Polyacrylonitrile-sulphur composite material

Patent metadata

Field	Value
Publication number	US-9252425-B2
Application number	US-201214115248-A
Country	US
Kind code	B2
Filing date	Mar 7, 2012
Priority date	Mar 2, 2011
Publication date	Feb 2, 2016
Grant date	Feb 2, 2016

Abstract

The invention relates to a method for preparing a polyacrylonitrile-sulfur composite material, in which, polyacrylonitrile is converted to cyclized polyacrylonitrile, and the cyclized polyacrylonitrile is reacted with sulfur to form a polyacrylonitrile-sulfur composite material. By a separation of the preparation method into two partial reactions, the reaction conditions are advantageously able to be optimized for the respective reactions and a cathode material is able to be provided for alkali-sulfur cells with improved electrochemical properties. In addition, the invention relates to a polyacrylonitrile-sulfur composite material, a cathode material, an alkali-sulfur cell or an alkali-sulfur battery as well as to an energy store.

First claim

What is claimed is:

1. A method comprising:
in a first step (a), applying polyacrylonitrile, without adding any sulfur matter to the polyacrylonitrile, to an environment by which the polyacrylonitrile is converted to cyclized polyacrylonitrile; and
in a second step (b) that is performed subsequent to performance of the first step (a), applying a mixture, including the cyclized polyacrylonitrile produced by the first step (a) and sulfur, to an environment by which the mixture forms a polyacrylonitrile-sulfur composite material.

2. The method of claim 1 , wherein step (a) takes place in an oxygen-containing atmosphere.

3. The method of claim 1 , wherein step (a) takes place at a temperature in a range of ≧150° C. to ≦500° C.

4. The method of claim 1 , wherein elemental sulfur is used in step (b).

5. The method of claim 1 , wherein sublimed elemental sulfur is used in step (b).

6. The method of claim 1 , wherein, in step (b), the weight ratio of sulfur to cyclized polyacrylonitrile is 1:1.

7. The method of claim 1 , wherein, in step (b), the weight ratio of sulfur to cyclized polyacrylonitrile is ≧1.5:1.

8. The method of claim 1 , wherein, in step (b), the weight ratio of sulfur to cyclized polyacrylonitrile is ≦20:1.

9. The method of claim 1 , wherein, in step (b), the weight ratio of sulfur to cyclized polyacrylonitrile is ≦15:1.

10. The method of claim 1 , wherein step (b) takes place in an inert gas atmosphere.

11. The method of claim 10 , wherein step (b) takes place in an argon or nitrogen atmosphere.

12. The method of claim 1 , wherein step (b) is at least intermittently carried out in the presence of a vulcanization catalyst.

13. The method of claim 1 , wherein step (b) is at least intermittently carried out in the presence of a vulcanization accelerator.

14. The method of claim 1 , wherein step (b) is at least intermittently carried out in the presence of a vulcanization inhibitor.

15. The method of claim 1 , wherein the method further comprises:
in a third step (c), at least one of removing and extracting excess and unbonded sulfur.

16. The method of claim 1 , further comprising using the polyacrylonitrile-sulfur composite material as cathode material of an alkali-sulfur cell.

17. The method of claim 1 , further comprising using the polyacrylonitrile-sulfur composite material as cathode material of a lithium-sulfur cell.

18. A polyacrylonitrile-sulfur composite material, comprising:
sulfur atoms, wherein, with respect to the total number of sulfur atoms in the polyacrylonitrile-sulfur composite material, a proportion of sulfur atoms bonded in thioamide units is ≦25 atom-percent.

19. The polyacrylonitrile-sulfur composite material of claim 18 , wherein the polyacrylonitrile-sulfur composite material is arranged as cathode material of an alkali-sulfur cell.

20. The polyacrylonitrile-sulfur composite material of claim 18 , wherein the polyacrylonitrile-sulfur composite material is formed by a method that includes: in a first step (a), converting polyacrylonitrile to cyclized polyacrylonitrile; and, in a second step (b), converting the cyclized polyacrylonitrile with sulfur to form a polyacrylonitrile-sulfur composite material.

