Methods for making hollow carbon materials and active materials for electrodes

Patent metadata

Field	Value
Publication number	US-9302914-B2
Application number	US-201414194089-A
Country	US
Kind code	B2
Filing date	Feb 28, 2014
Priority date	Feb 28, 2014
Publication date	Apr 5, 2016
Grant date	Apr 5, 2016

Abstract

In an example of a method for making a hollow carbon material, a carbon black particle is obtained. The carbon black particle has a concentric crystallite structure with an at least partially amorphous carbon core and a graphitic carbon shell surrounding the at least partially amorphous carbon core. The carbon black particle is exposed to any of a heat treatment, a chemical treatment, or an electrochemical treatment which removes the at least partially amorphous carbon core to form the hollow carbon material.

First claim

What is claimed is:

1. A method for making a hollow carbon material, the method comprising:
obtaining a carbon black particle having a concentric crystallite structure with an at least partially amorphous carbon core and a graphitic carbon shell surrounding the at least partially amorphous carbon core; and
exposing the carbon black particle to a chemical treatment with an inorganic acid or an electrochemical treatment with HClO 4 , thereby removing the at least partially amorphous carbon core to form the hollow carbon material.

2. The method as defined in claim 1 wherein the chemical treatment includes reacting the carbon black particle with the inorganic acid.

3. The method as defined in claim 2 wherein:
the inorganic acid is selected from HNO 3 and H 2 SO 4 ;
a concentration of the inorganic acid ranges from about 40% to about 75%;
and a reaction time is at least 20 hours.

4. The method as defined in claim 2 , further comprising exposing the carbon black particle and the inorganic acid to a temperature ranging from about 25° C. to about 70° C.

5. The method as defined in claim 1 wherein the electrochemical treatment includes electrochemically reacting the carbon black particle with a 0.05 M to 1 M HClO 4 solution at a temperature ranging from about 25° C. to about 550° C. and for a time ranging from about 2 hours to about 10 hours.

6. A method for making an active material for an electrode, the method comprising:
obtaining a carbon black particle having a concentric crystallite structure with an at least partially amorphous carbon core and a graphitic carbon shell surrounding the at least partially amorphous carbon core;
exposing the carbon black particle to any of a heat treatment, a chemical treatment, or an electrochemical treatment, thereby removing the at least partially amorphous carbon core to form a hollow carbon material; and
incorporating sulfur, tin, or tin oxide into a hollow core of the hollow carbon material, thereby forming a hollow carbon composite, wherein the sulfur is incorporated via melt infusing or vapor infusing, and wherein the tin or tin oxide is incorporated via an incipient wetness impregnation technique.

7. The method as defined in claim 6 wherein the heat treatment includes exposing the carbon black particle to i) air or ii) a controlled environment including from about 5% to about 50% of oxygen gas and from about 50% to about 95% of an inert gas, at a temperature ranging from about 200° C. to about 550° C. and for a time ranging from about 1 hour to about 10 hours.

8. The method as defined in claim 6 wherein the chemical treatment includes reacting the carbon black particle with an inorganic acid.

9. The method as defined in claim 8 wherein:
the inorganic acid is selected from HNO 3 and H 2 SO 4 ;
a concentration of the inorganic acid ranges from about 40% to about 75%;
and a reaction time is at least 20 hours.

10. The method ad defined in claim 8 , further comprising exposing the carbon black particle and the inorganic acid to a temperature ranging from about 25° C. to about 70° C.

11. The method as defined in claim 6 wherein the electrochemical treatment includes electrochemically reacting the carbon black particle with a 0.05M to 1M HCl O 4 solution at a temperature ranging from about 25° C. to about 550° C. and for a time ranging from about 2 hours to about 10 hours.

