Polypyrrole film and method of producing the same

• US 4,818,646 A
• Filed: 10/03/1986
• Issued: 04/04/1989
• Est. Priority Date: 10/03/1985
• Status: Expired due to Term

• Current Assignee: Ricoh Company Limited
• Original Assignee: Ricoh Company Limited
• Inventors: Takakubo, Masaaki, Ohsawa, Toshiyuki
• Primary Examiner(s): Niebling, John F.
• Assistant Examiner(s): MARQUIS, STEVEN
• Application Number:
  US06/915,000
• Time in Patent Office: 914 Days
• Field of Search: 429/212, 429/213, 204/59 R, 204/72, 252/518
• US Class Current: 429/213
• CPC Class Codes: C08G 61/124 with a five-membered ring containing one nitrogen atom in the ring
• CPC Class Codes: H01M 10/36 Accumulators not provided for in groups H01M10/05-H01M10/34
• CPC Class Codes: H01M 4/60 of organic compounds
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

A film of polypyrrole doped with a transition metal complex anion having a higher oxidation number of a redox couple consisting of transition metal complex anions and a method of producing the polypyrrole film by electrochemical polymerization are disclosed.

Claims

1. A film of polypyrrole doped with a transition metal complex anion having a higher oxidation number of a redox couple consisting of transition metal complex anions.

2. The film of polypyrrole as claimed in claim 1, wherein said polypyrrole is a polymer of pyrrole, a pyrrole derivative or a mixture thereof which is electrochemically polymerized by anodic oxidation on an anode in the presence of said transition metal complex anion having a higher oxidation number of a redox couple consisting of transition metal complex anions, and said pyrrole derivative being selected from the group consisting of 3-methylpyrrole, 3-ethylpyrrole, 3-n-propylpyrrole, 3-n-butylpyrrole, 3-decylpyrrole, 3-benzylpyrrole, 3-cyclohexylpyrrole, 3-methoxypyrrole, 3-ethoxypyrrole, 3,4-dimethylpyrrole, 3,4-diethylpyrrole, 3,4-di-n-propylpyrrole, 3,4-didodecylpyrrole, 3,4-dipropoxypyrrole, 3,4-difurylpyrrole, N-methylpyrrole, N-ethylpyrrole, N-n-propylpyrrole, N-n-butylpyrrole, N-phenylpyrrole, N-(p-tolyl)pyrrole, 3-chloropyrrole, 3-bromopyrrole, 3-iodopyrrole, 3,4-dichloropyrrole, 3,4-dibromopyrrole, and 3,4-diiodopyrrole.

3. The film of polypyrrole as claimed in claim 1, wherein said transition metal complex anion is selected from the group consisting of a cobalt complex anion, a chrome complex anion, a manganese complex anion, an iron complex anion, a titanium complex anion, a copper complex anion, a molybdenum complex anion, and a tungsten complex anion.

4. The film of polypyrrole as claimed in claim 3, wherein said cobalt complex anion is selected from the group consisting of Co(CN)₆^3-, Co(edta)^- (edta:

ethylenediamine-tetraacetate), Co(pdta)^- (pdta;

propylenediamine-tetra-acetate), Co(cydta)^- (cydta;

1,2-cyclohexanediamine-N,N,N'"'"',N'"'"'-tetraacetate), Co(tnta)^- (tnta;

trimethylene-diaminetetraacetate), Co(ata)(CO₃)^2-, (ata;

nitrilo-triacetate), Co(gly)(ata)^- (gly;

glycine), CoCl(edta)^2-, Co(NO₂)(edta)^2-, Co(edta) (ox)^-, Co(edtp)^- (edtp;

ethylenediaminetetrapropionate), Co(tnta)^- (tnta;

trimethylenediaminetetraacetate), Co(glygly)^2- (glygly;

glycylglycinate), Co(mal)₃^3- and Co(dtpa)^2- (dtpa;

diethylenetriaminepentaacetate).

5. The film of polypyrrole as claimed in claim 3, wherein said chrome complex anion is selected from the group consisting of Cr(CN)₆^3-, Cr(ox)₃^3- (ox:

oxalate), Cr(edta)^- (edta;

ethylenediaminetetraacetate), and Cr(mal)₃^3- (mal;

malonate).

6. The film of polypyrrole as claimed in claim 3, wherein said manganese complex anion is selected from the group consisting of Mn(edta)^- (edta:

ethylenediaminetetraacetate), and Mn(CN)₆^3-.

7. The film of polypyrrole as claimed in claim 3, wherein said iron complex anion is selected from the group consisting of Fe(edta)^- (edta:

ethylenediaminetraacetate), Fe(cat)₃^3- (cat;

catecholate), and Fe(CN)₆^3-.

8. The film of polypyrrole as claimed in claim 4, wherein said titanium complex anion is Ti(cat)₃^2- (cat:

catecholate).

9. The film of polypyrrole as claimed in claim 4, wherein said copper complex anion is selected from the group consisting of Cu(pdta)^2- (pdta:

propylenediaminetetraacetate), and Cu(glygly)^2- (glygly;

glycylglycinate).

