# US 2024/0204162 A1 · Methods, systems, and compositions for the liquid-phase deposition of thin films onto the surface of battery electrodes

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

- Number: US 2024/0204162 A1
- Document ID: US20240204162A1
- Status: Published application
- Kind: A1
- Application number: 18/594,876
- Filed: 2024-03-04
- Published: 2024-06-20
- Earliest claimed: 2017-06-20
- Assignees: Coreshell Technologies, Incorporated
- Applicants: Coreshell Technologies, Incorporated
- Inventors: Sourav Basu; Jonathan Tan
- Web page: https://patentgrep.com/patent/US20240204162A1

## CPC

- H01M 4/0402: {Methods of deposition of the material}
- B05C 5/00: Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work (B05C7/00 takes precedence; essentially involving spraying or electrostatic projection B05B)
- B05C 9/00: Apparatus or plant for applying liquid or other fluent material to surfaces by means not covered by any preceding group, or in which the means of applying the liquid or other fluent material is not important
- H01M 4/0409: {by a doctor blade method, slip-casting or roller coating}
- H01M 4/0419: {involving spraying}
- H01M 4/049: {Manufacturing of an active layer by chemical means}
- H01M 4/139: Processes of manufacture
- H01M 4/587: for inserting or intercalating light metals
- H01M 4/62: Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M 6/005: {Devices for making primary cells}
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- B05C 3/00: Apparatus in which the work is brought into contact with a bulk quantity of liquid or other fluent material
- B05D 1/02: performed by spraying
- B05D 1/18: performed by dipping
- B05D 1/26: performed by applying the liquid or other fluent material from an outlet device in contact with, or almost in contact with, the surface
- B05D 1/28: performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
- B05D 1/38: with intermediate treatment (intermediate treatment per se B05D3/00)
- C23C 18/1655: {Process features}
- H01M 4/36: Selection of substances as active materials, active masses, active liquids
- H01M 4/362: {Composites}
- H01M 4/38: of elements or alloys
- H01M 10/0409: {for cells with wound electrodes}
- H01M 10/0587: of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
- H01M 2004/021: {Physical characteristics, e.g. porosity, surface area}
- H01M 2004/027: {Negative electrodes}
- H01M 2004/028: {Positive electrodes}
- 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
- B05C: APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (spraying apparatus, atomising apparatus, nozzles B05B; plant for applying liquids or other fluent materials to objects by electrostatic spraying B05B5/08)
- B05D: PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (conveying articles or workpieces through baths of liquid B65G, e.g. B65G49/02)
- 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
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

Methods, systems, and compositions for the liquid-phase deposition (LPD) of thin films. The thin films can be coated onto the surface of porous components of electrochemical devices, such as battery electrodes. Embodiments of the present disclosure achieve a faster, safer, and more cost-effective means for forming uniform, conformal layers on non-planar microstructures than known methods. In one aspect, the methods and systems involve exposing the component to be coated to different liquid reagents in sequential processing steps, with optional intervening rinsing and drying steps. Processing may occur in a single reaction chamber or multiple reaction chambers.

## Claims

### Claim 1

A method for coating a thin film onto a surface of a lithium-ion battery electrode, comprising:
(a) providing the lithium-ion battery electrode onto a conveyance apparatus that comprises a series of rollers;
(b) transferring, by the conveyance apparatus, the lithium-ion battery electrode to a first reaction chamber comprising at least a first liquid solution comprising a first reagent;
(c) exposing, by the conveyance apparatus, active material of the lithium-ion battery electrode to the first liquid solution to produce a partially coated lithium-ion battery electrode having a layer comprising an adsorbed first reagent on the surface of the active material of the lithium-ion battery electrode;
(d) transferring, by the conveyance apparatus, the partially coated lithium-ion battery electrode to a second reaction chamber comprising a second liquid solution comprising at least a second reagent; and
(e) exposing, by the conveyance apparatus, the partially coated lithium-ion battery electrode to the second liquid solution, wherein the at least second reagent reacts with the adsorbed first reagent bonded onto the surface of the active material of the partially coated lithium-ion battery electrode to produce a fully coated lithium-ion battery electrode having an artificial solid-electrolyte interphase (SEI) comprising a monolayer of thin film coated onto the surface of the active material, the monolayer of thin film comprising a compound generated from the reaction of the second reagent and the adsorbed first reagent.

### Claim 2 (depends on 1)

The method of claim 1, wherein steps (a)-(e) are repeated to produce a coating comprising a plurality of thin films on the active material, the coating having an overall thickness between 0.5 nanometers (nm) and 100 micrometers (μm) amd the lithium-ion battery electrode has pores ranging in size of 0.1 nm to 100 μm.

