Low temperature formation of electrode having electrically conductive metal oxide surface

• US 5,827,580 A
• Filed: 03/27/1996
• Issued: 10/27/1998
• Est. Priority Date: 03/27/1996
• Status: Expired due to Fees

• Current Assignee: Regents of the University of California (University of California)
• Original Assignee: Regents of the University of California (University of California)
• Inventors: Kong, Fanping, Anders, Andre, Anders, Simone, Brown, Ian G., McLarnon, Frank R.
• Primary Examiner(s): PIANALTO, BERNARD D
• Application Number:
  US08/625,270
• Time in Patent Office: 944 Days
• Field of Search: 427/580, 427/126.3, 427/255.3
• US Class Current: 427/580
• CPC Class Codes: C23C 14/0042 Controlling partial pressure or flow rate of reactive or inert gases with feedback of measurements
• CPC Class Codes: C23C 14/083 of refractory metals or yttrium
• CPC Class Codes: H01M 4/26 Processes of manufacture
• CPC Class Codes: H01M 4/32 Nickel oxide or hydroxide electrodes
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

A low temperature process is disclosed for forming metal suboxides on substrates by cathodic arc deposition by either controlling the pressure of the oxygen present in the deposition chamber, or by controlling the density of the metal flux, or by a combination of such adjustments, to thereby control the ratio of oxide to metal in the deposited metal suboxide coating. The density of the metal flux may, in turn, be adjusted by controlling the discharge current of the arc, by adjusting the pulse length (duration of on cycle) of the arc, and by adjusting the frequency of the arc, or any combination of these parameters. In a preferred embodiment, a low temperature process is disclosed for forming an electrically conductive metal suboxide, such as, for example, an electrically conductive suboxide of titanium, on an electrode surface, such as the surface of a nickel oxide electrode, by such cathodic arc deposition and control of the deposition parameters. In the preferred embodiment, the process results in a titanium suboxide-coated nickel oxide electrode exhibiting reduced parasitic evolution of oxygen during charging of a cell made using such an electrode as the positive electrode, as well as exhibiting high oxygen overpotential, resulting in suppression of oxygen evolution at the electrode at full charge of the cell.

Claims

1. A low temperature process for forming a metal suboxide on a substrate surface in a deposition chamber which comprises forming said metal suboxide on the surface of said substrate by cathodic arc deposition while controlling at least one of:

a) the partial pressure of the oxygen present in the deposition chamber; and

b) the density of the metal flux.

2. The process of claim 1 which further comprises providing a negative bias on said substrate with respect to at least one of the electrodes used to form said cathodic arc.

3. The process of claim 1 which further comprises carrying out said process at a temperature ranging from about 0°

C. to about 100°

C.

4. A low temperature process for forming an improved electrode having a generally chemically non-reactive but electrically conductive film formed on the surface thereof which comprises forming on the surface of said electrode an electrically conductive metal suboxide by cathodic arc deposition in a deposition chamber while controlling the oxvgen partial pressure of an oxygen-containing gas in said chamber.

5. A low temperature process for forming an improved electrode for a rechargeable cell capable of suppressing evolution of gas at the electrode surface which comprises forming on the surface of said electrode an electrically conductive metal suboxide by cathodic arc deposition in a deposition chamber while controlling the oxygen partial pressure of an oxygen-containing gas in said chamber.

6. The process of claim 5 wherein said partial pressure of oxygen in said deposition chamber ranges from about 1 Pascal to about 3 Pascals.

7. The process of claim 5 wherein the temperature of said electrode surface during the deposition ranges from about 0°

C. to about 100°

C.

8. The process of claim 7 wherein said electrode comprises a positive electrode.

9. The process of claim 7 wherein said positive electrode comprises an electrode containing nickel oxide.

10. The process of claim 9 wherein said positive nickel oxide-containing electrode has a nickel oxide surface below said conductive metal oxide formed thereon.

11. The process of claim 7 wherein said conductive metal oxide formed on said positive electrode comprises a suboxide of titanium.

12. The process of claim 11 wherein said suboxide of titanium has the formula TiO_x, where x ranges from at least 1.6 to about 1.9.

13. The process of claim 11 wherein said suboxide of titanium has the formula TiO_x, where x ranges from at least 1.7 to about 1.8.

14. A low temperature process for forming an improved nickel oxide electrode for a rechargeable cell characterized by a reduced rate of parasitic evolution of oxygen during charging and reduced evolution of oxygen during overcharging of the cell which comprises:

a) forming a plasma of titanium ions between an anode and a titanium cathode in a deposition chamber;

b) maintaining in said chamber during said formation of said plasma, a partial pressure of oxygen, sufficient, relative to the density of the titanium ion flux in said plasma, to form on a surface of a nickel oxide electrode in said chamber, an electrically conductive titanium suboxide.

15. The process of claim 14 wherein said conductive titanium suboxide has the formula TiO_x, where x ranges from at least 1.6 to about 1.9.

16. The process of claim 14 wherein said conductive titanium suboxide has the formula TiO_x, where x ranges from at least 1.7 to about 1.8.

17. The process of claim 14 wherein the temperature of said nickel oxide electrode in said deposition chamber is maintained with a range of from about 0°

C. and about 100°

C.

18. The process of claim 14 wherein the temperature of said nickel oxide electrode in said deposition chamber is maintained with a range of from about 20°

C. and about 100°

C.

19. The process of claim 14 wherein the partial pressure of oxygen in said deposition chamber ranges from about 1 Pascal to about 3 Pascals.