12. A method for making an active material for an electrode, the method comprising:
obtaining a carbon black particle having a concentric crystallite structure with an at least partially amorphous carbon core and a graphitic carbon shell surrounding the at least partially amorphous carbon core;
exposing the carbon black particle to any of a heat treatment, a chemical treatment, or an electrochemical treatment, thereby removing the at least partially amorphous carbon core to form a hollow carbon material; and
incorporating sulfur into a hollow core of the hollow carbon material, thereby forming a hollow carbon composite, wherein the incorporating of the sulfur into the hollow core of the hollow carbon material includes:
mixing the hollow carbon material with elemental sulfur at a weight ratio ranging from 1:3 to 1:4, thereby forming a mixture;
encapsulating the mixture in a tube after exposing the tube to a vacuum below 200 mtorr; and
exposing the encapsulated mixture to an elevated temperature for a predetermined time, thereby infusing the elemental sulfur into the hollow core of the hollow carbon material.

13. The method as defined in claim 12 wherein:
infusing the elemental sulfur is accomplished via melt infusing;
the elevated temperature ranges from about 115° C. to about 165° C.; and
the predetermined time ranges from about 10 hours to about 20 hours.

14. The method as defined in claim 12 wherein:
infusing the elemental sulfur is accomplished via vapor infusing;
the elevated temperature ranges from about 444° C. to about 500° C.; and
the predetermined time ranges from about 10 hours to about 20 hours.

15. A method for making an active material for an electrode, the method comprising:
obtaining a carbon black particle having a concentric crystallite structure with an at least partially amorphous carbon core and a graphitic carbon shell surrounding the at least partially amorphous carbon core;
exposing the carbon black particle to any of a heat treatment, a chemical treatment, or an electrochemical treatment, thereby removing the at least partially amorphous carbon core to form a hollow carbon material; and
incorporating tin into a hollow core of the hollow carbon material, thereby forming a hollow carbon composite, wherein the incorporating of the tin into the hollow core of the hollow carbon material is accomplished by:
exposing the hollow carbon material to a solution including a tin precursor using an incipient wetness impregnation technique;
drying the hollow carbon material;
exposing the dried hollow carbon material to annealing to reduce the tin precursor and form a product including the tin in the hollow core of the hollow carbon material;
cooling the product in an H 2 /Ar atmosphere; and
gradually exposing the product to air.

16. A method for making an active material for an electrode, the method comprising:
obtaining a carbon black particle having a concentric crystallite structure with an at least partially amorphous carbon core and a graphitic carbon shell surrounding the at least partially amorphous carbon core;
exposing the carbon black particle to any of a heat treatment, a chemical treatment, or an electrochemical treatment, thereby removing the at least partially amorphous carbon core to form a hollow carbon material; and
incorporating tin oxide into a hollow core of the hollow carbon material, thereby forming a hollow carbon composite, wherein the incorporating of the tin oxide into the hollow core of the hollow carbon material is accomplished by:
exposing the hollow carbon material to a solution including a tin precursor using an incipient wetness impregnation technique;
drying the hollow carbon material;
exposing the dried hollow carbon material to annealing to reduce the tin precursor and form a product including the tin in the hollow core of the hollow carbon material;
cooling the product in an H 2 /Ar atmosphere; and
exposing the product to annealing in air or an oxidizing environment.

17. The method as defined in claim 12 wherein the heat treatment includes exposing the carbon black particle to i) air or ii) a controlled environment including from about 5% to about 50% of oxygen gas an

Assignees

• Gm Global Tech Operations Inc

Inventors

• Liu Zhongyi
• Xiao Qiangfeng
• Xiao Xingcheng
• Carpenter Michael K
• Cai Mei

Classifications

• H01M4/13

  Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof · CPC title

• H01M4/483

  for non-aqueous cells (H01M4/485 takes precedence) · CPC title

• C01B31/04 Primary

  Chemistry & Metallurgy · mapped topic

• H01M4/625

  Carbon or graphite · CPC title

• H01M10/052

  Li-accumulators · CPC title