# US 10,347,907 B2 · Volume change compensated silicon-silicon oxide-lithium composite material having nano silicon particles embedded in a silicon:silicon lithium silicate composite matrix, and cyclical ex-situ manufacturing processes

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- Number: US 10,347,907 B2
- Document ID: US10347907B2
- Status: Granted
- Kind: B2
- Application number: 15/691,780
- Filed: 2017-08-31
- Published: 2018-03-08
- Granted: 2019-07-09
- Earliest claimed: 2016-09-02
- Assignees: Eocell Ltd
- Applicants: EoCell Limited
- Inventors: Yuriy Matus; Yongbong Han; Michael Pak
- Web page: https://patentgrep.com/patent/US10347907B2

## CPC

- H01M 4/362: {Composites}
- H01M 4/04: Processes of manufacture in general
- H01M 4/0445: {Forming after manufacture of the electrode, e.g. first charge, cycling}
- H01M 4/386: {Silicon or alloys based on silicon}
- H01M 4/485: of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy (H01M4/505, H01M4/525 take precedence)
- H01M 4/139: Processes of manufacture
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 2004/027: {Negative electrodes}
- Y02E 60/10: Energy storage using batteries
- 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

A method for producing a volume change compensated (SSLC) material is disclosed. An initially prelithiated SSLC material is produced and delithiated to produce a delithiated SSLC material. Perform at least one iteration involving: (a) re-prelithiating the delithiated SSLC material to produce a re-prelithiated SSLC material; and (b) delithiating the re-prelithiated SSLC material produced in (a). At least one of the following is satisfied: (i) prior to performing the at least one iteration the initially prelithiated SSLC material is essentially completely lithiated; and (ii) at least one iteration produces a re-prelithiated SSLC material that is essentially completely prelithiated. In a final iteration, delithiating the re-prelithiated SSLC material produced in (a) completely delithiates the re-prelithiated SSLC material to produce the volume change compensated SSLC material. The aforesaid process is performed ex situ with respect to fabrication of an anode that contains the produced volume change compensated SSLC material.

## Claims

### Claim 1

A method for producing a volume change compensated silicon-silicon oxide-lithium composite (SSLC) material, the method comprising:
producing an initially prelithiated SSLC material;
delithiating the initially prelithiated material to produce a delithiated SSLC material; and
performing at least one iteration of a volume change compensation process comprising:
(a) re-prelithiating the delithiated SSLC material to produce a re-prelithiated SSLC material, and
(b) delithiating the re-prelithiated SSLC material produced in (a),
wherein at least one of the following is satisfied:
(i) prior to performing the at least one iteration of the volume change compensation process the initially prelithiated SSLC material is completely lithiated, and
(ii) the at least one iteration of the volume change compensation process produces a re-prelithiated SSLC material that is completely prelithiated,
wherein in a final iteration of the volume change compensation process, delithiating the re-prelithiated SSLC material produced in (a) comprises completely delithiating the re-prelithiated SSLC material to produce the volume change compensated SSLC material, and
wherein the volume change compensated SSLC material is produced ex situ with respect to fabrication of an anode that contains the produced volume change compensated SSLC material.

### Claim 2 (depends on 1)

The method of claim 1, wherein the volume change compensated SSLC material comprises a porous plastically deformable Si:Lithium Silicate Composite (Si:LSC) matrix having nano silicon particles embedded therein.

### Claim 3 (depends on 1)

The method of claim 1, wherein the initially prelithiated SSLC material and the re-prelithiated material produced during each iteration of the volume change compensation process are produced in slurry form.

### Claim 4 (depends on 1)

The method of claim 1, wherein the volume change compensation process is repeated 3-12 times.

### Claim 5 (depends on 1)

The method of claim 1, wherein in each iteration of the volume change compensation process, the re-prelithiated SSLC material is completely prelithiated.

### Claim 6 (depends on 1)

The method of claim 1, wherein in a selected iteration of the volume change compensation process, the re-prelithiated SSLC material has a higher lithium content than in another iteration of the volume change compensation process.

### Claim 7 (depends on 1)

The method of claim 1, wherein each delithiating of the re-prelithiated SSLC material completely delithiates the re-prelithiated SSLC material.

### Claim 8 (depends on 1)

The method of claim 1, wherein delithiating the initially prelithiated SSLC material and delithiating the re-prelithiated SSLC material comprises exposing the initially prelithiated SSLC material and exposing the re-prelithiated SSLC material, respectively, to a delithiating agent comprising at least one of a carboxylic acid, a sulfonic acid, and an alcohol.

