Electrode for energy storage devices and electrochemical supercapacitor based on said electrode

• US 7,382,603 B2
• Filed: 04/10/2006
• Issued: 06/03/2008
• Est. Priority Date: 10/14/2003
• Status: Active Grant

• Current Assignee: Powermers Inc.
• Original Assignee: Gen3 Partners, Inc.
• Inventors: Pivunov, Dmitry, Logvinov, Sergey, Timonov, Alexander
• Primary Examiner(s): THOMAS, ERIC W
• Application Number:
  US11/401,173
• Publication Number:
  US 20070065719A1
• Time in Patent Office: 785 Days
• Field of Search: 361/502, 361/503, 429/213, 252/62.2
• US Class Current: 361/503
• CPC Class Codes: H01G 11/48 Conductive polymers
• CPC Class Codes: H01G 11/50 specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
• CPC Class Codes: H01M 14/00 Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
• CPC Class Codes: H01M 2300/0085 Immobilising or gelification of electrolyte
• CPC Class Codes: H01M 4/137 Electrodes based on electro-active polymers
• CPC Class Codes: H01M 4/362 Composites
• CPC Class Codes: H01M 4/381 Alkaline or alkaline earth metals elements H01M4/40 takes precedence
• CPC Class Codes: H01M 4/388 Halogens
• CPC Class Codes: H01M 4/60 of organic compounds
• CPC Class Codes: H01M 4/602 Polymers
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02E 60/13 Energy storage using capacitors

Abstract

An electrode comprises an electrically conductive substrate, a layer of energy accumulating redox polymer deposited onto the substrate, the redox polymer comprising a polymer metal complex with a substituted tetra-dentate Schiff'"'"'s base selected from the group: poly-[Me(R, R′-Schiff-Y)], wherein Me is a transition metal; Y is a bridge group binding the atoms of Nitrogen in the Schiff'"'"'s base; R is an electron-donating substituent comprising a functional group (X)O—, —COO(X), where (X) is an alkali metal; R′ is Hydrogen or Halogen; and wherein the polymer metal complex has the following structure:

The electrochemical capacitor comprises a case housing the above-described positive electrode and a negative electrode disposed inside the case, and an electrolyte filling the space between the electrodes.

Claims

1. An electrode comprising an electrically conductive substrate, a layer of energy accumulating redox polymer deposited onto the substrate, the redox polymer comprising a polymer metal complex with a substituted tetra-dentate Schiff'"'"'s base selected from the group:

poly-[Me(R, R′

-Schiff-Y)],

wherein Me is a transition metal;

Y is a bridge group binding the atoms of Nitrogen in the Schiff base;

R is an electron-donating substituent comprising a functional group (X)O—

, —

COO(X), where (X) is an alkali metal selected from the group consisting of Li and Na;

R′

is Hydrogen or Halogen; and

wherein

the polymer metal complex has the following structure;

with n selected from the range from 2 to 50000.

2. The electrode according to claim 1, wherein the group Schiff-Y comprises Salen, which is a residue of bis(salicylaldehyde)-ethylenediamine.

3. The electrode according to claim 1, wherein the group Schiff-Y is Saltmen, which is a residue of bis(salicylaldehyde)-tetramethylethylenediamine.

4. The electrode according to claim 1, wherein the group Schiff-Y is Salphen, which is a residue of bis(salicylaldehyde)- o-phenylenediamine.

5. The electrode according to claim 1, wherein the transition metal is selected from the group consisting of Ni, Pd, Co, Cu, and Fe.

6. The electrode according to claim 1, wherein the conductive substrate is made of carbon fiber and has a complex relief surface.

7. The electrode according to claim 1, wherein the conductive substrate is made of carbon and has a metal coating.

8. The electrode according to claim 1, wherein the conductive substrate is made of metal and has a complex relief surface.

9. The electrode according to claim 1, wherein the conductive substrate is made of a polymer with electronic conduction made as a film, porous structure or foam.

10. An electrochemical capacitor comprising a case housing a positive electrode and a negative electrode disposed inside the case, and an electrolyte filling the space between the electrodes, wherein the positive electrode comprises an electrically conductive substrate, a layer of energy accumulating redox polymer deposited onto the substrate, the redox polymer comprising a polymer metal complex with a substituted tetra-dentate Schiff'"'"'s base selected from the group:

poly-[Me(R, R′

-Schiff-Y)],

wherein Me is a transition metal;

Y is a bridge group binding the atoms of Nitrogen in the Schiff base;

R is an electron-donating substituent comprising a functional group (X)O—

, —

COO(X), where (X) is an alkali metal selected from the group consisting of Li and Na;

R′

is Hydrogen or Halogen; and

wherein

the polymer metal complex has the following structure;

with n selected from the range from 2 to 50000.

