High energy electrochemical cell having composite solid-state anode

• US 5,147,739 A
• Filed: 08/01/1990
• Issued: 09/15/1992
• Est. Priority Date: 08/01/1990
• Status: Expired due to Term

• Current Assignee: EnerSys Advanced Systems, Inc. (EnerSys)
• Original Assignee: Honeywell Incorporated (Honeywell International Inc.)
• Inventors: Beard, Kirby W.
• Primary Examiner(s): Bell, Mark L.
• Assistant Examiner(s): Einsmann, Margaret V.
• Application Number:
  US07/561,134
• Time in Patent Office: 776 Days
• Field of Search: 429/194, 429/218
• US Class Current: 429/343
• CPC Class Codes: H01M 10/05 Accumulators with non-aqueous electrolyte H01M10/39 takes precedence
• CPC Class Codes: H01M 2300/0025 Organic electrolyte
• CPC Class Codes: H01M 4/0404 by coating on electrode collectors
• CPC Class Codes: H01M 4/0459 Electrochemical doping, intercalation, occlusion or alloying
• CPC Class Codes: H01M 4/13 Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
• CPC Class Codes: H01M 4/364 as mixtures
• CPC Class Codes: H01M 4/366 as layered products
• CPC Class Codes: H01M 4/38 of elements or alloys
• CPC Class Codes: H01M 4/405 Alloys based on lithium
• CPC Class Codes: H01M 4/485 of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy H01M4/505, H01M4/525 take precedence
• CPC Class Codes: H01M 4/505 of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
• 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 4/661 Metal or alloys, e.g. alloy coatings H01M4/669 take precedence
• CPC Class Codes: H01M 4/74 Meshes or woven material; Expanded metal
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

Composite anodes are disclosed which consist of composites comprising lithium or lithium anode substrate in combination with one or more lithium insertion compounds consisting of transition metal chalcogenides or oxides as a coating or dispersion. Both primary and secondary cells utilizing these anodes are described.

Claims

1. An improved composite anode for high rate non-aqueous electrochemical cells including both primary and secondary cells comprising:

(a) a reversible lithium intercalation material selected from transition metal chalcogenides having a metastable phase when contacted with lithium and the ability to reversibly transport lithium ions and having the general formula;

space="preserve" listing-type="equation">Li.sub.x M.sub.a X.sub.b

where

M is selected from transition metals having a reversible lithium insertion ability and a relatively low potential vs. lithium,

X is selected from O, S, and Se,

x, a and b are numbers representing relative combining rations where

space="preserve" listing-type="equation"><

x<

9

space="preserve" listing-type="equation">0.5≦

a≦

6 and

space="preserve" listing-type="equation">1.0≦

b≦

9;

(b) an amount of material selected from lithium or a lithium alloy or combinations thereof;

(c) wherein the node intercalation material is disposed to function as an intermediary ion transport medium between the lithium or lithium alloy and an electrolyte.

2. The composite anode of claim 1 wherein M is selected from one or more of Sc, Ti, Y, Zr, V, Nb, Mo, Ta, W, Cr, Mn, and Co.

3. The composite anode of claim 1 wherein M is selected from one or more of Sc(III), Ti(III), Y(III), Zr(IV), V(II), Nb(III), Mo(III), Ta(IV), W(III), Cr(II) and Mn(II) where the numerals refer to maximum theoretical oxidations states.

4. The composite anode of claim 3 wherein M is selected from Sc(II), Ti(II), Y(II), Zr(II), V(I), Nb(II), Mo(II), Ta(III), W(II), Cr(I) and Mn(I) where the numerals refer to the maximum theoretical oxidation states.

5. The composite anode of claim 1 wherein the intercalation material comprises compounds wherein M is selected from Sc, Ti, Y, Zr and combination thereof.

6. The composite anode of claim 1 wherein the intercalation material comprises compounds wherein M is selected from Sc, Ti, Y, Zr, V, Nb, Mo, Ta, W, Cr, Mn and combination thereof and wherein X is 0.

7. The composite anode of claim 1 wherein the lithium or lithium alloy and the lithium intercalation material form separate and distinct adjacent layers.

8. The composite anode of claim 5 wherein the lithium or lithium alloy and the lithium intercalation material form separate and distinct adjacent layers.

9. The composite anode of claim 6 wherein the lithium or lithium alloy and the lithium intercalation material form separate and distinct adjacent layers.

10. The composite anode of claim 1 wherein the lithium or lithium alloy is combined with the lithium intercalation material in the same layer.

11. The composite anode of claim 5 wherein the lithium or lithium alloy is combined with the lithium intercalation material in the same layer.

12. The composite of claim 6 wherein the lithium or lithium alloy is combined with the lithium intercalation material in the same layer.