### Claim 3 (depends on 1)

The method of claim 1, wherein the first liquid solution includes (1) a metalorganic compound and an organic solvent or (2) an aqueous solution including a cationic compound.

### Claim 4 (depends on 3)

The method of claim 3, wherein the organic solvent includes at least one of isopropyl alcohol, ethanol, 2-methoxyethanol, pyridine, tetrahydrofuran, hexane, or toluene.

### Claim 5 (depends on 3)

The method of claim 3, wherein the metalorganic compound includes least one of aluminum tri-sec butoxide. titanium ethoxide, niobium ethoxide, trimethyl aluminum, or zirconium tert-butoxide.

### Claim 6 (depends on 3)

The method of claim 3, wherein the cationic compound includes at least one of zinc acetate, cadmium chloride, zinc chloride, zirconium chloride, and zinc sulfate.

### Claim 7 (depends on 1)

The method of claim 1, wherein the second liquid solution includes (1) at least an oxidizing agent in an organic solvent when the first liquid solution comprises at least a metal organic compound and an organic solvent or (2) at least an anionic precursor in an aqueous solution when the first liquid solution comprises at least an aqueous solution including a cationic compound.

### Claim 8 (depends on 7)

The method of claim 7, wherein the oxidizing agent includes at least one of water, thioacetamide, or sodium sulfate.

### Claim 9 (depends on 7)

The method of claim 7, wherein the second liquid solution includes at least one of ammonia or hydrazine.

### Claim 10 (depends on 1)

The method of claim 1, wherein the active material is deposited on a substrate, the substrate is in the form of a foil, sheet, or film; and the substrate is comprised of an organic material including at least one of a polyimide, a polyethylene, a polyether ether ketone (PEEK), a polyester, or a polyethylene napthalate (PEN).

### Claim 11 (depends on 1)

The method of claim 1, wherein the active material is deposited on a substrate, the substrate is in the form of a foil, sheet, or film; and the substrate is comprised of at least one of copper, aluminum, or stainless steel.

### Claim 12 (depends on 1)

The method of claim 1, wherein the compound generated by the reaction of the adsorbed first reagent and the second reagent comprises one or more transition metal dichalcogenides having a formula MX2, where M is a transition metal and X is S or Se.

### Claim 13 (depends on 1)

The method of claim 1, wherein the compound generated by the reaction of the adsorbed first reagent and the second reagent comprises at least one of polyethylene oxide (PEO), poly vinyl alcohol (PVA), poly methyl methacrylate (PMMA), poly dimethyl siloxane (PDMS), or poly vinyl pyrrolidone (PVP).

### Claim 14 (depends on 1)

The method of claim 1, wherein the lithium-ion battery electrode comprises at least one of graphite, Si, Sn, a Si-graphite composite, a Sn-graphite composite, or lithium metal.

### Claim 15 (depends on 1)

The method of claim 1, wherein the lithium-ion battery electrode comprises at least one of LiNixMnyCozO2, LiNixCoyAlzO2, LiMnxNiyOz, LiMnO2, LiFePO4, LiMnPO4, LiNiPO4, LiCoPCO4 LiCoPO4, LiV2O5, sulfur or LiCoO2 where x, y, and z are stoichiometric coefficients.

### Claim 16 (depends on 15)

The method of claim 15, wherein the lithium-ion battery electrode comprises at least one of LiNi0.33Mn0.33Co0.33O2, LiNi0.5Mn0.4Co0.1O2, LiNi0.5Mn0.3Co0.2O2, LiNi0.6Mn0.2Co0.2O2, LiNi0.7Mn0.2Co0.1O2, LiNi0.8Mn0.1Co0.1O2, LiNi0.9Mn0.05Co0.05O2, or LiNi0.4Mn0.4Co0.2O2.

### Claim 17 (depends on 1)

The method of claim 1, wherein the lithium-ion battery electrode and the partially coated lithium-ion battery electrode are exposed to the first liquid solution and the second liquid solution by at least one of submerging, spraying, slot die coating, or gravure roller coating.

### Claim 18 (depends on 1)

The method of claim 1, further comprising:
rinsing the partially coated lithium-ion battery electrode with a first rinsing solution in a first rinsing chamber, the first rinsing solution comprising a first rinsing solvent to produce a saturated first layer on the partially coated lithium-ion battery electrode and a first residual solution comprising the first rinsing solvent and unreacted first reagent;
rinsing the fully coated lithium-ion battery electrode with a second rinsing solution in a second rinsing chamber, the second rinsing solution comprising a second rinsing solvent to produce a saturated monolayer of thin film on the fully coated lithium-ion battery electrode and a second residual solution comprising the second rinsing solvent and unreacted second reagent;
passing the first residual solution and the second residual solution through one or more filtration apparatuses coupled to the first rinsing chamber and the second rinsing chamber, wherein the one or more filtration apparatuses separate an amount of the first rinsing solvent from unreacted first reagent and an amount of the second rinsing solvent from unreacted second reagent; and
recycling the amount of the first rinsing solvent to the first rinsing solution and the amount of the second rinsing solvent to the second rinsing solution.

