Rechargeable thin film battery and method for making the same

• US 6,982,132 B1
• Filed: 08/14/2000
• Issued: 01/03/2006
• Est. Priority Date: 10/15/1997
• Status: Expired due to Fees

• Current Assignee: Trustees of Tufts College
• Original Assignee: Trustees of Tufts College
• Inventors: Liu, Te-Yang, Goldner, Ronald B., Goldner, Mark A., Gerouki, Alexandra, Haas, Terry E.
• Primary Examiner(s): Crepeau, Jonathan
• Application Number:
  US09/638,444
• Time in Patent Office: 1,968 Days
• Field of Search: 429/149, 429/152, 429/160, 429/161, 429/162, 429/319, 429/322, 4292311-2314, 429/231.8, 429/231.95, 429/245, 429/218.1, 296/231, 296/235, 204/192.11
• US Class Current: 429/162
• CPC Class Codes: E06B 9/24 Screens or other constructions affording protection against light, especially against sunshine; Similar screens for privacy or appearance; Slat blindsoperating, guiding or securing devices or arrangements for roll-type closures E06B9/56; free-hanging flexible screens A47H23/00
• CPC Class Codes: G02F 1/1525 characterised by a particular ion transporting layer, e.g. electrolyte
• CPC Class Codes: G02F 1/161 Gaskets; Spacers; Sealing of cells; Filling or closing of cells
• CPC Class Codes: G02F 2001/1502 complementary cell
• CPC Class Codes: G02F 2001/1536 additional, e.g. protective, layer inside the cell
• CPC Class Codes: G02F 2001/1555 Counter electrode
• CPC Class Codes: H01M 10/0436 Small-sized flat cells or batteries for portable equipment
• CPC Class Codes: H01M 10/0525 Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• CPC Class Codes: H01M 10/0562 Solid materials
• CPC Class Codes: H01M 10/0585 of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
• CPC Class Codes: H01M 2300/0068 inorganic
• CPC Class Codes: H01M 4/0471 involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
• CPC Class Codes: H01M 4/131 Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• CPC Class Codes: H01M 4/133 Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
• CPC Class Codes: H01M 4/661 Metal or alloys, e.g. alloy coatings H01M4/669 take precedence
• CPC Class Codes: H01M 4/667 in the form of layers, e.g. coatings
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product
• CPC Class Codes: Y02T 10/70 Energy storage systems for electromobility, e.g. batteries
• CPC Class Codes: Y10T 29/49115 including coating or impregnating

Abstract

A rechargeable, stackable, thin film, solid-state lithium electrochemical cell, thin film lithium battery and method for making the same is disclosed. The cell and battery provide for a variety configurations, voltage and current capacities. An innovative low temperature ion beam assisted deposition method for fabricating thin film, solid-state anodes, cathodes and electrolytes is disclosed wherein a source of energetic ions and evaporants combine to form thin film cell components having preferred crystallinity, structure and orientation. The disclosed batteries are particularly useful as power sources for portable electronic devices and electric vehicle applications where high energy density, high reversible charge capacity, high discharge current and long battery lifetimes are required.

Claims

1. A rechargeable, stackable thin film electrochemical cell for a thin film, solid-state battery comprising:

a dense, non-porous, thin film, unannealed inorganic cathode comprised of a first reversible lithium insertion material, said cathode formed by irradiating a depositing cathode film with an ion source having an ion beam energy of less than 100 eV;

a dense, non-porous, thin film, inorganic anode comprised of a second reversible lithium insertion material;

said first and second insertion materials having intrinsically anisotropic crystallographic lithium ion diffusion directions;

a dense, non-porous, thin film, inorganic, solid-state electrolyte disposed between said cathode and said anode films, said electrolyte film forming a first and second interface respectively with said cathode and anode films;

a first crystallographic lithium ion diffusion direction of said first insertion material aligned in a predominately non-parallel orientation to said cathode-electrolyte interface; and

a second crystallographic lithium ion diffusion direction of said second insertion material aligned in a predominately non-parallel orientation to said anode-electrolyte interface.

