# US 11,998,988 B2 · Methods for the production of nanocomposites for high temperature electrochemical energy storage devices

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- Number: US 11,998,988 B2
- Document ID: US11998988B2
- Status: Granted
- Kind: B2
- Application number: 16/923,189
- Filed: 2020-07-08
- Published: 2021-01-14
- Granted: 2024-06-04
- Earliest claimed: 2019-07-09
- Assignees: Saudi Arabian Oil Company
- Applicants: Saudi Arabian Oil Company
- Inventors: Muhammad Arsalan; Edreese Alsharaeh; Yasmin Mussa
- Web page: https://patentgrep.com/patent/US11998988B2

## CPC

- B22F 9/04: starting from solid material, e.g. by crushing, grinding or milling ({C22C1/1084 takes precedence}; crushing, grinding or milling, in general, see the relevant subclasses, e.g. B02C)
- H01M 4/364: {as mixtures}
- C01B 21/064: with boron
- C01B 21/0648: {After-treatment, e.g. grinding, purification (transformation of hexagonal into cubic or wurtzitic boron nitride C04B35/5831)}
- C01B 32/194: After-treatment
- C01B 32/198: Graphene oxide
- C01G 51/04: Oxides
- C01G 51/05: Hydroxides; Oxyhydroxides
- C04B 35/01: based on oxide ceramics
- C04B 35/522: {Graphite (C04B35/536 takes precedence)}
- C04B 35/583: based on boron nitride
- H01G 11/32: Carbon-based
- H01G 11/36: Nanostructures, e.g. nanofibres, nanotubes or fullerenes
- H01G 11/46: Metal oxides
- H01M 4/04: Processes of manufacture in general
- H01M 4/133: Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M 4/136: Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
- H01M 4/139: Processes of manufacture
- H01M 4/1393: of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M 4/1397: of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
- H01M 4/366: {as layered products}
- H01M 4/38: of elements or alloys
- H01M 4/52: of nickel, cobalt or iron
- 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 10/052: Li-accumulators
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- B22F 2009/043: {by ball milling}
- B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites
- B82Y 40/00: Manufacture or treatment of nanostructures
- C01P 2004/64: Nanometer sized, i.e. from 1-100 nanometer
- C01P 2004/80: Particles consisting of a mixture of two or more inorganic phases
- C01P 2006/40: Electric properties
- C04B 2235/3267: MnO2
- C04B 2235/386: Boron nitrides
- C04B 2235/425: Graphite
- C04B 2235/449: Organic acids, e.g. EDTA, citrate, acetate, oxalate
- 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
- Y02E 60/13: Energy storage using capacitors
- Y02T 10/70: Energy storage systems for electromobility, e.g. batteries
- B22F: WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER (making alloys by powder metallurgy C22C); APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- C01G: COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts or peroxyacids C01B15/00; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium, or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds containing nitrogen, other non-metals and metal C01B21/082}; metal amides C01B21/092; nitrites C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; compounds having molecular sieve properties but not having base-exchange properties C01B37/00; compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites, C01B39/00; cyanides C01C3/08; salts of cyanamide C01C3/16; thiocyanates C01C3/20)
- C04B: LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE {(roofing granules E04D7/005)}; CERAMICS (devitrified glass-ceramics C03C10/00); REFRACTORIES; TREATMENT OF NATURAL STONE
- 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)
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02T: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION

## Abstract

Presented here are nanocomposites and rechargeable batteries. In certain embodiments, nanocomposites a nanocomposite is resistant to thermal runaway, and useful as an electrode material in rechargeable batteries that are safe, reliable, and stable when operated at high temperature and high pressure. The present disclosure also provides methods of preparing rechargeable batteries. For example, rechargeable batteries that include nanocomposites of the present disclosure as an electrode material have, in some embodiments, an enhanced performance and stability over a broad temperature range from room temperature to high temperatures. These batteries fill an important need by providing a safe and reliable power source for devices operated at high temperatures and pressures such as downhole equipment used in the oil industry.

## Claims

### Claim 1

A method of preparing a thermally stable nanoparticle/graphene/boron nitride (BN) nanocomposite, the method comprising steps of:
ball-milling a mixture comprising a metal salt, graphene, and boron nitride; and
calcinating the mixture, wherein calcinating the mixture comprises heating the mixture in an oven, wherein the temperature of the oven is increased to a temperature in the range of 325 to 375° C. and subsequently held at that temperature for at least 1 hour.

### Claim 2 (depends on 1)

The method according to claim 1, wherein the metal salt is a cobalt salt.