10. The film of polypyrrole as claimed in claim 4, wherein said molybdenum complex anion is Mo(CN)₈^3-.

11. The film of polypyrrole as claimed in claim 4, wherein said tungsten complex anion is selected the group consisting of W(CN)₈^3- and WCl_5-.

12. A method of producing a polypyrrole film by electrochemically polymerizing pyrrole or a mixture of pyrrole and a pyrrole derivative by anodic oxidation so as to deposit a polypyrrole on an anode in the presence of a transition metal complex anion having a higher oxidation number of a redox couple consisting of transition metal complex anions.

13. The method of producing a polypyrrole film as claimed in claim 12, wherein said pyrrole derivative is selected from the group consisting of 3-methylpyrrole, 3-ethylpyrrole, 3-n-propylpyrrole, 3-n-butylpyrrole, 3-decylpyrrole, 3-benzylpyrrole, 3-cyclohexylpyrrole, 3-methoxypyrrole, 3-ethoxypyrrole, 3,4-dimethylpyrrole, 3,4-diethylpyrrole, 3,4-di-n-propylpyrrole, 3,4-didodecylpyrrole, 3,4-dipropoxypyrrole, 3,4-difurylpyrrole, N-methylpyrrole, N-ethylpyrrole, N-n-propylpyrrole, N-n-butylpyrrole, N-phenylpyrrole, N-(p-tolyl)pyrrole, 3-chloropyrrole, 3-bromopyrrole, 3-iodopyrrole, 3,4-dichloropyrrole, 3,4-dibromopyrrole, and 3,4-diiodopyrrole.

14. The method of producing a polypyrrole film as claimed in claim 12, wherein said transition metal complex anion is selected from the group consisting of a cobalt complex anion, a chrome complex anion, a manganese complex anion, an iron complex anion, a titanium complex anion, a copper complex anion, a molybdenum complex anion, and a tungsten complex anion.

15. The method of producing a polypyrrole film as claimed in claim 12, wherein said transition metal complex anion is a cobalt complex anion selected from the group consisting of Co(CN)₆^3-, Co(edta)-(edta:

ethylenediaminetetraacetate), Co(pdta)^- (pdta propylenediaminetetraacetate), Co(cydta)^- (cydta;

1,2-cyclohexanediamine-N,N,N'"'"',N'"'"'-tetraacetate), Co(tnta)^- (tnta;

trimethylenediaminetetraacetate), Co(ata)(CO₃)² -(ata;

nitrilotriacetate), Co(gly)(ata)^- (gly;

glycine), CoCl(edta)^2-, Co(NO₂)(edta)^2-, Co(edta)(ox)^-, Co(edtp)^- (edtp;

ethylenediaminetetrapropionate), Co(tnta)^- (tnta;

trimethylenediaminetetraacetate), Co(glygly)^2- (glygly glycylglycinate), Co(mal)₃^3- and Co(dtpa)^2- (dtpa;

diethylenetriaminepentaacetate).

16. The method of producing a polypyrrole film as claimed in claim 12, wherein said transition metal complex anion is a chrome complex anion selected from the group consisting of Cr(CN)₆^3-, Cr(ox)₃^3- (ox:

oxalate), Cr(edta)^- (edta;

ethylenediaminetetraacetate), and Cr(mal)₃^3- (mal;

malonate).

17. The method of producing a polypyrrole film as claimed in claim 12, wherein said anode is partially provided at the surface thereof with a material having a smaller electric resistivity than the electric resistivity of said anode.

18. A method of producing an electroconductive polypyrrole film by electrochemically polymerizing pyrrole or a mixture of pyrrole and a pyrrole derivative by anodic oxidation in the presence of a tris(oxalato)chromate ion, Cr(ox)₃^3- (ox:

oxalate), in an aqueous solution, with the potential of an anode being regulated by a reference electrode, said pyrrole derivative being selected from the group consisting of 3-methylpyrrole, 3-ethylpyrrole, 3-n-propylpyrrole, 3-n-butylpyrrole, 3-decylpyrrole, 3-benzylpyrrole, 3-cyclohexylpyrrole, 3-methoxypyrrole, 3-ethoxypyrrole, 3,4-dimethylpyrrole, 3,4-diethylpyrrole, 3,4-di-n-propylpyrrole, 3,4-didodecylpyrrole, 3,4-dipropoxypyrrole, 3,4-difurylpyrrole, N-methylpyrrole, N-ethylpyrrole, N-n-propylpyrrole, N-n-butylpyrrole, N-phenylpyrrole, N-(p-tolyl)pyrrole, 3-chloropyrrole, 3-bromopyrrole, 3-iodopyrrole, 3,4-dichloropyrrole, 3,4-dibromopyrrole, and 3,4-diiodopyrrole.

19. The method of producing an electroconductive polypyrrole film as claimed in claim 18, wherein said anodic oxidation is performed at temperatures between 0°

C. and the freezing point of said aqueous solution.

20. A secondary battery comprising a cathode system in which a cathode comprises a polypyrrole film doped with a transition metal complex anion having a higher oxidation number of a redox couple consisting of transition metal complex anions.