2. The cell of claim 1 wherein said electrolyte comprises a material selected from the group consisting of lithium phosphorus oxynitride, lithium aluminum germanium phosphate, and lithium aluminum silicate.

3. The cell of claim 2 wherein said electrolyte is deposited as an amorphous material structure formed by exposing one electrode surface to at least one source of energetic ions, said ions having an elemental composition which comprises at least one first component element of said electrolyte, said ion source having an ion beam energy of less than 100 eV, and thermally evaporating onto said electrode surface a material having an elemental composition which comprises at least one second component element of said electrolyte, wherein said energetic ions and said thermally evaporated material combine to form a thin film of said electrolyte.

4. The cell of claim 1 wherein said first reversible lithium insertion material is selected from the group consisting of cobalt oxide, nickel oxide, manganese oxide, vanadium oxide, titanium oxide, iron oxide, chromium oxide, and mixed metal oxides comprising at least two metals selected from the group consisting of cobalt, nickel, manganese, vanadium, titanium, iron and chromium.

5. The cell of claim 4 wherein said cathode first insertion material is a hexagonal crystalline material and said material lithium ion diffusion direction aligned in a predominately non-parallel orientation to said cathode-electrolyte interface is an (003) plane, said orientation being formed without annealing by exposing a surface of either said electrolyte or a first current collector to at least one source of energetic ions, said ions having an elemental composition which comprises at least one component element of said cathode, said ion source having an ion beam energy of less than 100 eV, and thermally evaporating onto said surface a material having an elemental composition which comprises at least one second component element of said cathode, wherein said energetic ions and said thermally evaporated material combine on said surface to form a dense, thin film cathode.

6. The cell of claim 1 wherein said second reversible lithium insertion material is selected from the group consisting of carbon, tin oxide, indium oxide, indium tin oxide and amorphous glasses comprising tin oxide.

7. The cell of claim 6 wherein said anode second insertion material is a hexagonal crystalline material and said material lithium ion diffusion direction aligned in a predominately non-parallel orientation to said anode-electrolyte interface is a c-plane, said c-plane orientation being formed without annealing by exposing a surface of either said electrolyte or a second current collector to at least one source of energetic ions, said ion source having an ion beam energy of less than 100 eV, and thermally evaporating onto said surface a material having an elemental composition which comprises at least one component element of said second insertion material, wherein said energetic ions and said thermally evaporated material interact on said surface to form a dense, thin film anode.

8. The cell of claim 1 further comprised of a first thin film current collector electrically connected to said cathode and a second thin film current collector electrically connected to said anode.

9. The cell of claim 8 wherein said first and second current collectors are comprised a metal selected from the group consisting of aluminum, copper, cobalt, nickel, chromium and alloys of the same.

10. The cell of claim 8 wherein said first and second current collectors consist of an electronically conductive lithium ion blocking layer, said blocking layer providing a barrier to lithium ion diffusion and transport through said current collectors, said blocking layer having a high oxidation resistance to said first insertion material during cell operation.

11. The cell of claim 10 wherein said first and second current collectors are comprised of a metal nitride or mixed metal nitride comprising at least one metallic element selected from the group consisting of titanium, vanadium, zirconium, hafnium, niobium, and tantalum.

12. The cell of claim 1 wherein said first insertion material is cobalt oxide, said second insertion material is graphite and said electrolyte is lithium phosphorous oxide.