13. An electrochemical cell comprising:

(a) a composite anode consisting of;

a reversible lithium intercalation material selected from transition metal chalcogenides having a metastable phase when contacted with lithium and the ability to reversibly transport lithium ions and having the general formula;

space="preserve" listing-type="equation">Li.sub.x M.sub.a X.sub.b

where

M is selected from transition metals having a reversible lithium insertion ability and relatively low potential vs. lithium,

X is selected from O, S, and Se,

x, a and b are numbers representing relative combining ratios where

space="preserve" listing-type="equation">0<

x<

9

space="preserve" listing-type="equation">0.5≦

a≦

6 and

space="preserve" listing-type="equation">1.0≦

b≦

9;

an amount of lithium, lithium alloy or a combination thereof,

wherein the anode intercalation material is disposed to function as an intermediary ion transport medium to minimize direct contact between the lithium or lithium alloy and an electrolyte;

(b) a compatible cathode having a cathode active material and a current collector; and

(c) an electrolyte system.

14. The electrochemical cell of claim 13 wherein the cathode comprises an active metal material and a current collector and the electrolyte system further comprises a solid-state electrolyte separator.

15. The electrochemical cell of claim 13 wherein the cathode further comprises at least a second reversible lithium intercalation compound selected from a group compatible with the intercalation material of the anode and wherein the electrolyte system is non-aqueous with or without co-solvents.

16. The electrochemical cell of claim 15 wherein the intercalation compound of the anode and the cathode are the same varying in the degree of lithium intercalation such that the anode is Li doped and the cathode is Li depleted.

17. The electrochemical cell of claim 15 wherein the electrolyte system is a non-aqueous organic ester-based electrolyte solution containing an amount of lithium salt.

18. The electrochemical cell of claim 15 wherein the intercalation compound of the cathode has a potential of at least 4.0 V versus lithium and >

200 mAh/gm reversible capacity.

21. The electrochemical cell of claim 13 where in M is selected from Sc, Ti, Y, and Zr and combination thereof and wherein the electrolyte comprises non-aqueous organic ester-based electrolyte solution containing an amount of at least one lithium salt.

22. The electrochemical cell of claim 13 wherein the cathode active material is selected from a group consisting of SO₂, SOCl₂, (CF)_n, FeS₂, CuF₂, MnO₂, Bi₂ Pb₂ O₅, V₂ O₅ and the electrolyte is selected from non-aqueous electrolytes with or without co-solvents.

23. The electrochemical cell of claim 21 wherein the cathode active material is selected from a ground consisting of SO₂, SOCl₂, (CF)_n, FeS₂, CuF₂, MnO₂, Bi₂ Pb₂ O₅, V₂ O₅ and the electrolyte is selected from non-aqueous electrolytes with or without co-solvents.

25. The electrochemical cell of claim 22 wherein the anode intercalation compound is selected from Li_x TiO₂, Li_x Ti₂ O₃ (where 0<

x≦

2.0) and mixtures thereof.

19. An active metal non-aqueous electrochemical cell comprising:

(a) a composite anode further comprising;

an amount of first material consisting essentially of reversible lithium intercalation material selected from transition metal chalcogenides having a metastable phase when contacted with lithium and the ability to reversibly transport lithium ions and having the general formula;

space="preserve" listing-type="equation">Li.sub.x M.sub.a X.sub.b

where

M is selected from transition metals having a reversible lithium insertion ability and the relatively low potential vs. lithium,

X is selected from O, S, and Se,

x, a and b are numbers representing relative combining ratios where

space="preserve" listing-type="equation">0<

x<

9

space="preserve" listing-type="equation">0.5≦

a≦

6 and

space="preserve" listing-type="equation">1.0≦

b≦

9;

an amount of a second material consisting essentially of lithium, lithium alloy or a combination thereof,

wherein the anode intercalation material functions as an intermediary ion transport medium to minimize direct contact between the lithium or lithium alloy and an electrolyte, and

wherein the first and second materials are disposed to form separate layers or combine as a dispersion of the second material in the first configured as a distinct layer;

(b) a cathode having a cathode active material comprising a third material int he form of a reversible lithium intercalation compound compatible with that of the anode; and

(c) a non-aqueous electrolyte system.

20. The electrochemical cell of claim 19 wherein the first and second anode material are in the form of a layered structure selected from the first material forming a coating on said second material and laminates thereof of the first and second materials.

24. The electrochemical cell of claim 20 wherein the anode intercalation compound is selected from Li_x TiO₂, Li_x Ti₂ O₃ (where 0<

x≦

2.0) and mixtures thereof.

26. The electrochemical cell of claim 19 wherein the second material is mixed as a distinct dispersion in the first material.

27. The electrochemical call of claim 19 wherein the anode comprises an amount of lithium covered by a layer of the first material which thereby forms the electrolyte and separator for the cell.