11. The capacitor according to claim 10, wherein the negative electrode comprises an active material containing the same alkali metal contained in the composition of the electron-donating substituent of the redox polymer of the positive electrode.

12. The capacitor according to claim 10, wherein the electrolyte is a solution of a compound in an organic solvent, which compound is soluble in the solvent to a concentration of no less than 0.01 mol/l and which contains ions electrochemically inactive within the range of potentials from −

3.0 to +1.5 V.

13. The capacitor according to claim 12, wherein the compound is a salt of the alkali metal contained in the electron-donating substituent of the energy-accumulating redox polymer of the positive electrode, the salt of the alkali metal selected from the group consisting of perchlorates, tetrafluoroborates, and hexafluorophosphates.

14. The capacitor according to claim 12, wherein the organic solvent is selected from the group consisting of acetonitrile, dimethyl ketone, and propylene carbonate.

15. The capacitor according to claim 10, wherein the electrolyte comprises a stabilizer.

16. The capacitor according to claim 10, wherein the electrolyte comprises a thickener for transitioning the electrolyte into a gel-like state.

17. The capacitor according to claim 10, further comprising a separator disposed between the electrodes and dividing an internal space of the capacitor into a cathode and an anode space.

18. The capacitor according to claim 10, wherein the case is made of a material resistant to the action of the electrolyte.

19. The capacitor according to claim 10, further comprising a device for pouring an electrolyte, a safety valve and a fastening element mounted on the case of the capacitor.

20. The capacitor according to claim 10, wherein the group Schiff-Y is Salen, which is a residue of bis(salicylaldehyde)-ethylenediamine.

21. The capacitor according to claim 10, wherein the group Schiff-Y is Saltmen, which is a residue of bis(salicylaldehyde)-tetramethylethylenediamine.

22. The capacitor according to claim 10, wherein the group Schiff-Y is Salphen, which is a residue of bis(salicylaldehyde)-o-phenylenediamine.

23. The capacitor according to claim 10, wherein the transition metal is selected from the group consisting of Ni, Pd, Co, Cu, and Fe.

24. The capacitor according to claim 10, wherein the conductive substrate is made of carbon fiber and has a complex relief surface.

25. The capacitor according to claim 10, wherein the conductive substrate is made of carbon and has a metal coating.

26. The capacitor according to claim 10, wherein the conductive substrate is made of metal and has a complex relief surface.

27. The capacitor according to claim 10, wherein the conductive substrate is made of a polymer with electronic conduction made as a film, porous structure or foam.

28. The capacitor according to claim 10, wherein the negative electrode comprises an electrically conductive substrate, a layer of energy accumulating redox polymer deposited onto the substrate, the redox polymer comprising a polymer metal complex with a substituted tetra-dentate Schiff'"'"'s base selected from the group:

poly-[Me(R, R′

-Schiff-Y)],

wherein Me is a transition metal;

Y is a bridge group binding the atoms of Nitrogen in the Schiff base;

R is an electron-donating substituent comprising a functional group (X)O—

, —

COO(X), where (X) is an alkali metal contained in the composition of the electron-donating substituent of the energy-accumulation redox polymer of the positive electrode;

R′

is Hydrogen or Halogen; and

wherein

the polymer metal complex has the following structure;

with n selected from the range from 2 to 50000.

29. The capacitor according to claim 28, wherein the group Schiff-Y of the said redox polymer of the negative electrode is Salen, which is a residue of bis(salicylaldehyde)-ethylenediamine.

30. The capacitor according to claim 28, wherein the group Schiff-Y of the said redox polymer of the negative electrode is Saltmen, which is a residue of bis(salicylaldehyde)-tetramethylethylenediamine.

31. The capacitor according to claim 28, wherein the group Schiff-Y of the said redox polymer of the negative electrode is Salphen, which is a residue of bis(salicylaldehyde)-phenylenediamine.

32. The capacitor according to claim 28, wherein the transition metal of the said redox polymer of the negative electrode is selected from the group consisting of Ni, Pd, Co, Cu, and Fe.

33. The capacitor according to claim 28, wherein the said conductive substrate of the negative electrode is made of carbon fiber and has a complex relief surface.

34. The capacitor according to claim 28, wherein the said conductive substrate of the negative electrode is made of carbon and has a metal coating.

35. The capacitor according to claim 28, wherein the said conductive substrate of the negative electrode is made of metal and has a complex relief surface.

36. The capacitor according to claim 28, wherein the said conductive substrate of the negative electrode is made of a polymer with electronic conduction made as a film, porous structure or foam.