IP Library Granted Patent US 11,459,242
Granted Patent B2
US 11,459,242 · App. 16/743,389 · Granted Oct 4, 2022

Stabilized electrodes for ion batteries and methods of making the same

Inventors: Nathan Richard Neale (Denver, CO); Gerard Zachary Carroll (Golden, CO); Gregory Frank Pach (Denver, CO); Maxwell Connor Schulze (Golden, CO); Trevor Russell Martin (Lakewood, CO)
Assignee: Alliance for Sustainable Energy, LLC
C01B33/12H01M4/386H01M10/0525H01M10/0562B82Y30/00B82Y40/00C01P2004/64H01M2300/0094
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Quick Facts
Patent No.
US 11,459,242
App. No.
16/743,389
Granted
Oct 4, 2022
Kind
B2
Abstract

The present disclosure relates to a silicon nanoparticle that includes a core of silicon having an outer surface that includes *SiH 3-x R x , where *Si is a silicon atom on the outer surface of the core, the first layer covers at least a portion of the outer surface, R is a ligand that includes at least one of —O—R′, —C—R′, —N—R′, —Si—R′, and/or —S—R′, and R′ is a functional group that includes at least one of carbon, oxygen, nitrogen, hydrogen, sulfur, and/or phosphorus.

Claims (36)

1. A silicon nanoparticle (Si NP) comprising:

a core of silicon having an outer surface comprising *SiH 3-x R x where 1≤x≤3;

a first layer that covers at least a portion of the outer surface; and

a second layer comprising at least one of a binder, a conductive material, or an electrolyte, wherein:

*Si is a silicon atom on the outer surface of the Si NP,

the first layer is positioned between the core and the second layer,

R is a ligand comprising at least one of —O—R′, —C—R′, —N—R′, —Si—R′, or —S—R′, and

R′ is a functional group comprising at least one of boron, carbon, oxygen, nitrogen, hydrogen, sulfur, or phosphorus.

2. The silicon nanoparticle of claim 1 , wherein the core has an average particle size between 1 nm and 500 nm.

3. The silicon nanoparticle of claim 2 , wherein the average particle size is between 3 nm and 75 nm.

4. The silicon nanoparticle of claim 1 , wherein R′ is derived from a reactant.

5. The silicon nanoparticle of claim 4 , wherein the reactant comprises at least one of N-methyl-2-pyrrolidone, 1-hexene, 1-hexanol, 1-hexanethiol, 1-dodecene, 1-dodecanol, 1-dodecanethiol, 1-octadecene, 1-octadecanol, 1-octadecanethiol, polyethylene glycol methyl ether, polyethylene oxide vinyl ether, phenol, aniline, benzoic acid, benzaldehyde, styrene, 2-naphthol, 2-vinylnaphthalene, 2-naphthalenemethanol, 4-vinyl biphenyl, 4-phenyl phenol, 4-biphenyl methanol, 4-biphenyl carboxaldehyde, 4-terphenylol, 4-terphenyl thiol, 4-phenylazophenol, polyacrylic acid, polyacrylonitirile, polyethylene oxide, acrylic acid, lithium acrylate, benzene-1,4-dicarboxaldehyde, benzene-1,3-dicarboxaldehyde, benzene-1,3,5-tricarboxaldehyde, 4-formylbenzoic acid, 4-(4-formylphenoxy)benzaldehyde, tris(4-formylphenyl)amine, 2,5-thiophenedicarboxaldehyde, 2,6-pyridinedicarboxaldehyde, thieno[3,2-b]thiophene-2,5-dicarboxaldehyde, or 2,5-dimethoxybenzene-1,4-dicarboxaldehyde.

6. The silicon nanoparticle of claim 1 , wherein R′ comprises at least one of an alkyl group, an alkenyl group, an alkynyl group, a carbonyl group, an aromatic, a halo group, an ester, an ether, a carboxylic acid, a carboxylate, an aldehyde, an alcohol, an alkoxide, an amine, an amide, an imine, an imide, a diimide (azo group), a nitrile, a cyanate, a nitroso, an oxime, a nitro, a thiol, a thiolate, a sulfonyl, a sulfonic acid, a sulfonate, a sulfonamide, a phosphonic acid, a phosphonate, or a thiol carbonyl.

7. The silicon nanoparticle of claim 1 , wherein the binder comprises at least one of polyethylene oxide (PEO), polyvinylidene fluoride, styrene butadiene rubber, polyacrylonitrile, carboxymethyl cellulose, polyacrylic acid, lithium polyacrylate, Nafion, polyacetylene, polyphenylene acetylene, or polyphenylene imide.

8. The silicon nanoparticle of claim 1 , wherein the conductive material comprises at least one of carbon black, an amorphous carbon, a glassy carbon, a single walled carbon nanotube, a multiwalled carbon nanotube, a functionalized carbon nanotube, graphene, graphene oxide, a functionalized graphene oxide, or a carbon fiber.

9. The silicon nanoparticle of claim 1 , wherein the electrolyte comprises at least one of diethyl carbonate, ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, propylene carbonate, glyme, diglyme, tetraglyme, or a polymer.

