# US 11,309,613 B2 · Organized nanoparticulate and microparticulate coatings and methods of making and using same

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- Number: US 11,309,613 B2
- Document ID: US11309613B2
- Status: Granted
- Kind: B2
- Application number: 16/060,779
- Filed: 2016-12-12
- Published: 2018-10-25
- Granted: 2022-04-19
- Earliest claimed: 2015-12-10
- Assignees: Cornell University
- Applicants: Cornell University
- Inventors: Mun Sek Kim; Snehashis Choudhury; Lin Ma; Lynden A. Archer
- Web page: https://patentgrep.com/patent/US11309613B2

## CPC

- H01M 4/139: Processes of manufacture
- B01D 71/021: {Carbon}
- B01D 71/027: {Silicium oxide}
- C02F 1/44: by dialysis, osmosis or reverse osmosis {(general membrane separation processes B01D61/00, membrane modules B01D63/00, electrodialysis C02F1/4693, combination of membrane modules and bioreactors C02F3/1268)}
- H01G 11/28: arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
- H01G 11/36: Nanostructures, e.g. nanofibres, nanotubes or fullerenes
- H01G 11/38: Carbon pastes or blends; Binders or additives therein
- H01G 11/46: Metal oxides
- H01G 11/52: Separators
- H01G 11/86: specially adapted for electrodes (carbonisation or activation of carbon for the manufacture of electrodes H01G11/34)
- H01M 4/13: Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M 50/403: Manufacturing processes of separators, membranes or diaphragms
- H01M 50/417: Polyolefins
- H01M 50/431: Inorganic material
- H01M 50/449: having a layered structure
- C02F 2305/08: Nanoparticles or nanotubes
- H01G 11/84: Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- Y02E 60/10: Energy storage using batteries
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28)
- C02F: TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE (separation in general B01D; special arrangements on waterborne vessels of installations for treating water, waste water or sewage, e.g. for producing fresh water, B63J; adding materials to water to prevent corrosion C23F; treating radioactively-contaminated liquids G21F9/04; regeneration of reactants for recirculation into processes, see the relevant places for the processes)
- 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)
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

Organized materials on a substrate. The organized materials are monolayer(s) of close-packed nanoparticles and/or microparticles. The organized materials can be formed by transfer of one or more monolayers to a substrate from a coating composition on which a monolayer of close-packed nanoparticles and/or microparticles is formed. Organized materials on a substrate can be used in devices such as, for example, batteries, capacitors, and wearable electronics.

## Claims

### Claim 1

A method of making an organized material on a substrate, wherein the organized material comprises one or more monolayers of nanoparticles disposed on at least a surface of a substrate and each monolayer of the layer is a close-packed arrangement of the nanoparticles, comprising:
a) providing a coating composition in a container comprising:
a monolayer of organized materials disposed on a liquid material comprising water and one or more additional liquid components that have lower surface tension than water, wherein the one or more additional liquid components is/are one or more alcohols;
and
b) transferring the monolayer of organized materials to the substrate, wherein the organized material on the substrate is formed.

### Claim 2 (depends on 1)

The method of claim 1, wherein the monolayer of organized materials is transferred by dip coating.

### Claim 3 (depends on 1)

The method of claim 1, wherein the monolayer of organized materials is transferred continuously to a substrate that is translated through the monolayer.

### Claim 4 (depends on 1)

The method of claim 1, wherein the method is a continuous process.

### Claim 5 (depends on 1)

The method of claim 1, wherein the one or more additional liquid components that have lower surface tension than water results in a surface tension gradient and formation of the organized materials.

### Claim 6 (depends on 1)

The method of claim 1, wherein the organized material comprises particles having at least one dimension of 10 nm to 5,000 nm.

### Claim 7 (depends on 6)

The method of claim 6, wherein the organized material comprises inorganic particles, organic particles, or a combination thereof.

### Claim 8 (depends on 7)

The method of claim 7, wherein the inorganic particles are metal and/or metalloid particles, metal and/or metalloid oxide particles, or a combination thereof.