13. The cell of claim 1 wherein

said cathode first insertion material is a hexagonal crystalline material and said material lithium ion diffusion direction aligned in a predominately non-parallel orientation to said cathode-electrolyte interface is an (003) plane, said cathode orientation being formed without annealing by exposing a surface of either said electrolyte or said first current collector to at least one source of first energetic ions, said first ions having an elemental composition which comprises at least one component element of said cathode, said first ion source having an ion beam energy of less than 100 eV, and thermally evaporating onto said surface a first material having an elemental composition which comprises at least one second component element of said cathode, wherein said first energetic ions and said first thermally evaporated material combine on said surface to form a dense, thin film cathode;

and

said anode second insertion material is a hexagonal crystalline material and said material lithium ion diffusion direction aligned in a predominately non-parallel orientation to said anode-electrolyte interface is a c-plane, said anode orientation being formed without annealing by exposing a surface of either said electrolyte or said second current collector to at least one source of second energetic ions, said second ion source having an ion beam energy of less than 100 eV, and thermally evaporating onto said surface a second material having an elemental composition which comprises at least one first component element of said anode, wherein said second energetic ions and said second thermally evaporated material interact on said surface to form a dense, thin film anode.

14. A multicell, stackable, rechargeable thin film, solid-state battery comprising:

a plurality of thin film battery cells of claim 1, each cathode of said cells electrically connected to a first thin film current collector, each anode of said cells electrically connected to a second thin film current collector;

a first portion of said cells being connected to one another in a stacked series relationship, wherein each of said stacked, series-connected cells is separated from an adjacent stacked, series-connected cell by a shared current collector comprised of an electronically conductive, oxidation resistant, lithium ion blocking layer material; and

a second portion of said cells being connected to one another in a parallel relationship, wherein the cathode of each of said parallel-connected cells is electrically connected to the cathode of said adjacent parallel-connected cells by means of said first current collectors and wherein the anode of each of said parallel-connected cells is connected to the anode of said adjacent parallel-connected cells by means of said second current collectors.

15. The battery of claim 14 wherein said battery has a specific energy of at least 500 Watt-hours per kilogram.

16. The battery of claim 14 wherein said battery has an energy density of at least 1000 Watt-hours per liter.

17. The battery of claim 14 wherein each of said cell electrolytes is deposited as an amorphous material structure formed by exposing an electrode surface to at least one source of energetic ions, said ions having an elemental composition which comprises at least one first component element of said electrolyte, said ion source having an ion beam energy of less than 100 eV, and thermally evaporating onto said electrode surface a material having an elemental composition which comprises at least one second component element of said electrolyte, wherein said energetic ions and said thermally evaporated material combine on said electrode surface to form said electrolyte film.

18. The battery of claim 17 wherein each of said cell cathodes is formed on a surface of said first current collector or of said electrolyte by exposing said surface to at least one source of energetic ions, said ions having an elemental composition which comprises at least one first component element of said cathode, said ion source having an ion beam energy of less than 100 eV, and thermally evaporating onto said surface a material having an elemental composition which comprises at least one second component element of said cathode, wherein said energetic ions and said thermally evaporated material combine to form a thin film cathode on said surface.

19. The battery of claim 17 wherein each of said cell anodes is formed on a surface of said second current collector or of said electrolyte by exposing said surface to at least one source of second energetic ions, said second ion source having an ion beam energy of less than 100 eV, and thermally evaporating onto said surface a first anode material having an elemental composition which comprises at least one first component element of said second insertion material, wherein said second energetic ions and said thermally evaporated anode material interact on said surface to form a dense, non porous, thin film anode on said surface.

20. The battery of claim 14 wherein the electrolyte, cathode and anode of each cell are formed by an ion beam assisted deposition process.

21. The battery of claim 14 wherein said electrolyte comprises a material selected from the group consisting of lithium phosphorus oxynitride, lithium aluminum germanium phosphate, and lithium aluminum silicate.

22. The battery of claim 14 wherein said first reversible lithium insertion material is selected from the group consisting of cobalt oxide, nickel oxide, manganese oxide, vanadium oxide, titanium oxide, iron oxide, chromium oxide, and mixed metal oxides comprising at least two elements selected from the group consisting of cobalt, nickel, manganese, vanadium, titanium, iron and chromium.

23. The battery of claim 14 wherein said second reversible lithium insertion material is selected from the group consisting of carbon, tin oxide, indium oxide, and indium tin oxide.

