Plating metal negative electrodes under protective coatings

• US 6,402,795 B1
• Filed: 08/25/1998
• Issued: 06/11/2002
• Est. Priority Date: 02/18/1998
• Status: Expired due to Term

• Current Assignee: PolyPlus Battery Company
• Original Assignee: PolyPlus Battery Company
• Inventors: Visco, Steven J., De Jonghe, Lutgard C., Chu, May-Ying
• Primary Examiner(s): CHANEY, CAROL DIANE
• Application Number:
  US09/139,603
• Time in Patent Office: 1,386 Days
• Field of Search: 296/235, 429/236, 429/218.1, 429/218.95
• US Class Current: 29/623.5
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/054 Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
• CPC Class Codes: H01M 10/0562 Solid materials
• CPC Class Codes: H01M 10/446 Initial charging measures
• CPC Class Codes: H01M 4/0438 by electrochemical processing electroless electrochemical plating C23C18/54
• CPC Class Codes: H01M 4/045 Electrochemical coating; Electrochemical impregnation
• CPC Class Codes: H01M 4/0452 from solutions
• CPC Class Codes: H01M 4/0459 Electrochemical doping, intercalation, occlusion or alloying
• CPC Class Codes: H01M 4/0461 Electrochemical alloying
• CPC Class Codes: H01M 4/12 of consumable metal or alloy electrodes use of alloy compositions as active materials H01M4/38
• CPC Class Codes: H01M 4/134 Electrodes based on metals, Si or alloys
• CPC Class Codes: H01M 4/1395 of electrodes based on metals, Si or alloys
• CPC Class Codes: H01M 4/661 Metal or alloys, e.g. alloy coatings H01M4/669 take precedence
• CPC Class Codes: H01M 50/46 Separators, membranes or diaphragms characterised by their combination with electrodes
• CPC Class Codes: Y10T 29/49108 Electric battery cell making
• CPC Class Codes: Y10T 29/49115 including coating or impregnating

Abstract

A method for forming lithium electrodes having protective layers involves plating lithium between a lithium ion conductive protective layer and a current collector of an “electrode precursor.” The electrode precursor is formed by depositing the protective layer on a very smooth surface of a current collector. The protective layer is a glass such as lithium phosphorus oxynitride and the current collector is a conductive sheet such as a copper sheet. During plating, lithium ions move through the protective layer and a lithium metal layer plates onto the surface of the current collector. The resulting structure is a protected lithium electrode. To facilitate uniform lithium plating, the electrode precursor may include a “wetting layer” which coats the current collector.

Claims

1. A method of fabricating an alkali metal electrode, the method comprising:

(a) providing an alkali metal electrode precursor in an electrochemical cell, the electrode precursor including a current collector, a wetting layer, and a glassy or amorphous protective layer forming a substantially impervious layer which is a single ion conductor conductive to ions of an alkali metal; and

(b) plating the alkali metal through the protective layer to form a layer of the alkali metal between the current collector and the protective layer to form the alkali metal electrode.

2. The method of claim 1, wherein the alkali metal electrode precursor further comprises a wetting layer located between and adherent to the current collector and the protective layer, wherein the wetting layer (i) intercalates alkali metal ions conducted by the single ion conductor or (ii) alloys with the alkali metal having ions conducted by the single ion conductor.

3. The method of claim 1, wherein the electrochemical cell is a discharged battery and wherein plating the alkali metal to form the electrode is an initial charging operation.

4. The method of claim 3, wherein the battery is a primary battery.

5. The method of claim 3, further comprising transporting the discharged battery prior to plating the alkali metal to form the alkali metal electrode.

6. The method of claim 1, further comprising (c) removing the alkali metal electrode from the electrochemical cell.

7. The method of claim 6, further comprising (d) assembling a battery including the alkali metal electrode.

8. The method of claim 1, wherein the alkali metal electrode is provided in a primary battery selected from the group consisting of lithium manganese dioxide batteries, lithium (CF)_x batteries, lithium thionyl chloride batteries, lithium sulfur dioxide batteries, lithium iron sulfide batteries (Li/FeS₂), lithium polyaniline, and lithium iodine batteries.

9. The method of claim 1, wherein the alkali metal electrode is provided in a secondary battery selected from the group consisting of lithium-sulfur batteries, lithium cobalt oxide batteries, lithium nickel oxide batteries, lithium manganese oxide batteries, and lithium vanadium oxide batteries.

10. An alkali metal electrode precursor comprising:

a current collector;

a glassy or amorphous protective layer forming a substantially impervious layer which is a single ion conductor conductive to ions of an alkali metal; and

a wetting layer located between and adherent to the current collector and the protective layer, wherein the wetting layer (i) intercalates alkali metal ions conducted by the single ion conductor or (ii) alloys with the alkali metal having ions conducted by the single ion conductor;

wherein the alkali metal electrode precursor does not comprise an alkali metal.

11. The alkali metal electrode precursor of claim 10, wherein the current collector is a layer of metal.

12. The alkali metal electrode precursor of claim 11, wherein the metal is selected from the group consisting of copper, nickel, stainless steel, and zinc.

