storage material precursor gas comprises silane or germane, and the continuous porous lithium storage layer has a total content of silicon, germanium or a combination thereof of at least 40 atomic %.

### Claim 3 (depends on 1)

The method of claim 1, wherein the metal layer comprises stainless steel, titanium, nickel, or copper, or a combination thereof.

### Claim 4 (depends on 1)

The method of claim 1, wherein the metal oxide layer comprises an oxide of nickel, an oxide of copper, an oxide of titanium, or a combination thereof.

### Claim 5 (depends on 1)

The method of claim 1, wherein the metal oxide layer has an average thickness of at least 0.02 μm.

### Claim 6 (depends on 1)

The method of claim 1, further comprising forming by chemical vapor deposition, lithium storage nanowires over the metal layer in one or more areas not occupied by the first pattern of metal oxide, wherein the lithium storage nanowires comprise a metal silicide and amorphous silicon.

### Claim 7 (depends on 6)

The method of claim 6, wherein the lithium storage nanowires are formed in a common step with formation of the continuous porous lithium storage layer.

### Claim 8 (depends on 1)

The method of claim 1, further comprising depositing a functional composition over the metal layer in one or more areas not occupied by the first pattern of metal oxide.

### Claim 9 (depends on 8)

The method of claim 8, wherein the functional composition is further deposited over the continuous porous lithium storage layer.

### Claim 10 (depends on 8)

The method of claim 8, wherein the functional composition is deposited by screen printing, inkjet printing, gravure printing, offset printing, flexographic printing, curtain coating, spray coating, spin coating, or slot die coating.

### Claim 11 (depends on 8)

The method of claim 8, wherein the functional composition comprises silicon-containing particles in a binder matrix.

### Claim 12 (depends on 8)

The method of claim 8, wherein the functional composition comprises an electrically conductive material comprising metal nanowires, metal particles, a conductive polymer, a conductive metal oxide, or combinations thereof.

### Claim 13 (depends on 1)

The method of claim 1, further comprising:
providing an electrically conductive current collector precursor comprising a metal layer; and
forming the first pattern of a first metal oxide layer overlaying the metal layer, thereby forming the current collector.

### Claim 14 (depends on 13)

The method of claim 13, wherein forming the first pattern of a metal oxide comprises oxidation of a surface portion of the metal layer.

### Claim 15 (depends on 14)

The method of claim 14, further comprising: i) forming a patterned resist over a non-patterned metal oxide; ii) etching or dissolving areas of metal oxide not covered by the patterned resist; and iii) and removing the patterned resist.

### Claim 16 (depends on 14)

The method of claim 14, further comprising applying a pattern of an oxidation resistant material prior to oxidation.

### Claim 17 (depends on 13)

The method of claim 13, wherein forming the first pattern of metal oxide comprises depositing a metal oxide or metal oxide precursor over the current collector precursor.

### Claim 18 (depends on 17)

The method of claim 17, further comprising depositing vaporized metal oxide through a shadow mask.

### Claim 19 (depends on 17)

The method of claim 17, further comprising printing the metal oxide precursor over the current collector precursor and treating the printed metal oxide precursor to form the first pattern of metal oxide.

### Claim 20 (depends on 17)

The method of claim 17, further comprising: i) forming a patterned resist over a non-patterned metal oxide; ii) etching or dissolving areas of the metal oxide not covered by the patterned resist; and iii) and removing the patterned resist.