Method for the manufacture of electrode for energy-storage devices

• US 7,563,354 B2
• Filed: 03/24/2005
• Issued: 07/21/2009
• Est. Priority Date: 09/25/2002
• Status: Active Grant

• Current Assignee: Powermers Inc.
• Original Assignee: Gen3 Partners, Inc.
• Inventors: Kogan, Sam, Shkolnik, Nik, Vasiljeva, Svetlana Viktorovna, Logvinov, Sergey Anatolijevich, Timonov, Alexander Mikhailovich, Pivunov, Dmitriy Ivanovich
• Primary Examiner(s): Wilkins; Harry
• Assistant Examiner(s): Mendez; Zulmariam
• Application Number:
  US11/088,509
• Publication Number:
  US 20050217998A1
• Time in Patent Office: 1,580 Days
• Field of Search: 205/198, 205/106, 205/107, 205/108, 205/317, 205/316
• US Class Current: 205/316
• CPC Class Codes: C08G 12/06 Amines
• CPC Class Codes: H01G 11/86 specially adapted for electrodes carbonisation or activation of carbon for the manufacture of electrodes H01G11/34
• CPC Class Codes: H01G 9/0036 Formation of the solid electrolyte layer
• CPC Class Codes: H01M 4/0438 by electrochemical processing electroless electrochemical plating C23C18/54
• CPC Class Codes: H01M 4/0452 from solutions
• CPC Class Codes: H01M 4/0466 Electrochemical polymerisation
• CPC Class Codes: H01M 4/137 Electrodes based on electro-active polymers
• CPC Class Codes: H01M 4/606 containing aromatic main chain polymers
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02E 60/13 Energy storage using capacitors

Abstract

Application of a redox polymer of the poly-[Me(R-Salen)] type onto a conducting substrate is accomplished by the method of electrochemical polymerization. Said polymerization is accomplished by supplying a voltage between the substrate (that serves as an anode) and a counter electrode (that serves as a cathode), with both of them being submerged into the electrolyte containing an organic solvent and the compounds capable of dissolving in said solvent. The process is accompanied by the production of electrochemically inactive (at concentrations of no less than 0.01 mol/l) ions within the range of potentials from −3.0 V to +1.5 V, and metal complex [Me(R-Salen)] dissolved at a concentration of no less than 5-10⁻⁵ mol/l, (where: Me is a transition metal having at least two different degrees of oxidation, R is an electron-donating substituent, Salen is a residue of bis-(salicylaldehyde)-ethylenediamine in Schiff'"'"'s base.

Claims

1. A method of manufacturing an electrode for use in an energy-storage device, the method comprising:

applying a voltage in a pulse mode between a conducting substrate serving as an anode and a counter electrode serving as a cathode, wherein both the conducting substrate and the counter electrode are submerged into an electrolyte comprising no less than 5×

10<sup>−

5</sup> mol/L of a metal complex [Me(R-Salen)] in an organic solvent and compounds capable of dissolving in the organic solvent and producing electrochemically inactive ions at concentrations of no less than 0.01 mol/L within a potential range from about −

3.0 V to about +1.5 V, wherein;

Me is a transition metal having at least two different degrees of oxidation,

R is an electron-donating substituent, and

Salen is a residue of bis-(salicylaldehyde)-ethylenediamine, to form on the conducting substrate an energy-accumulating layer comprising a redox polymer {poly-[Me(R-Salen)]},

wherein;

the pulse mode comprises a plurality of breaks of 0V between pulses of the voltage applied, wherein the duration of the breaks is selected to allow the metal complex to diffuse into the redox polymer, and

the conducting substrate comprising the energy-accumulating layer provides an electrode having a specific energy capacity suitable for use in an energy-storage device.

2. The method of claim 1, wherein each voltage pulse is applied for a duration from about 1 second to about 30 minutes with a pulse ratio of up to 3600.

3. The method of claim 1, wherein the conducting substrate is a conductive material that is electrochemically inactive within the potential range from about −

3.0 V to about +1.5 V.

4. The method of claim 3, wherein the conducting substrate is a carbon material.

5. The method of claim 3, wherein the conducting substrate is a carbon material with a metal coating.

6. The method of claim 3, wherein the conducting substrate is a metal.

7. The method of claim 3, wherein the conducting substrate is an electrically conductive polymer in the form of a film, a porous structure, or a solid foam.

8. The method of claim 1, wherein the organic solvent comprises acetonitrile, dimethyl ketone, or propylene carbonate.

9. The method of claim 1, wherein the compounds are salts comprising a cation selected from tetrabutyl ammonium, tetraethyl ammonium, and tetramethyl ammonium, and an anion selected from perchlorates, tetrafluoroborates, and hexafluorophosphates.

10. The method of claim 1, wherein the transition metal Me is selected from the group consisting of Ni, Pd, Co, Cu, Fe and combinations thereof.

11. The method of claim 1, wherein the electron-donating substituent R is selected from —

OCH₃, —

OC₂H₅, —

OH, and —

CH₃.

12. The method of claim 1, wherein the energy-accumulating layer is formed at a substrate potential no higher than the potential of nonreversible oxidation of the redox polymer.

13. The method of claim 1, further comprising circulating the electrolyte while the energy-accumulating layer is being formed.

14. A method of manufacturing an electrode for use in an energy-storage device, the method comprising:

applying an electrical potential in a pulse mode between an electrode and a counter electrode in an electrolyte comprising one or more salts and a metal complex [Me(R-Salen)] in a solvent, wherein;

Me is a transition metal having at least two different degrees of oxidation,

R is an electron-donating substituent, and

Salen is a residue of bis-(salicylaldehyde)-ethylenediamine;

wherein the pulse mode comprises breaks of 0V between pulses of the electrical potential, the pulses of the electrical potential being adapted to form a redox polymer layer on the electrode, the redox polymer layer comprising {poly-[Me(R-Salen)]}, and the breaks of 0V comprising a time interval adapted to allow the metal complex to diffuse into the redox polymer layer, and

wherein the redox polymer layer so formed on the electrode has a specific energy of at least about 290 J/g.

15. The method of claim 14, wherein Me is selected from Ni, Pd, Co, Cu, Fe and combinations thereof, and R is selected from —

OCH₃, —

OC₂H₅, —

OH, and —

CH₃.

16. The method of claim 14, wherein the one or more salts comprise cations selected from tetrabutyl ammonium, tetraethyl ammonium, and tetramethyl ammonium, and anions selected from perchlorates, tetrafluoroborates, and hexafluorophosphates.

17. The method of claim 14, comprising circulating the electrolyte while applying the electrical potential in a pulse mode.

18. The method of claim 14, wherein the electrical potential is in the range of about +0.85V and about +1.3V versus a silver-chloride electrode.

19. The method of claim 14, wherein each pulse of the electrical potential is applied for a duration between about 1 second to about 30 minutes.

20. The method of claim 14, wherein the pulse mode comprises a pulse ratio of up to 3600.