### Claim 9 (depends on 8)

The method of claim 8, wherein the metal and/or metalloid particles comprise aluminum, copper, gold, lithium, magnesium, manganese, molybdenum, nickel, tin, titanium, zinc, silver, silicon, boron, germanium, sulfur, or a combination thereof and/or the metal oxide and/or the metalloid oxide particles comprise alumina, cobalt oxides, cupric oxides, hafnium oxides, iron oxides, lithium oxide, nickel oxides, manganese oxides, molybdenum oxides, palladium oxides, silver oxides, sodium oxide, tin oxides, titanium oxides, zinc oxide, germanium oxide, boron oxides, silicon oxides, or a combination thereof.

### Claim 10 (depends on 7)

The method of claim 7, wherein the organic particles are carbon-material particles or polymer particles.

### Claim 11 (depends on 10)

The method of claim 10, wherein the carbon-material particles are selected from carbon nanotubes (CNTs), functionalized CNTs, graphene, graphene oxides, reduced graphene oxides, graphites, fullerenes, buckytubes, diamond, amorphous carbons, vapor-grown carbon nanofibers, Super P carbon, Ketjen Black carbon, carbon fibers, hard carbons, hollow carbon nanoparticles, microporous carbon nanoparticles, mesoporous carbon nanoparticles, carbon nanorattles, and combinations thereof and/or the polymer particles are selected from polyaniline nanoparticles, polyacrylic acid, polyacrylates, polyacrylonitriles, polycarbonates, polyethers, polyolefins, polyimides, polymethylmethacrylate, polystyrenes, halogenated analogs thereof, and combinations thereof.

### Claim 12 (depends on 1)

The method of claim 1, wherein the substrate comprises a reactive metal and/or metalloid external surface, a carbon surface, silicon oxide surface, or a silicon carbide surface or the substrate comprises a material selected from metal oxides, metal nitrides, metal carbonates, and non-metals.

### Claim 13 (depends on 1)

The method of claim 1, wherein two or more monolayers are formed on the substrate.

### Claim 14 (depends on 13)

The method of claim 13, wherein all of the monolayers comprise the same material or at least two of the monolayers comprise different materials.

### Claim 15 (depends on 1)

The method of claim 1, wherein the substrate comprises a first surface and a second surface and wherein the first surface and second surface are opposite surfaces of the substrate.

### Claim 16 (depends on 15)

The method of claim 15, wherein at least one monolayer disposed on the first surface is a different material than at least one monolayer disposed on the second surface of the substrate.

### Claim 17 (depends on 16)

The method of claim 16, wherein the substrate is a current collector, electrode, or separator.

### Claim 18

A method of making an organized material on a substrate, wherein the organized material comprises one or more monolayers of organized materials disposed on at least a surface of a substrate and each monolayer is a close-packed arrangement of the organized materials, comprising:
a) providing a coating composition in a container comprising:
a monolayer of organized materials disposed on a liquid material comprising water and one or more additional liquid components that have lower surface tension than water, or
a monolayer of organized materials disposed on a liquid material comprising water and a surfactant, wherein the surfactant does not function as a dispersant in the coating composition; and
b) transferring the monolayer of organized materials to the substrate,
wherein the organized material on the substrate is formed,
wherein additional materials are added to the coating composition as the monolayer of organized materials is transferred to the substrate.

### Claim 19

A method of making an organized material on a substrate, wherein the organized material comprises one or more monolayers of organized materials disposed on at least a surface of a substrate and each monolayer is a close-packed arrangement of the organized materials, comprising:
a) providing a coating composition in a container comprising:
a monolayer of organized materials disposed on a liquid material comprising water and one or more additional liquid components that have lower surface tension than water, or
a monolayer of organized materials disposed on a liquid material comprising water and a surfactant, wherein the surfactant does not function as a dispersant in the coating composition; and
b) transferring the monolayer of organized materials to the substrate,
wherein the organized material on the substrate is formed,
wherein the monolayer is transferred to a second substrate by physically contacting the organized material on the substrate with the second substrate and application of pressure.