### Claim 9 (depends on 8)

The method of claim 8, wherein the delithiating agent comprises at least one of: formic acid (methanoic acid), HCOOH (pKa=3.8); acetic acid (ethanoic acid), CH3COOH (pKa=4.7); propionic acid (propanoic acid), CH3CH2COOH (pKa=4.9); butyric acid (butanoic acid), CH3CH2CH2COOH (pKa=4.8);valeric acid (pentanoic acid), CH3CH2CH2CH2COOH (pKa=4.8); caprioc acide (hexanoic acide), CH3CH2CH2CH2CH2COOH (pKa=4.9); oxalic acid (ethanedioic acid), (COOH)(COOH)(pKa=1.2);lactic acid (2-hydroxypropanoic acid), CH3CHOHCOOH (pKa=3.9); malic acid (2-hydroxybutanedioic acid), (COOH)CH2CHOH(COOH) (pKa=3.4); citric acid (2-hydroxypropane- 1,2,3 -tricarboxylic acid), CH2(COOH)COH(COOH)CH2(COOH) (pKa=3.1); benzoic acid (Benzenecarboxylic acid [IUPAC ] or phenylmethanoic acid, non-IUPAC), C6H5COOH (pKa=4.2); carbonic acid (hydroxymethanoic acid, non-IUPAC name), OHCOOH or H2CO3 (pKa=3.6); phenol (carbolic acid or hydroxybenzene, non-IUPAC names), C6H5OH (pKa=9.9); uric acid (7,9-Dihydro-1H -purine-2,6,8(3H)-trione), C5H4N4O3 (pKa=−1.1); taurine (2-aminoethanesulfonic acid), C2H7NO3S (pKa=9.0); p-toluenesulfonic acid (4-methylbenzenesulfonic acid), CH3C6H4SO3H (pKa=−2.8); and trifluoromethanesulfonic acid, CF3SO3H (pka=−12).

### Claim 10 (depends on 8)

The method of claim 8, wherein the delithiating agent comprises at least one of:
(a) a monohydric alcohol selected from among: methanol, CH3OH; ethanol, C2H5OH; propan-2-ol, C3H7OH; butan-1-ol, C4H9OH; pentan-1-ol, C5H11OH; and hexadecan-1-ol, C16H33OH;
(b) a polyhydric alcohol selected from among: ethane-1,2-diol, C2H4(OH)2; propane-1,2-diol, C3H6(OH)2; propane-1,2,3-triol, C3H5(OH)3; butane-1,2,3,4-tetraol, C4H6(OH)4; pentane-1,2,3,4,5-penotol, C5H7(OH)5; hexane-1,2,3,4,5,6-hexol, C6H8(OH)6; and heptane-1,2,3,4,5,6,7-heptol, C7H9(OH)7;
(c) an unsaturated aliphatic alcohol selected from among prop-2-ene-1-ol, C3H5OH; 3,7-dimethylocta-2,6-dien-1-ol, C10H17OH; and prop-2-yn-1-ol, C3H3OH;
(d) an alicyclic alcohol selected from among: cyclohexane-1,2,3,4,5,6-hexol, C6H6(OH)6; and 2-(2-propyl)-5-methyl-cyclohexane-1-ol, C10H19OH; and
(e) polyvinyl alcohol (PVA) [CH2CH(OH)]n.

### Claim 11

A method for fabricating an anode for a lithium ion battery, comprising:
producing a volume change compensated silicon:silicon oxide:lithium composite (SSLC) material by:
producing an initially prelithiated SSLC material;
delithiating the initially prelithiated material to produce a delithiated SSLC material; and
performing at least one iteration of a volume change compensation process comprising:
(a) re-lithiating the delithiated SSLC material to produce a re-prelithiated SSLC material, and
(b) delithiating the re-prelithiated SSLC material produced in (a);
wherein at least one of the following is satisfied:
(i) prior to performing the at least one iteration of the volume change compensation process the initially prelithiated SSLC material is completely lithiated, and
(ii) at least one iteration of the volume change compensation process produces a re-prelithiated SSLC material that is completely prelithiated,
wherein in a final iteration of the volume change compensation process, delithiating the re-prelithiated SSLC material produced in (a) comprises completely delithiating the re-prelithiated SSLC material to produce the volume change compensated SSLC material, and
after producing the volume change compensated SSLC material, fabricating an anode structure containing the produced volume change compensated SSLC material.