Mixed ionic electronic conductor coatings for redox electrodes

• US 6,210,832 B1
• Filed: 09/01/1998
• Issued: 04/03/2001
• Est. Priority Date: 09/01/1998
• Status: Expired due to Term

• Current Assignee: PolyPlus Battery Company
• Original Assignee: PolyPlus Battery Company
• Inventors: Visco, Steven J., Chu, May-Ying
• Primary Examiner(s): Kalafut, Stephen
• Assistant Examiner(s): WILLS, MONIQUE M
• Application Number:
  US09/145,401
• Time in Patent Office: 945 Days
• Field of Search: 429/212, 429/231.95, 429/218.1, 29/623.5
• US Class Current: 429/218.1
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/06 Lead-acid accumulators semi-lead accumulators H01M10/20
• CPC Class Codes: H01M 2004/028 Positive electrodes
• CPC Class Codes: H01M 4/02 Electrodes composed of, or comprising, active material
• CPC Class Codes: H01M 4/366 as layered products
• CPC Class Codes: H01M 4/525 of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
• CPC Class Codes: H01M 4/581 Chalcogenides or intercalation compounds thereof
• CPC Class Codes: H01M 4/583 Carbonaceous material, e.g. graphite-intercalation compounds or CFx
• CPC Class Codes: H01M 4/62 Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02T 10/70 Energy storage systems for electromobility, e.g. batteries

Abstract

Disclosed is a redox electrode for a battery cell that has a coating to mitigate plugging by precipitated discharge products. The coating comprises a mixed ionic electronic conductor (MIEC) which is applied to the surface of a redox electrode. The presence of the MIEC coating allows for rapid removal of discharge product precipitates from redox electrodes since it is capable of conducting both electrons and ions. As a result, the chemical action necessary to remove such precipitates may take place on both the electrolyte side of the precipitate and at the precipitate/electrode interface. MIEC coatings in accordance with the present invention may be composed of any suitable material having ionic conductivity for a metal ion in a negative electrode with which the redox electrode is to be paired in a battery cell, and reversible redox capacity. Examples include titanium sulfide (TiS₂), iron sulfide (FeS₂), and cobalt oxides.

Claims

1. A positive redox electrode comprising:

a) an electrochemically active material;

b) an electronically conductive material mixed with the electrochemically active materials so that electrons move between the electrochemically active material and the electronically conductive material;

c) a mixed ionic electronic conductor material coating said electronically conductive material, said mixed ionic electronic conductor material having ionic conductivity for a metal ion in a negative electrode with which the redox electrode is to be paired in a battery cell, and reversible redox capacity.

2. The redox electrode of claim 1, further comprising:

c) an ionically conductive material mixed with the electrochemically active materials so that ions move between the ionically conductive material and the electrochemically active material.

3. The redox electrode of claim 1, wherein said electrochemically active material is selected from the group consisting of elemental sulfur, a metal sulfide, a metal polysulfide, and combinations thereof, wherein said metal is selected from the group consisting of alkali metals, alkaline earth metals, and mixtures of alkali and alkaline earth metals.

4. The redox electrode of claim 1, wherein said electrochemically active material comprises a lithium polysulfide.

5. The redox electrode of claim 2, wherein said ionically conductive material is a liquid, gel or solid.

6. The redox electrode of claim 1, wherein said electronically conductive material comprises carbon.

7. The redox electrode of claim 6, wherein said electronically conductive material is in the form of paper, a solid matrix, fibers, or particles.

8. The redox electrode of claim 1, wherein said mixed ionic electronic conductor material comprises TiS₂.

9. The redox electrode of claim 1, wherein said mixed ionic electronic conductor material comprises FeS₂.

10. The redox electrode of claim 1, wherein said mixed ionic electronic conductor material comprises cobalt oxide.

11. The redox electrode of claim 1, wherein said mixed ionic electronic conductor material has a thickness of about 1000 Å

to 5 μ

m.

12. A battery cell comprising:

a) a positive electrode comprising a mixture of

i) an electrochemically active material, and

ii) an electronically conductive material mixed with the electrochemically active materials so that electrons move between the electrochemically active material and the electronically conductive material,

iii) a mixed ionic electronic conductor material coating said electronically conductive material, said mixed ionic electronic conductor material having ionic conductivity for a metal ion in a negative electrode with which the redox electrode is to be paired in a battery cell, and reversible redox capacity,

b) a negative electrode including a metal or metal ion; and

c) an electrolyte separator.

13. The battery cell of claim 12, wherein said redox electrode further comprises:

ii) an ionically conductive material mixed with the electrochemically active materials so that ions move between the ionically conductive material and the electrochemically active material.

14. The battery cell of claim 12, wherein said electrochemically active material is selected from the group consisting of elemental sulfur, a metal sulfide, a metal polysulfide, and combinations thereof, wherein said metal is selected from the group consisting of alkali metals, alkaline earth metals, and mixtures of alkali and alkaline earth metals.

15. The battery cell of claim 12, wherein said first electrochemically active material comprises a lithium polysulfide.

16. The battery cell of claim 12, wherein said electronically conductive material comprises carbon.

17. The battery cell of claim 16, wherein said electronically conductive material is in the form paper, a solid matrix, fibers, or particles.

18. The battery cell of claim 12, wherein said mixed ionic electronic conductor material comprises TiS₂.

19. The battery cell of claim 12, wherein said mixed ionic electronic conductor material comprises FeS₂.

20. The battery cell of claim 12, wherein said mixed ionic electronic conductor material comprises cobalt oxide.

21. The battery cell of claim 12, wherein said mixed ionic electronic conductor material has a thickness of about 1000 Å

to 5 μ

m.

22. The battery cell of claim 12, wherein said battery cell has a thin film format.

23. A method of making a redox electrode, comprising:

a) coating an electronic conductor with a mixed ionic electronic conductor material coating with ionic conductivity for a metal ion in a negative electrode with which the redox electrode is to be paired in a battery cell, and reversible redox capacity;

b) combining an electrochemically active material, and the coated electronic conductor material; and

c) forming the electrode from the combined material.

24. The method of claim 23, further comprising combining an ionically conductive material with the electrode materials in b).

25. The method of claim 23, wherein said electronic conductor comprises fibers or particles, and step b) of said method further comprises:

i) homogenizing the electrode components;

and step c) of said method further comprises;

ii) preparing a film of the homogenized electrode components on a current collector; and

iii) drying the film.

26. The method of claim 23, wherein said electronic conductor comprises paper or a solid matrix, and step b) of said method further comprises:

iv) impregnating the electronic conductor with the electrochemically active material and the ionically conductive material;

and step c) of said method further comprises;

v) drying the impregnated electronic conductor.