13. The alkali metal electrode precursor of claim 10, wherein the current collector is a metallized plastic sheet.

14. The alkali metal electrode precursor of claim 10, wherein the wetting layer comprises a material that alloys with the alkali metal.

15. The alkali metal electrode precursor of claim 14, wherein the wetting layer material is selected from the group consisting of silicon, magnesium, aluminum, lead, silver, and tin.

16. The alkali metal electrode precursor of claim 10, wherein the wetting layer comprises a material that intercalates ions of the alkali metal.

17. The alkali metal electrode precursor of claim 10, wherein the wetting layer material is selected from the group consisting of carbon, titanium sulfide, and iron sulfide.

18. The alkali metal electrode precursor of claim 10, wherein protective layer is conductive to lithium ions.

19. The alkali metal electrode precursor of claim 10, wherein protective layer includes at least one of a lithium silicate, a lithium borate, a lithium aluminate, a lithium phosphate, a lithium phosphorus oxynitride, a lithium silicosulfide, a lithium borosulfide, a lithium aluminosulfide, and a lithium phosphosulfide.

20. The alkali metal electrode precursor of claim 10, wherein the protective layer has a thickness of between about 50 angstroms and 5 micrometers.

21. The alkali metal electrode precursor of claim 20, wherein the protective layer has a thickness of between about 500 angstroms and 2000 angstroms.

22. The alkali metal electrode precursor of claim 10, wherein the protective layer has a conductivity of between about 10⁻

8 and about 10<sup>−

2</sup> (ohm-cm)<sup>−

1</sup>.

23. A battery or a battery precursor comprising:

a) a positive electrode comprising a source of mobile alkali metal ions on charge;

b) a precursor to an alkali metal negative electrode including

a current collector,

a glassy or amorphous protective layer forming a substantially impervious layer which is a single ion conductor conductive to ions of an alkali metal, and

a wetting layer located between and adherent to the current collector and the protective layer, wherein the wetting layer (i) intercalates alkali metal ions conducted by the single ion conductor or (ii) alloys with the alkali metal having ions conducted by the single ion conductor; and

c) an electrolytes;

wherein the precursor does not include an alkali metal.

24. The battery or battery precursor of claim 23, wherein the alkali metal comprises at least one of lithium and sodium.

25. The battery or battery precursor of claim 23, wherein the protective layer includes at least one of a lithium silicate, a lithium borate, a lithium aluminate, a lithium phosphate, a lithium phosphor nitride, a lithium silicosulfide, a lithium borosulfide, a lithium aluminosulfide, and a lithium phosphosulfide.

26. The battery or battery precursor of claim 23, wherein the protective layer has a thickness of between about 50 angstroms and 3000 angstroms.

27. The battery or battery precursor of claim 23, wherein the electrolyte is a liquid electrolyte.

28. The battery or battery precursor of claim 23, wherein the electrolyte is a polymer or gel electrolyte.

29. The battery or battery precursor of claim 23, wherein the positive electrode includes an electrochemically active material is selected from the group consisting of sulfides of the alkali metal, polysulfides of the alkali metal, and combinations thereof.

30. The battery or battery precursor of claim 23, wherein the battery or battery precursor is a primary battery selected from the group consisting of lithium manganese dioxide-batteries, lithium (CF)_x batteries, lithium thionyl chloride batteries, lithium sulfur dioxide batteries, lithium iron sulfide batteries (Li/FeS₂), lithium polyaniline, and lithium iodine batteries.

31. The battery or battery precursor of claim 23, wherein the battery or battery precursor is a secondary battery selected from the group consisting of lithium-sulfur batteries, lithium cobalt oxide batteries, lithium nickel oxide batteries, lithium manganese oxide batteries, and lithium vanadium oxide batteries.

32. A method of fabricating an alkali metal-sulfide battery, the method comprising:

(a) providing an alkali metal electrode precursor in an electrochemical cell, the electrode precursor including a current collector and a glassy or amorphous protective layer forming a substantially impervious layer which is a single ion conductor conductive to ions of an alkali metal,

(b) providing a metal-sulfide positive electrode; and

(c) plating the alkali metal through the protective layer to form a layer of the alkali metal between the current collector and the protective layer to form the alkali metal-sulfide battery.

33. The method of claim 32, wherein the alkali metal electrode precursor further comprises a wetting layer located between and adherent to the current collector and the protective layer, wherein the wetting layer (i) intercalates alkali metal ions conducted by the single ion conductor or (ii) alloys with the alkali metal having ions conducted by the single ion conductor.

34. The method of claim 32, wherein the electrochemical cell is a discharged battery and wherein plating the alkali metal to form the electrode is an initial charging operation.

35. The method of claim 34, wherein the discharged battery is a primary battery.

36. The method of claim 34, further comprising transporting the discharged battery prior to plating the alkali metal to form an alkali metal electrode.

37. The method of claim 34, wherein the discharged battery is a secondary battery.