24. The battery of claim 14 wherein said first and second current collectors are comprised of a metal selected from the group consisting of aluminum, copper, cobalt, nickel, chromium and alloys of the same.

25. The battery of claim 14 wherein said first reversible insertion material is cobalt oxide, said second reversible insertion material is graphite carbon, said electrolyte is lithium phosphorous oxynitride, said first and second current collectors is an aluminum copper alloy, and said shared current collector is titanium nitride.

26. A folded battery configuration of the multicell, stackable, rechargeable, thin film battery of claim 14 comprising:

a plurality of multi-cell stacks of electrochemical cells, said cells in said stacks electrically connected in series, each of said stacks having an exposed cathode current collector at a proximal end surface, each of said stacks having an exposed anode current collector at a distal end surface;

a first flexible current collector electrically connected to a plurality of said exposed cathode current collectors;

a second flexible current collector electrically connected to a plurality of said exposed anode current collectors;

an electrically insulating material disposed between each of said stacks, said insulating material maintaining separation between said first and said second flexible current collectors so as to prevent electrical contact between said current collectors upon bending said flexible current collectors;

a first battery terminal in electrical contact with said first flexible current collector, said first flexible current collector so configured as to provide a plurality of bends for making electrical contact with said first terminal; and

a second battery terminal in electrical contact with said second flexible current collector, said second flexible current collector so configured as to provide a plurality of bends for making electrical contact with said second terminal;

wherein the number of said multi-cell stacks, the number of said cells in said stacks, and the number and spacing of said bends in said first and said second flexible current collectors are selected so as to establish a characteristic battery operating voltage and current capacity.

35. The cell of claim 7 wherein said energetic ions have an elemental composition which comprises at least one second component element of said second insertion material.

36. The cell of claim 13 wherein said second energetic ions have an elemental composition which comprises at least one second component element of said second insertion material.

37. The battery of claim 19 wherein said second energetic ions have an elemental composition which comprises at least one second component element of said second insertion material.

27. A low temperature deposition method for making a solid-state, thin film lithium electrochemical cell comprising the steps of:

depositing a first thin film current collector on a substrate;

exposing a surface of said first current collector to at least one source of first energetic ions, said first ions having an elemental composition which comprises at least one component element of a first reversible lithium insertion material, said first ion source having an ion beam energy of less than 100 eV;

thermally evaporating onto said first current collector surface a first evaporant material having an elemental composition which comprises at least one second component element of said first insertion material;

combining said first energetic ions and said first evaporant material on said first current collector surface to form said first insertion material on said first current collector surface;

exposing a surface of said first insertion material to at least one source of second energetic ions, said second ions having an elemental composition which comprises at least one first component element of an electrolyte, said first ion source having an ion beam energy of less than 100 eV;

thermally evaporating onto said first insertion material surface a second evaporant material having an elemental composition which comprises at least one second component element of said electrolyte;

combining said second energetic ions and said second evaporant material to form a thin film electrolyte on said first insertion material surface;

exposing a surface of said electrolyte to at least one source of third energetic ions, said ion source having an ion beam energy of less than 100 eV;

thermally evaporating onto said electrolyte surface a third evaporant material having an elemental composition which comprises at least one component element of said second insertion material;

contacting said third evaporant material with said third energetic ions on said electrolyte surface to form said second insertion material; and

depositing a second current collector on a surface of said second insertion material.

28. The method of claim 27 wherein said first insertion material, said second insertion material, said electrolyte, and said second current collector deposition steps are inverted so that said second insertion material is deposited on said first current collector surface, said electrolyte is deposited on said second insertion material surface, said first insertion material is deposited on said electrolyte surface, and said second current collector is deposited on said first insertion material surface.

29. The method of claim 27 wherein said electrolyte is formed from a material selected from the group consisting of lithium phosphorus oxynitride, lithium aluminum germanium phosphate and lithium aluminum silicate.

