# US 11,027,978 B2 · Silicon nanoparticle-containing hydrogen polysilsesquioxane, calcined product thereof, production method therefor, active material, negative electrode, and lithium ion battery

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- Number: US 11,027,978 B2
- Document ID: US11027978B2
- Status: Granted
- Kind: B2
- Application number: 16/313,866
- Filed: 2017-01-11
- Published: 2019-05-23
- Granted: 2021-06-08
- Earliest claimed: 2016-06-30
- Assignees: Jnc Corporation; Jnc Petrochemical Corporation
- Applicants: Jnc Corporation; Jnc Petrochemical Corporation
- Inventors: Yoshihito Takano; Tetsuro Kizaki; Hirotsuna Yamada; Masakazu Kondo; Akira Takahashi
- Web page: https://patentgrep.com/patent/US11027978B2

## CPC

- C01B 33/02: Silicon (forming single crystals or homogeneous polycrystalline material with defined structure C30B)
- C08G 77/12: containing silicon bound to hydrogen
- H01M 4/1395: of electrodes based on metals, Si or alloys
- H01M 4/38: of elements or alloys
- H01M 4/382: {Lithium (H01M4/405 takes precedence)}
- H01M 4/386: {Silicon or alloys based on silicon}
- H01M 4/58: of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- Y02E 60/10: Energy storage using batteries
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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 silicon nanoparticle-containing hydrogen polysilsesquioxane calcined product to be covered by the invention, represented by general formula SiOx2Hy2 (0.3<x2<1.5, 0.01<y2<0.35), containing 5% by weight to 65% by weight of silicon nanoparticles having a volume-basis mean particle size of more than 10 nanometers and less than 500 nanometers, having a chemical bond between a surface of the silicon nanoparticles and a silicon oxide structure derived from hydrogen polysilsesquioxane, having a Si—H bond, and substantially containing no carbon is silicon oxide applicable to a negative electrode active material for a secondary battery having excellent discharging capacity, initial charging and discharging efficiency and cycle characteristics.

## Claims

### Claim 1

A silicon nanoparticle-containing hydrogen polysilsesquioxane calcined product, represented by general formula SiOx2Hy2 (0.3<x2<1.5, 0.01<y2<0.35),
containing 5% by weight to 65% by weight of silicon nanoparticles having a volume-basis mean particle size of more than 10 nanometers and less than 500 nanometers,
having a chemical bond between a surface of the silicon nanoparticles and a silicon oxide structure derived from hydrogen polysilsesquioxane,
having a Si—H bond, and
substantially containing no carbon.

### Claim 2 (depends on 1)

The silicon nanoparticle-containing hydrogen polysilsesquioxane calcined product according to claim 1, wherein, in a spectrum measured by infrared spectroscopy, a ratio (I1/I2) of intensity (I1) of peak 1 in 820 to 920 cm−1 arising from the Si—H bond to intensity (I2) of peak 2 in 1000 to 1200 cm−1 arising from a Si—O—Si bond is in the range of 0.01 to 0.35.

### Claim 3 (depends on 1)

The silicon nanoparticle-containing hydrogen polysilsesquioxane calcined product according to claim 1, wherein, in a spectrum measured by infrared spectroscopy, among peaks arising from Si—O—Si, a ratio (I2-1/I2-2) of intensity (I2-1) of a peak (peak 2-1) at about 1170 cm−1 to intensity (I2-2) of a peak (peak 2-2) at about 1070 cm−1 is more than 1.

### Claim 4 (depends on 1)

A negative electrode active material for a lithium ion battery, containing the silicon nanoparticle-containing hydrogen polysilsesquioxane calcined product according to claim 1.

### Claim 5 (depends on 4)

A negative electrode for a lithium ion battery, containing the negative electrode active material for the lithium ion battery according to claim 4.

### Claim 6 (depends on 5)

A lithium ion battery, having the negative electrode for the lithium ion battery according to claim 5.