### Claim 19 (depends on 18)

The method of claim 18, wherein the one or more filtration apparatuses perform at least one of membrane separation, chemical precipitation, ion-exchange, electrochemical removal, physical adsorption, or flow filtration chromatography; and
the method comprises:
recycling recovered unreacted first reagent back to the first liquid solution; and
recycling recovered unreacted second reagent back to the second liquid solution.

### Claim 20 (depends on 1)

The method of claim 1, wherein the compound generated is selected from one of the following groups:
(a) binary oxides of type AxOy, where A is an alkali metal, alkali-earth metal, transition metal, semimetal or metalloid and x and y are stoichiometric coefficients;
(b) ternary oxides of type AxByOz, where A and B are any combination of alkali metal, alkali-earth metal, transition metal, semimetal or metalloid and x, y and z are stoichiometric coefficients;
(c) quaternary oxides of type AwBxCyOz, where A, B and C are any combination of alkali metal, alkali-earth metal, transition metal, semimetal or metalloid and w, x, y and z are stoichiometric coefficients;
(d) binary halides of type AxBy, where A is an alkali metal, alkali-earth metal, transition metal, semimetal or metalloid, B is a halogen and x and y are stoichiometric coefficients;
(e) ternary halides of type AxByCz, where A and B are any combination of alkali metal, alkali-earth metal, transition metal, semimetal or metalloid, C is a halogen and x, y and z are stoichiometric coefficients;
(f) quaternary halides of type AwBxCyDz, where A, B and C are any combination of alkali metal, alkali-earth metal, transition metal, semimetal or metalloid, D is a halogen and w, x, y and z are stoichiometric coefficients;
(g) binary nitrides of type AxNy, where A is an alkali metal, alkali-earth metal, transition metal, semimetal or metalloid and x and y are stoichiometric coefficients;
(h) ternary nitrides of type AxByNz, where A and B are any combination of alkali metal, alkali-earth metal, transition metal, semimetal or metalloid and x, y and z are stoichiometric coefficients;
(i) quaternary nitrides of type AwBxCyNz, where A, B and C are any combination of alkali metal, alkali-earth metal, transition metal, semimetal or metalloid and w, x, y and z are stoichiometric coefficients;
(j) binary chalcogenides of type AxBy, where A is an alkali metal, alkali-earth metal, transition metal, semimetal or metalloid, B is a chalcogen and x and y are stoichiometric coefficients;
(k) ternary chalcogenides of type AxByCz, where A and B are any combination of alkali metal, alkali-earth metal, transition metal, semimetal or metalloid, C is a chalcogen and x, y and z are stoichiometric coefficients;
(l) quaternary chalcogenides of type AwBxCyDz, where A, B and C are any combination of alkali metal, alkali-earth metal, transition metal, semimetal or metalloid, D is a chalcogen and w, x, y and z are stoichiometric coefficients;
(m) binary carbides of type AxCy, where A is an alkali metal, alkali-earth metal, transition metal, semimetal or metalloid and x and y are stoichiometric coefficients;
(n) binary oxyhalides of type AxByOz, where A is an alkali metal, alkali-earth metal, transition metal, semimetal or metalloid, B is a halogen and x, y and z are stoichiometric coefficients;
(o) binary arsenides of type AxAsy, where A is an alkali metal, alkali-earth metal, transition metal, semimetal or metalloid and x and y are stoichiometric coefficients;
(p) ternary arsenides of type AxByAsz, where A and B are any combination of alkali metal, alkali-earth metal, transition metal, semimetal or metalloid and x, y and z are stoichiometric coefficients;
(q) quaternary arsenides of type AwBxCyAsz, where A, B and C are any combination of alkali metal, alkali-earth metal, transition metal, semimetal or metalloid and w, x, y and z are stoichiometric coefficients;
(r) binary phosphates of type Ax(PO4)y, where A is an alkali metal, alkali-earth metal, transition metal, semimetal or metalloid and x and y are stoichiometric coefficients;
(s) ternary phosphates of type AxBy(PO4)z, where A and B are any combination of alkali metal, alkali-earth metal, transition metal, semimetal or metalloid and x, y and z are stoichiometric coefficients; and
(t) quaternary phosphates of type AwBxCy(PO4)z, where A, B and C are any combination of alkali metal, alkali-earth metal, transition metal, semimetal or metalloid and w, x, y and z are stoichiometric coefficients.