Plating metal negative electrodes under protective coatings

• US 20010041294A1
• Filed: 07/09/2001
• Published: 11/15/2001
• Est. Priority Date: 02/18/1998
• Status: Active Grant

• Current Assignee: PolyPlus Battery Company
• Original Assignee: PolyPlus Battery Company
• Inventors: Visco, Steven J., De Jonghe, Lutgard C., Chu, May-Ying
• Granted Patent: US 6,723,140 B2
• Time in Patent Office: Days
• US Class Current: 429/231.9
• 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 electrode, the method comprising:

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

(b) electrolytically transporting ions of the alkali metal through the protective layer to intercalate into the carbon to form the electrode.

2. The method of

claim 1

, wherein the electrochemical cell is a discharged battery and wherein electrolytically transporting the alkali metal ions to form the electrode is an initial charging operation.

3. The method of

claim 2

, wherein the battery is a primary battery.

4. The method of

claim 1

, further comprising (c) removing the electrode from the electrochemical cell.

5. The method of

claim 4

, further comprising (d) assembling a battery including the electrode.

6. The method of

claim 1

, wherein the material that intercalates ions of the alkali metal is selected from the group consisting of carbon, titanium sulfide, and iron sulfide.

7. The method of

claim 6

, wherein the material that intercalates ions of the alkali metal is carbon.

8. An 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 material that intercalates ions of the alkali metal located between and adherent to the current collector and the protective layer;

a material that intercalates ions of the alkali metal located between and adherent to the current collector and the protective layer;

wherein the electrode precursor does not comprise an alkali metal.

9. The alkali metal electrode precursor of

claim 8

, wherein the current collector is a layer of metal.

10. The alkali metal electrode precursor of

claim 8

, wherein the metal in the layer of metal is selected from the group consisting of copper, nickel, stainless steel, and zinc.

11. The alkali metal electrode precursor of

claim 8

, wherein the current collector is a metallized plastic sheet.

12. The alkali metal electrode precursor of

claim 8

, wherein the material that intercalates ions of the alkali metal is selected from the group consisting of carbon, titanium sulfide, and iron sulfide.

13. The alkali metal electrode precursor of

claim 8

, wherein the material that intercalates ions of the alkali metal is carbon.

14. The alkali metal electrode precursor of

claim 8

, wherein protective layer is conductive to lithium ions.

15. The alkali metal electrode precursor of

claim 8

, wherein protective layer includes at least one of a lithium silicate, a lithium borate, a lithium aluminate, lithium oxide, a lithium phosphate, a lithium phosphorus oxynitride, a lithium silicosulfide, a lithium borosulfide, a lithium aluminosulfide, and a lithium phosphosulfide.

16. The alkali metal electrode precursor of

claim 8

, wherein the protective layer has a thickness of between about 50 angstroms and 5 micrometers.

17. The alkali metal electrode precursor of

claim 16

, wherein the protective layer has a thickness of between about 500 angstroms and 2000 angstroms.

18. The alkali metal electrode precursor of

claim 8

, wherein the protective layer has an ionic conductivity of between about 10⁻

8 and about 10<sup>−

2</sup> (ohm-cm)<sup>−

1</sup>.

19. 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 layer of material that intercalates ions of the alkali metal located between and adherent to the current collector and the protective layer; and

c) an electrolyte;

wherein the precursor does not include an alkali metal.

20. The battery or battery precursor of

claim 19

, wherein the alkali metal comprises at least one of lithium and sodium.

21. The battery or battery precursor of

claim 19

, 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.

22. The battery or battery precursor of

claim 19

, wherein the protective layer has a thickness of between about 50 angstroms and 3000 angstroms.

23. The battery or battery precursor of

claim 19

, wherein the electrolyte is a liquid electrolyte.

24. The battery or battery precursor of

claim 19

, wherein the electrolyte is a polymer or gel electrolyte.

25. The battery or battery precursor of

claim 19

, wherein the positive electrode includes an electrochemically active metal oxide.

26. A method of fabricating a battery, the method comprising:

(a) providing an electrode precursor in an electrochemical cell, the electrode precursor comprising (i) a current collector, (ii) 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 (iii) sandwiched between the current collector and the protective layer, a material that intercalates ions of the alkali metal;

(b) providing a positive electrode; and

(c) transporting alkali metal ions through the protective layer to intercalate alkali metal ions into the intercalation material and form the battery.

27. The method of

claim 26

, wherein the electrochemical cell is a discharged battery and wherein transporting the alkali metal ions to form the electrode is an initial charging operation.

28. The method of

claim 27

, wherein the discharged battery is a secondary battery.

29. The method of

claim 26

, wherein the positive electrode is a metal oxide electrode.

30. The method of

claim 29

, wherein the positive electrode is selected from the group consisting of lithium manganese oxide, lithium cobalt oxide, lithium nickel oxide, lithium vanadium oxide, and mixed oxides of any of these compounds.