10. The silicon nanoparticle of claim 9 , wherein the polymer comprises at least one of polyethylene oxide or polyacrylonitrile.

11. The silicon nanoparticle of claim 1 , wherein the electrolyte comprises at least one of lithium phosphate oxynitride, lithium hexfluorophosphate, lithium fluorosulfonimide, or lithium trifluoromethylsulfonimide.

12. The silicon nanoparticle of claim 1 , further comprising a gap positioned between the first layer and the second layer.

13. The silicon nanoparticle of claim 1 , wherein at least one of the first layer or the second layer is capable of volume expansion and contraction as a result of mass transfer of an ion into and out of the core.

14. The silicon nanoparticle of claim 13 , wherein the ion is at least one of a lithium ion or a magnesium ion.

15. A method comprising:

reacting, in a mixture, a silicon nanoparticle (Si NP) with a reactant, wherein:

the Si NP has a silicon core

having an outer surface comprising a silicon-hydrogen group (*SiH x ) where 1≤x≤3,

*Si is a silicon atom on the outer surface of the Si NP, and

the reacting results in the forming of a functionalized Si NP comprising:

a silicon core with the outer surface comprising *SiH 3-x R x where 1≤x≤3;

a first layer that covers at least a portion of the outer surface; and

a second layer comprising at least one of a binder, a conductive material, or an electrolyte, wherein:

the first layer is positioned between the core and the second layer,

R is a ligand comprising at least one of —O—R′, —C—R′, —N—R′, —Si—R′, or —S—R′, and

R′ is a functional group comprising at least one of boron, carbon, oxygen, nitrogen, hydrogen, sulfur, or phosphorus.

16. The method of claim 15 , wherein the reactant comprises at least one of an alkenyl group, an alkynyl group, a carbonyl group, an aromatic, a halo group, an ester, an ether, an epoxide, a carboxylic acid, a carboxylate, an aldehyde, an alcohol, an alkoxide, a peroxide, an amine, an amide, an imine, an imide, a diimide (azo group), a nitrile, a cyanate, a nitroso, an oxime, a nitro, a thiol, a thiolate, a sulfonyl, a sulfonic acid, a sulfonate, a sulfonamide, a phosphonic acid, a thiol carbonyl, or a phosphonate.

17. The method of claim 15 , wherein R′ comprises at least one of an alkyl group, an alkenyl group, an alkynyl group, a carbonyl group, an aromatic, a halo group, an ester, an ether, a carboxylic acid, a carboxylate, an aldehyde, an alcohol, an alkoxide, an amine, an amide, an imine, an imide, a diimide (azo group), a nitrile, a cyanate, a nitroso, an oxime, a nitro, a thiol, a thiolate, a sulfonyl, a sulfonic acid, a sulfonate, a sulfonamide, a phosphonic acid, a phosphonate, or a thiol carbonyl.

18. The method of claim 15 , wherein the reactant comprises at least one of N-methyl-2-pyrrolidone, 1-hexene, 1-hexanol, 1-hexanethiol, 1-dodecene, 1-dodecanol, 1-dodecanethiol, 1-octadecene, 1-octadecanol, 1-octadecanethiol, polyethylene glycol methyl ether, polyethylene oxide vinyl ether, phenol, aniline, benzoic acid, benzaldehyde, styrene, 2-naphthol, 2-vinylnaphthalene, 2-naphthalenemethanol, 4-vinyl biphenyl, 4-phenyl phenol, 4-biphenyl methanol, 4-biphenyl carboxaldehyde, 4-terphenylol, 4-terphenyl thiol, 4-phenylazophenol, polyacrylic acid, polyacrylonitirile, polyethylene oxide, acrylic acid, lithium acrylate, benzene-1,4-dicarboxaldehyde, benzene-1,3-dicarboxaldehyde, benzene-1,3,5-tricarboxaldehyde, 4-formylbenzoic acid, 4-(4-formylphenoxy)benzaldehyde, tris(4-formylphenyl)amine, 2,5-thiophenedicarboxaldehyde, 2,6-pyridinedicarboxaldehyde, thieno[3,2-b]thiophene-2,5-dicarboxaldehyde, or 2,5-dimethoxybenzene-1,4-dicarboxaldehyde.

Assignments (3)
CHANGE OF NAME Recorded Dec 16, 2025
From: ALLIANCE FOR SUSTAINABLE ENERGY, LLC
To: ALLIANCE FOR ENERGY INNOVATION, LLC
Reel/Frame 073993/0276 →
CONFIRMATORY LICENSE Recorded Jan 11, 2021
From: NATIONAL RENEWABLE ENERGY LABORATORY
To: UNITED STATES DEPARTMENT OF ENERGY
Reel/Frame 054877/0530 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 15, 2020
From: NEALE, NATHAN RICHARD; CARROLL, GERARD ZACHARY; PACH, GREGORY FRANK; SCHULZE, MAXWELL CONNOR; MARTIN, TREVOR RUSSELL
To: ALLIANCE FOR SUSTAINABLE ENERGY, LLC
Reel/Frame 051523/0528 →