30. The method of claim 27 wherein said first reversible lithium insertion material is formed from a material selected from the group consisting of cobalt oxide, nickel oxide, manganese oxide, vanadium oxide, titanium oxide, iron oxide, chromium oxide, and mixed metal oxides comprising at least two metals selected from the group consisting of cobalt, nickel, manganese, vanadium, titanium, iron and chromium.

31. The method of claim 27 wherein said second reversible lithium insertion material is formed from a material selected from the group consisting of carbon, graphite, tin oxide, indium oxide, and indium tin oxide.

32. The method of claim 27 wherein said first and second current collectors are selected from the group consisting of aluminum, copper, cobalt, nickel, chromium and an aluminum-copper alloy.

33. The method of claim 27 wherein said electrolyte, said first insertion material and said second insertion material are deposited at an average deposition rate of at least ten angstroms per second.

34. The method of claim 27 wherein said electrolyte, said first insertion material and said second insertion material are deposited at an average deposition rate of at least twenty five angstroms per second.

38. The method of claim 27 wherein said third energetic ions have an elemental composition which comprises at least one second component element of said second insertion material.

39. The method of claim 27 wherein said first insertion material is cobalt oxide, said second insertion material is graphite and said electrolyte is lithium phosphorous oxide.

40. A folded battery configuration of multi-cell, stackable, rechargeable, thin film solid-state batteries comprising:

a plurality of multi-cell stacks of electrochemical cells, each cell comprised of

a dense, non-porous, thin film, unannealed inorganic cathode comprised of a first reversible lithium insertion material;

a dense, non-porous, thin film inorganic anode comprised of a second reversible lithium insertion material;

said first and second insertion materials having intrinsically anisotropic crystallographic lithium ion diffusion directions;

a dense, non-porous, thin film, inorganic, solid-state electrolyte disposed between said cathode and said anode films, said electrolyte film forming a first and second interface respectively with said cathode and anode films;

a first crystallographic lithium ion diffusion direction of said first insertion material aligned in a predominantly non-parallel orientation to said cathode-electrolyte interface; and

a second crystallographic lithium ion diffusion direction of said second insertion material aligned in a predominantly non-parallel orientation to said anode-electrolyte interface;

each cathode of said cells electrically connected to a first thin film current collector;

each anode of said cells electrically connected to a second thin film current collector;

a first portion of said cells being connected to one another in a stacked series relationship, wherein each of said stacked, series-connected cells is separated from an adjacent stacked, series-connected cell by a shared current collector comprised of an electronically conductive, oxidation resistant, lithium ion blocking layer material;

a second portion of said cells being connected to one another in a parallel relationship, wherein the cathode of each of said parallel-connected cells is electrically connected to the cathode of said adjacent parallel-connected cells by means of said first current collectors and wherein the anode of said parallel-connected cells is connected to the anode of said adjacent parallel-connected cells by means of said second current collectors;

each of said stacked portion of series-connected cells and said stacked portion of parallel-connected cells being electrically connected in series, each of said stacks having an exposed cathode current collector at a proximal end surface and an exposed anode current collector at a distal end surface;

a first flexible current collector electrically connected to a plurality of said exposed cathode current collectors;

a second flexible current collector electrically connected to a plurality of exposed anode current collectors;

an electrically insulating material disposed between each of said stacks, said insulating material maintaining a separation between said first and said second flexible current collectors so as to prevent electrical contact between said current collectors upon bending said flexible current collectors;

a first battery terminal in electrical contact with said first flexible current collector, said firs flexible current collector so configured as to provide a plurality of bends for making electrical contact with said first terminal; and

a second battery terminal in electrical contact with said second flexible current collector, said second flexible current collector so configured as to provide a plurality of bends for making electrical contact with said second terminal;

wherein the number of said multi-cell stacks, the number of said cells in said stacks, and the number and spacing of bends in said first and said second flexible current collectors are selected so as to establish a characteristic battery operating voltage and current capacity.