### Claim 7

A production method for a silicon nanoparticle-containing hydrogen polysilsesquioxane calcined product, represented by general formula SiOx2Hy2 (0.3<x2<1.5, 0.01<y2<0.35), containing 5% by weight to 65% by weight of silicon nanoparticles having a volume-basis mean particle size of more than 10 nanometers and less than 500 nanometers, having a chemical bond between a surface of the silicon nanoparticles and a silicon oxide structure derived from hydrogen polysilsesquioxane, having a Si—H bond, and substantially containing no carbon, and including a step of calcining silicon nanoparticle-containing hydrogen polysilsesquioxane, represented by general formula SiOx1Hy1 (0.25<x1<1.35, 0.16<y1<0.90), containing 5% by weight to 65% by weight of silicon nanoparticles having a volume-basis mean particle size of more than 10 nanometers and less than 500 nanometers, and having a chemical bond between a surface of the silicon nanoparticles and hydrogen polysilsesquioxane.

### Claim 8 (depends on 7)

The production method according to claim 7, wherein, in a spectrum measured by infrared spectroscopy, a ratio (I1/I2) of intensity (I1) of peak 1 in 820 to 920 cm−1 arising from a Si—H bond to intensity (I2) of peak 2 in 1000 to 1200 cm−1 arising from a Si—O—Si bond is in the range of 0.01 to 0.35.

### Claim 9 (depends on 7)

The production method according to claim 7, wherein, in a spectrum measured by infrared spectroscopy, among peaks arising from Si—O—Si, a ratio (I2-1/I2-2) of intensity (I2-1) of a peak (peak 2-1) at about 1170 cm−1 to intensity (I2-2) of a peak (peak 2-2) at about 1070 cm1 is more than 1.

### Claim 10 (depends on 7)

The production method according to claim 7, wherein the calcination is performed at a temperature of 600° C. to 900° C. under a non-oxidizing atmosphere.

### Claim 11 (depends on 10)

The production method according to claim 10, wherein the non-oxidizing atmosphere is a hydrogen gas atmosphere, or a mixed gas atmosphere of 2% by volume or more of a hydrogen gas and an inert gas.

### Claim 12

A silicon nanoparticle-containing hydrogen polysilsesquioxane, represented by general formula SiOx1Hy1 (0.25<x1<1.35, 0.16<y1<0.90), containing 5% by weight to 65% by weight of silicon nanoparticles having a volume-basis mean particle size of more than 10 nanometers and less than 500 nanometers, and having a chemical bond between a surface of the silicon nanoparticles and hydrogen polysilsesquioxane.

### Claim 13 (depends on 12)

The silicon nanoparticle-containing hydrogen polysilsesquioxane according to claim 12, wherein, in a spectrum measured by infrared spectroscopy, among peaks arising from Si—O—Si, a ratio (I2-1/I2-2) of intensity (I2-1) of a peak (peak 2-1) at about 1170 cm−1 to intensity (I2-2) of a peak (peak 2-2) at about 1070 cm−1 is more than 1.

### Claim 14

A production method for silicon nanoparticle-containing hydrogen polysilsesquioxane, represented by general formula SiOx1Hy1 (0.25<x1<1.35, 0.16<y1<0.90), containing 5% by weight to 65% by weight of silicon nanoparticles having a volume-basis mean particle size of more than 10 nanometers and less than 500 nanometers, and having a chemical bond between a surface of the silicon nanoparticles and hydrogen polysilsesquioxane, and including a step of allowing hydrolysis and a condensation reaction of a silicon compound represented by formula (1) in the presence of silicon nanoparticles:
HSi(R)3 (1)
wherein, R is halogen, hydrogen or a group selected from substituted or unsubstituted alkoxy having 1 to 10 carbons, substituted or unsubstituted aryloxy having 6 to 20 carbons, and substituted or unsubstituted arylalkoxy having 7 to 30 carbons, which is identical with or different from each other, in which, in the substituted or unsubstituted alkoxy having 1 to 10 carbons, the substituted or unsubstituted aryloxy having 6 to 20 carbons, and the substituted or unsubstituted arylalkoxy having 7 to 30 carbons, arbitrary hydrogen may be replaced by halogen.