### Claim 3 (depends on 1)

The method according to claim 1, wherein the metal salt is selected from the group consisting of cobalt (II) halide, cobalt (II) acetate, cobalt (II) hydroxide, cobalt (II) sulfate, cobalt (II) nitrate, and hydrates thereof.

### Claim 4 (depends on 1)

The method of claim 1, wherein the temperature of the oven is increased to a temperature in the range of 345 to 355° C. at a rate of 3 to 15° C./min and subsequently held at that temperature for 1 to 10 hours.

### Claim 5 (depends on 1)

A thermally stable nanoparticle/graphene/boron nitride (BN) nanocomposite prepared by the method of claim 1, wherein the nanoparticle/graphene/BN nanocomposite comprises nanoparticles, graphene, and boron nitride and has stable electrochemical properties at a temperature of at least 150° C.

### Claim 6 (depends on 5)

The nanocomposite of claim 5, wherein the nanoparticles are metal oxide nanoparticles.

### Claim 7 (depends on 6)

The nanocomposite of claim 6, wherein the metal oxide nanoparticles are Co3O4 nanoparticles.

### Claim 8 (depends on 7)

The nanocomposite of claim 7, wherein the Co3O4 nanoparticles make up 0.1% to 10% of the nanocomposite by weight.

### Claim 9 (depends on 7)

The nanocomposite of claim 7, wherein the Co3O4 nanoparticles make up 50% to 99.8% of the nanocomposite by weight.

### Claim 10 (depends on 5)

The nanocomposite of claim 5, wherein the boron nitride is in the form of hexagonal boron nitride.

### Claim 11 (depends on 5)

A method of preparing a nanoparticle/graphene/BN/sulfur (S) nanocomposite comprising ball-milling a mixture of the nanocomposite of claim 5 and sulfur.

### Claim 12 (depends on 11)

A nanoparticle/graphene/BN/S nanocomposite prepared by the method of claim 11.

### Claim 13

A method of preparing an electrode comprising:
mixing a nanocomposite with one or more conductive agents, a binding agent, and an optional additive in a solvent to obtain a slurry, wherein the nanocomposite comprises nanoparticles, graphene, and boron nitride; and
calcinating the mixture;
coating a foil substrate with the slurry to form a film; and
drying the film under vacuum.

### Claim 14 (depends on 13)

An electrode prepared by the method of claim 13.

### Claim 15

A method of preparing an electrode comprising:
dispersing one or more conductive agents in a solvent to prepare a first solution;
preparing a second solution of a binding agent with an optional additive in a solvent;
dispersing a nanocomposite in a solvent to prepare a third solution, wherein the nanocomposite comprises nanoparticles, graphene, and boron nitride;
mixing the first, second, and third solutions to obtain a slurry;
coating a foil substrate with the slurry to form a film; and
drying the film under vacuum.

### Claim 16 (depends on 15)

An electrode prepared by the method of claim 15.

### Claim 17 (depends on 12)

A method of preparing an electrode comprising:
mixing the nanocomposite of claim 12 with one or more conductive agents and a binding agent in a solvent to form a slurry;
coating a foil substrate with the slurry to form a film; and
drying the film under vacuum.

### Claim 18 (depends on 17)

An electrode prepared by the method of claim 17.

### Claim 19

A lithium-ion battery comprising an anode, a cathode, an electrolyte and a separator between the anode and the cathode, wherein the anode comprises a nanocomposite, wherein the nanocomposite comprises nanoparticles, graphene, and boron nitride.

### Claim 20 (depends on 19)

The lithium-ion battery of claim 19, wherein
(i) at 25° C., the lithium-ion battery has a specific capacity in the range of 30 mAh/g to 100 mAh/g; and
(ii) at 150° C., the lithium-ion battery has a specific capacity in the range of 100 to 500 mAh/g.

### Claim 21 (depends on 19)

The lithium-ion battery of claim 19, wherein, after 100 charge-discharge cycles at 150° C., the lithium-ion battery has a coulombic efficiency of at least 90% at 150° C.

### Claim 22 (depends on 12)

A lithium-sulfur battery comprising an anode, a cathode, an electrolyte and a separator between the anode and the cathode, wherein the cathode comprises the nanocomposite of claim 12.

### Claim 23 (depends on 22)

The lithium-sulfur battery of claim 22, wherein after 10 charge-discharge cycles at 25° C., at least 60% capacity is retained.

### Claim 24 (depends on 23)

The lithium-sulfur battery of claim 23, wherein after an additional 40 charge-discharge cycles, the capacity loss is less than 35% relative to the capacity at the end of the 10th cycle.