Method for manufacturing an energy storage device

• US 20070234537A1
• Filed: 03/23/2007
• Published: 10/11/2007
• Est. Priority Date: 03/24/2006
• Status: Active Grant

• Current Assignee: Powermers Inc.
• Original Assignee: Gen3 Partners, Inc.
• Inventors: Kogan, Sam, Logvinov, Sergey, Timonov, Alexander, Chepurnaya, Irina
• Granted Patent: US 7,888,229 B2
• Time in Patent Office: Days
• US Class Current: 29/25.30
• CPC Class Codes: H01G 11/02 using combined reduction-oxidation reactions, e.g. redox arrangement or solion
• CPC Class Codes: H01G 11/22 Electrodes
• CPC Class Codes: H01G 11/24 characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
• CPC Class Codes: H01G 11/26 characterised by their structure, e.g. multi-layered, porosity or surface features
• CPC Class Codes: H01G 11/58 Liquid electrolytes
• CPC Class Codes: H01G 9/15 Solid electrolytic capacitors H01G11/00 takes precedence
• CPC Class Codes: Y02E 60/13 Energy storage using capacitors

Abstract

The present invention relates to methods of manufacturing an electrochemical energy storage device, such as a hybrid capacitor. The method comprises saturating a porous electrically conductive material in a solution comprising an organic solvent and a metal complex or a mixture of metal complexes; assembling a capacitor comprising the positive electrode made of porous electrically conductive material saturated with a metal complex, a negative electrode, and a separator in a casing; introducing the electrolyte solution into the casing; sealing the casing; and subsequent charge-discharge cycling of the capacitor. The charge-discharge cycling deposits a layer of an energy-accumulating redox polymer on the positive electrode. The electrolyte solution for filling the hybrid capacitor contains an organic solvent, a metal complex, and substances soluble to a concentration of no less than 0.01 mol/L and containing ions that are electrochemically inactive within the range of potentials between −3.0 V to +1.5 V.

Claims

1. A method of manufacturing a hybrid capacitor comprising:

(a) saturation of a porous electrically conductive material by soaking it in a solution containing;

an organic solvent; and

a metal complex able to form a stacked redox polymer, or a mixture of said metal complexes, the concentration of a said complex in a said solution is no less than 0.0001 mol/L;

the porous electrically conductive material is soaked in a said solution until the porous electrically conductive material saturated with a said metal complex or a mixture of metal complexes is obtained;

(b) assembly of a capacitor, which implies the placement of the positive electrode made of a said porous electrically conductive material saturated with a metal complex or a mixture of metal complexes obtained by soaking a said porous electrically conductive material in a said solution, a negative electrode, and a separator that separates the positive electrode and the negative electrode in a casing;

introducing an electrolyte solution into the casing, and hermetic sealing of the casing, the said electrolyte solution containing;

an organic solvent;

a metal complex able to form stacked redox polymers or a mixture of said metal complexes;

and a substance soluble in a given solvent to a concentration of no less than 0.01 mol/L and containing ions that are electrochemically inactive within the range of potentials between −

3.0 V to +1.5 V.

(c) execution of no less than one cycle of charging-discharging of the capacitor.

2. The method of claim 1, wherein the porous electrically conductive material is an electronically conductive material with a high specific surface area, which is electrochemically inactive at potentials between −

3.0 V and +1.5 V.

3. The method of claim 2, wherein the porous electrically conductive material is a carbon material with a high specific surface area.

4. The method of claim 2, wherein the porous electrically conductive material is a carbon material coated with metal.

5. The method of claim 2, wherein the porous electrically conductive material is a metal with a high specific surface area.

6. The method of claim 2, wherein the porous electrically conductive material is an electronically conductive polymer in the form of a film, porous structure, or solid foam.

7. The method of claim 1, wherein the organic solvent is selected from the group consisting of acetonitrile, ethanol, alkyl carbonate solvents, and combinations thereof.

8. The method of claim 1, wherein the metal complex is a transition metal complex with a substituted tetradentate Schiff base, a said transition metal having at least two different oxidation states, a said metal complex having a planar structure with the deviation from the plane of no more than 0.1 nm and a branched system of conjugated π

-bonds.

9. The method of claim 8, wherein the metal complex is a metal complex [M(R-Salen)], wherein:

M is a transition metal having at least two different oxidation states,

R a substituent in a Schiff base,

Salen is a residue of bis(salicylaldehyde)ethylenediamine in a Schiff base.

10. The method of claim 9, wherein the transition metal M in the metal complex is selected from the group consisting of Ni, Pd, Co, Cu, Fe.

11. The method of claim 9, wherein the substituent R in the metal complex is selected from the group consisting of H—

and electron-donating substituents CH₃O—

, C₂H₅O—

, HO—

, —

CH₃.

12. The method of claim 8, wherein the metal complex is a metal complex [M(R-Saltmen)], wherein:

M is a transition metal having at least two different oxidation states,

R is a substituent in a Schiff base,

Saltmen is a residue of bis(salicylaldehyde)tetramethylethylenediamine in a Schiff base.

13. The method of claim 12, wherein the transition metal M in a metal complex is selected from the group consisting of Ni, Pd, Co, Cu, Fe.

14. The method of claim 12, wherein the substituent R in a metal complex is selected from the group consisting of H—

and electron-donating substituents CH₃O—

, C₂H₅O—

, HO—

, —

CH₃.

15. The method of claim 1, wherein the temperature of the solution, in which the porous electrically conductive material is soaked, is maintained between 20°

C. and 50°

C.

16. The method of claim 1, wherein the solution, in which the porous electrically conductive material is soaked, may additionally contain substances soluble in the said solution to a concentration of no less than 0.01 mol/L and containing ions that are electrochemically inactive within the range of potentials between −

3.0 V to +1.5 V.

17. The method according to claim 16, wherein the soluble substances in the solution, in which the porous electrically conductive material is soaked, are salts of tetramethylammonium, tetraethylammonium, or tetrabutylammonium—

tetrafluoroborates, perchlorates, hexafluorophosphates.

18. The method of claim 1, wherein the soluble substances in the electrolyte solution are salts of tetramethylammonium, tetraethylammonium, or tetrabutylammonium-tetrafluoroborates, perchlorates, hexafluorophosphates.

19. The method of claim 1, wherein the current density for charging and discharging of the capacitor is between 0.1 mA/cm² and 500 mA/cm².