21. An alkali-sulfur cell or battery, comprising:
an alkali-containing anode;
a cathode; and
an electrolyte that includes at least one electrolytic solvent and at least one conducting salt;
wherein:
the cathode includes a polyacrylonitrile-sulfur composite material that at least one of:
is formed by a method that includes: in a first step (a), converting polyacrylonitrile to cyclized polyacrylonitrile; and, in a second step (b), converting the cyclized polyacrylonitrile with sulfur to form a polyacrylonitrile-sulfur composite material; and
includes polysulfide chains with a chain length of ≧2 to ≦4 sulfur atoms, which are covalently bonded on both sides intermolecularly to a cyclized polyacrylonitrile strand; and

at least one of:
the electrolytic solvent is selected from a group consisting of cyclic ethers, acyclic ethers, and combinations thereof; and
the conducting salt is lithium bis(trifluoromethylsulphonyl)imide.

22. The alkali-sulfur cell or battery of claim 21 , wherein the alkali-sulfur cell or battery is arranged as, or as a part of, an energy store of an electric vehicle, a hybrid vehicle, an electric tool, an electric unit, a screwdriver, a gardening device, a portable computer, a mobile telecommunications unit, a Personal Digital Assistant (PDA), or a high energy storage system of a building.

23. The method of claim 1 , wherein the environment to which the polyacrylonitrile is applied in the first step (a) is different than the environment to which the cyclized polyacrylonitrile is applied in the second step (b).

24. The method of claim 23 , wherein the environment to which the polyacrylonitrile is applied in the first step (a) is an oxygen-containing atmosphere and the environment to which the cyclized polyacrylonitrile is applied in the second step (b) is an inert gas-containing environment.

25. The method of claim 1 , wherein the first step (a) is performed at a different temperature than a temperature at which the second step (b) is performed.

26. The method of claim 25 , wherein the temperature to which the polyacrylonitrile is subjected in the first step (a) is approximately 250° C. and the temperature to which the cyclized polyacrylonitrile is subjected in the second step (b) is approximately 330° C.

27. The method of claim 1 , wherein a duration of the first step (a) is different than a duration of the second step (b).

28. The method of claim 27 , wherein the duration of the first step (a) is less than the duration of the second step (b).

29. The method of claim 28 , wherein the duration of the first step (a) is approximately one hour and the duration of the second step (b) is approximately six hours.

30. The method of claim 1 , wherein the first step (a) is performed used a cyclizing catalyst, and the second step (b) is performed using at least one of a vulcanization catalyst, a vulcanization accelerator, and a vulcanization inhibitor.

31. The method of claim 1 , wherein the first step (a) further produces water and the second step (b) further produces hydrogen sulfide.

32. The method of claim 1 , wherein the polyacrylonitrile-sulfur composite material includes polysulfide chains with a chain length of ≧2 to ≦4 sulfur atoms, which are covalently bonded on both sides intermolecularly to a cyclized polyacrylonitrile strand.

33. The method of claim 32 , wherein the bonding on both sides is intermolecularly to two cyclized polyacrylonitrile strands.

34. The method of claim 32 , further comprising arranging the polyacrylonitrile-sulfur composite material as cathode material of an alkali-sulfur cell.

35. The method of claim 1 , wherein the polyacrylonitrile-sulfur composite material includes sulfur atoms, and, with respect to the total number of sulfur atoms in the polyacrylonitrile-sulfur composite material, a proportion of sulfur atoms bonded in thioamide units is ≦25 atom-percent.

36. The method of claim 35 , further comprising arranging the polyacrylonitrile-sulfur composite material as cathode material of an alkali-sulfur cell.

Assignees

• Wegner Marcus
• Grimminger Jens
• Tenzer Martin
• Fanous Jens
• Bosch Gmbh Robert

Inventors

• Wegner Marcus
• Grimminger Jens
• Tenzer Martin
• Fanous Jens

Classifications

• H01M4/364 Primary

  as mixtures · CPC title

• H01M4/049

  Manufacturing of an active layer by chemical means · CPC title

• H01M4/137

  Electrodes based on electro-active polymers · CPC title

• H01M10/3954

  containing additives or special arrangement in the sulfur compartment · CPC title

• H01M4/1399

  of electrodes based on electro-active polymers · CPC title