### Claim 20

A method of making an organized material on a substrate, wherein the organized material comprises one or more monolayers of nanoparticles disposed on at least a surface of a substrate and each monolayer of the layer is a close-packed arrangement of the nanoparticles, comprising:
a) providing a coating composition in a container comprising:
a monolayer of organized materials disposed on a liquid material comprising water and a surfactant, wherein a mixture of the materials and water is formed and, subsequently, the surfactant is added, and wherein the surfactant does not function as a dispersant in the coating composition;
and
b) transferring the monolayer of organized materials to the substrate,
wherein the organized material on the substrate is formed, and
wherein addition of the surfactant results in a surface tension gradient and formation of the organized monolayer of materials.

### Claim 21 (depends on 20)

The method of claim 20, wherein the monolayer of organized materials is transferred by dip coating.

### Claim 22 (depends on 20)

The method of claim 20, wherein the monolayer of organized materials is transferred continuously to a substrate that is translated through the monolayer.

### Claim 23 (depends on 20)

The method of claim 20, wherein the method is a continuous process.

### Claim 24 (depends on 20)

The method of claim 20, wherein the organized material comprises particles having at least one dimension of 10 nm to 5,000 nm.

### Claim 25 (depends on 20)

The method of claim 20, wherein the organized material comprises inorganic particles, organic particles, or a combination thereof.

### Claim 26 (depends on 25)

The method of claim 25, wherein the inorganic particles are metal and/or metalloid particles, metal and/or metalloid oxide particles, or a combination thereof.

### Claim 27 (depends on 26)

The method of claim 26, wherein the metal and/or metalloid particles comprise aluminum, copper, gold, lithium, magnesium, manganese, molybdenum, nickel, tin, titanium, zinc, silver, silicon, boron, germanium, sulfur, or a combination thereof and/or the metal oxide and/or the metalloid oxide particles comprise alumina, cobalt oxides, cupric oxides, hafnium oxides, iron oxides, lithium oxide, nickel oxides, manganese oxides, molybdenum oxides, palladium oxides, silver oxides, sodium oxide, tin oxides, titanium oxides, zinc oxide, germanium oxide, boron oxides, silicon oxides, or a combination thereof.

### Claim 28 (depends on 25)

The method of claim 25, wherein the organic particles are carbon-material particles or polymer particles.

### Claim 29 (depends on 28)

The method of claim 28, wherein the carbon-material particles are selected from carbon nanotubes (CNTs), functionalized CNTs, graphene, graphene oxides, reduced graphene oxides, graphites, fullerenes, buckytubes, diamond, amorphous carbons, vapor-grown carbon nanofibers, Super P carbon, Ketjen Black carbon, carbon fibers, hard carbons, hollow carbon nanoparticles, microporous carbon nanoparticles, mesoporous carbon nanoparticles, carbon nanorattles, and combinations thereof and/or the polymer particles are selected from polyaniline nanoparticles, polyacrylic acid, polyacrylates, polyacrylonitriles, polycarbonates, polyethers, polyolefins, polyimides, polymethylmethacrylate, polystyrenes, halogenated analogs thereof, and combinations thereof.

### Claim 30 (depends on 20)

The method of claim 20, wherein the substrate comprises a reactive metal and/or metalloid external surface, a carbon surface, silicon oxide surface, or a silicon carbide surface or the substrate comprises a material selected from metal oxides, metal nitrides, metal carbonates, and non-metals.

### Claim 31 (depends on 20)

The method of claim 20, wherein two or more monolayers are formed on the substrate.

### Claim 32 (depends on 31)

The method of claim 31, wherein all of the monolayers comprise the same material or at least two of the monolayers comprise different materials.

### Claim 33 (depends on 20)

The method of claim 20, wherein the substrate comprises a first surface and a second surface and wherein the first surface and second surface are opposite surfaces of the substrate.

### Claim 34 (depends on 33)

The method of claim 33, wherein at least one monolayer disposed on the first surface is a different material than at least one monolayer disposed on the second surface of the substrate.

### Claim 35 (depends on 20)

The method of claim 20, wherein the substrate is a current collector, electrode, or separator.