Manufacturing method of carbon-silicon composite

• US 9,981,993 B2
• Filed: 07/08/2015
• Issued: 05/29/2018
• Est. Priority Date: 07/17/2014
• Status: Active Grant

• Current Assignee: OCI Company Limited (OCI Holdings Co. Ltd.)
• Original Assignee: OCI Company Limited (OCI Holdings Co. Ltd.)
• Inventors: Jeong, Eun-Hye, Kim, Yo-Seop, Jung, Sung-Ho, Ha, Jeong-Hyun
• Primary Examiner(s): Douyette, Kenneth J
• Application Number:
  US14/793,742
• Publication Number:
  US 20160020465A1
• Time in Patent Office: 1,056 Days
• CPC Class Codes: C07F 7/0803 Compounds with Si-C or Si-Si linkages
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 4/0471 involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
• CPC Class Codes: H01M 4/133 Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
• CPC Class Codes: H01M 4/134 Electrodes based on metals, Si or alloys
• CPC Class Codes: H01M 4/1393 of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
• CPC Class Codes: H01M 4/1395 of electrodes based on metals, Si or alloys
• CPC Class Codes: H01M 4/366 as layered products
• CPC Class Codes: H01M 4/386 Silicon or alloys based on silicon
• CPC Class Codes: H01M 4/587 for inserting or intercalating light metals
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

Disclosed herein are a manufacturing method of a carbon-silicon composite, including: (a) preparing a slurry solution including silicon (Si)-block copolymer core-shell particles; (b) mixing the slurry solution with a carbon raw material to manufacture a mixed solution; (c) performing a primary carbonization process on the mixed solution, followed by pulverization, to manufacture a primary carbon-silicon composite; and (d) performing a secondary carbonization process on the primary carbon-silicon composite, followed by pulverization, to manufacture a secondary carbon-silicon composite, the carbon-silicon composite, an anode for a secondary battery manufactured by applying the carbon-silicon composite, and a secondary battery including the anode for a secondary battery.

Claims

1. A manufacturing method of a carbon-silicon composite, comprising:

(a) preparing a slurry solution including silicon (Si)-block copolymer core-shell particles;

(b) mixing the slurry solution with a carbon raw material to manufacture a mixed solution;

(c) performing a primary carbonization process on the mixed solution to form silicon (Si) block copolymer core-shell carbonization particles captured and dispersed in carbonaceous matrix, followed by pulverization, to manufacture a primary carbon-silicon composite; and

(d) performing a secondary carbonization process on the primary carbon-silicon composite, followed by pulverization, to manufacture a secondary carbon-silicon composite,

wherein the carbon raw material is selected from coal tar pitch, petroleum pitch, or combinations thereof.

2. The manufacturing method of claim 1, wherein the secondary carbonization process in (d) is performed at a temperature higher than that of the primary carbonization process.

3. The manufacturing method of claim 1, wherein the pulverization in (c) and (d) is performed by a milling.

4. The manufacturing method of claim 1, wherein the silicon (Si)-block copolymer core-shell particles in the slurry solution satisfies dispersion conditions of 1≤

D90/D50≤

1.5, and 2 nm<

D50<

160 nm.

5. The manufacturing method of claim 1, wherein the carbon raw material in (b) further comprises at least one selected from the group consisting of natural graphite, artificial graphite, soft carbon, hard carbon, pitch, calcined coke, graphene, carbon nanotube, and combinations thereof.

6. The manufacturing method of claim 5, wherein the pitch includes components insoluble in quinoline (QI) of 0 wt % to 20 wt %, and has a softening point (SP) of 10°

C. to 120°

C.

7. The manufacturing method of claim 1, wherein the primary carbonization process in (c) is performed under a pressure of 1 to 20 bar at 400°

C. to 600°

C. for 1 to 24 hours.

8. The manufacturing method of claim 1, wherein the primary carbon-silicon composite after the pulverization in (c) satisfies dispersion conditions of 1≤

D90/D50≤

2.5, and 3 μ

m<

D50<

10 μ

m.

9. The manufacturing method of claim 1, wherein the secondary carbonization process in (d) is performed under a pressure of 0.5 to 20 bar at 900°

C. to 1400°

C. for 0.5 to 24 hours.

10. The manufacturing method of claim 1, wherein the secondary carbon-silicon composite after the pulverization in (d) satisfies dispersion conditions of 1≤

D90/D50≤

2, and 3 μ

m<

D50<

10 μ

m.

11. A carbon-silicon composite manufactured by the manufacturing method of claim 1.

12. The carbon-silicon composite of claim 11, wherein a mass ratio of silicon (Si) to carbon (C) is 1:

99 to 10;

90.

13. An anode for a secondary battery manufactured by coating an anode slurry on an anode current collector, the anode slurry including:

the carbon-silicon composite of claim 12;

a conductive material;

a binder; and

a thickening agent.

14. A secondary battery comprising the anode for a secondary battery of claim 13.