Alkaline cell with improved cathode

• US 6,596,438 B2
• Filed: 06/13/2001
• Issued: 07/22/2003
• Est. Priority Date: 06/13/2001
• Status: Expired due to Term

• Current Assignee: Duracell U.S. Operations, Inc. (Berkshire Hathaway Incorporated)
• Original Assignee: Gillette Company (The Procter & Gamble Company)
• Inventors: Zeng, Shuming
• Primary Examiner(s): WEINER, LAURA S
• Application Number:
  US09/880,651
• Publication Number:
  US 20030008211A1
• Time in Patent Office: 769 Days
• Field of Search: 429/232, 429/224, 429/229, 429/206
• US Class Current: 429/232
• CPC Class Codes: H01M 4/043 involving compressing or compaction
• CPC Class Codes: H01M 4/06 Electrodes for primary cells
• CPC Class Codes: H01M 4/08 Processes of manufacture
• CPC Class Codes: H01M 4/625 Carbon or graphite
• CPC Class Codes: H01M 6/08 with cup-shaped electrodes
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

An alkaline electrochemical cell having a cathode comprising manganese dioxide and conductive graphitized mesophase pitch-based carbon fibers having an increased BET surface area of between about 10 and 60 m²/g, desirably between about 10 and 50 m²/g, preferably between about 30 and 50 m²/g by heat treatment between 800 and 1200° C. with potassium hydroxide. The treated graphitized mesophase pitch-based carbon fibers can comprise between about 1 and 100 percent by weight of the total graphite material in the cathode, typically between about 5 and 50 percent by weight of the total graphite. The total graphite in the cathode desirably comprises between about 4 and 10 percent by weight of the cathode. The graphite can be the mixtures of the graphitized mesophase pitch-based carbon fibers with flaky crystalline graphites including expanded graphites. The graphitized mesophase pitch-based carbon fibers have a mean average diameter typically between about 1 and 10 micron. The use of said carbon fibers in the cathode increases cathode conductivity and results in improved cell performance.

Claims

1. An electrochemical cell comprising an anode, an aqueous alkaline electrolyte, and a cathode comprising manganese dioxide and graphite material, wherein said graphite material comprises graphitized carbon fibers having an average BET surface area of between 10 and 60 m²/g.

2. The electrochemical cell of claim 1 wherein the cell is an alkaline cell having an anode comprising zinc.

3. The electrochemical cell of claim 1 wherein said electrolyte comprises an aqueous solution of potassium hydroxide.

4. The electrochemical cell of claim 1 wherein said carbon fibers having an average BET surface area of between 10 and 50 m²/g.

5. The electrochemical cell of claim 4 wherein said carbon fibers comprises graphitized mesophase pitch-based carbon fibers.

6. The electrochemical cell of claim 5 wherein the graphite material in said cathode comprises a mixture of said graphitized mesophase pitch-based carbon fibers and flaky crystalline graphite.

7. The electrochemical cell of claim 5 wherein the graphite material in said cathode comprises a mixture of said graphitized mesophase pitch-based carbon fibers and expanded graphite.

8. The electrochemical cell of claim 1 wherein said carbon fibers having an average BET surface area of between 30 and 50 m²/g.

9. The electrochemical cell of claim 8 wherein said carbon fibers comprises graphitized mesophase pitch-based carbon fibers.

10. The electrochemical cell of claim 1 wherein said carbon fibers have a crystalline size Lc in the crystal “

c”

direction of between 50 and 300 Angstrom and a crystalline size La in the crystal “

a”

direction of between 100 to 300 Angstrom.

11. The electrochemical cell of claim 1 wherein said carbon fibers have a crystalline size Lc in the crystal “

c”

direction of between 100 and 200 Angstrom and a crystalline size La in the crystal “

a”

direction of between 100 to 300 Angstrom.

12. The electrochemical cell of claim 1 wherein said carbon fibers comprises between 4 and 10 percent by weight of the cathode.

13. The electrochemical cell of claim 1 wherein the weight ratio of said carbon fibers to said manganese dioxide is between about 1:

25 (0.04) to 1;

10 (0.10).

14. The electrochemical cell of claim 1 wherein said carbon fibers comprises graphitized mesophase pitch-based carbon fibers.

15. The electrochemical cell of claim 14 wherein the graphite material in said cathode comprises between 4 and 10 percent by weight of said cathode and said graphitized mesophase pitch-based carbon fibers comprises between about 1 and 100 percent by weight of said graphite material.

16. The electrochemical cell of claim 14 wherein the graphite material in said cathode comprises between 4 and 10 percent by weight of said cathode and said graphitized mesophase pitch-based carbon fibers comprises between about 5 and 50 percent by weight of said graphite material.

17. The electrochemical cell of claim 1 wherein said carbon fibers comprises graphitized mesophase pitch-based carbon fibers which have been treated by heating said graphitized mesophase pitch-based carbon fibers with potassium hydroxide at a temperature between about 800°

C. and 1200°

C.

18. The electrochemical cell of claim 1 wherein said carbon fibers comprises graphitized mesophase pitch-based carbon fibers which have been treated by heating said graphitized mesophase pitch-based carbon fibers with potassium hydroxide at a temperature between about 800°

C. and 1200°

C. for a period between about 1 and 2 hours.

19. The electrochemical cell of claim 1 wherein said carbon fibers have a mean average diameter of between 1 and 10 micron.

20. The electrochemical cell of claim 1 wherein said carbon fibers have a mean average diameter of between 1 and 10 micron and a mean average length of between 40 and 150 microns.

21. An electrochemical cell comprising an anode, an aqueous alkaline electrolyte, and a cathode comprising manganese dioxide and graphite material, wherein said graphite material comprises graphitized mesophase pitch-based carbon fibers having an average BET surface area of between 10 and 60 m²/g.

22. An electrochemical cell comprising an anode, an aqueous alkaline electrolyte, and a cathode comprising manganese dioxide and graphite material, wherein said graphite material comprises graphitized mesophase pitch-based carbon fibers having an average BET surface area of between 10 and 50 m²/g.

23. The electrochemical cell of claim 22 wherein said graphitized mesophase pitch-based carbon fibers comprises between 4 and 10 percent by weight of said cathode.

25. The electrochemical cell of claim 23 wherein said graphitized mesophase pitch-based carbon fibers comprises between 4 and 10 percent by weight of said cathode.

24. An electrochemical cell comprising an anode, an aqueous alkaline electrolyte, and a cathode comprising manganese dioxide and graphite material, wherein said graphite material comprises graphitized mesophase pitch-based carbon fibers having an average BET surface area of between 30 and 50 m²/g.

26. An electrochemical cell comprising an anode, an aqueous alkaline electrolyte, and a cathode comprising manganese dioxide and graphite material, wherein said graphite material comprises graphitized carbon fibers having an average BET surface area of between 10 and 60 m²/g and wherein said carbon fibers have a crystalline size Lc in the crystal “

c”

direction of between 50 and 300 Angstrom and a crystalline size La in the crystal “

a”

direction of between 100 to 300 Angstrom.

27. The electrochemical cell of claim 26 wherein said carbon fibers have a crystalline size Lc in the crystal “

c”

direction between 100 and 200 Angstrom.

28. The electrochemical cell of claim 26 wherein said carbon fibers have an average BET surface area of between 30 and 50 m²/g.

29. The electrochemical cell of claim 26 wherein said carbon fibers comprises graphitized mesophase pitch-based carbon fibers.