Rugged, gel-free, lithium-free, high energy density solid-state electrochemical energy storage devices

• US 9,853,325 B2
• Filed: 09/28/2016
• Issued: 12/26/2017
• Est. Priority Date: 06/29/2011
• Status: Active Grant

• Current Assignee: Space Charge, LLC
• Original Assignee: Space Charge, LLC
• Inventors: Sweeney, Daniel C., Read, John B.
• Primary Examiner(s): Cantelmo, Gregg
• Application Number:
  US15/279,254
• Publication Number:
  US 20170069932A1
• Time in Patent Office: 454 Days
• CPC Class Codes: H01G 11/04 Hybrid capacitors
• CPC Class Codes: H01G 11/46 Metal oxides
• CPC Class Codes: H01G 11/56 Solid electrolytes, e.g. gels; Additives therein
• 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 2008/1293 Fuel cells with solid oxide electrolytes
• CPC Class Codes: H01M 2300/0077 based on zirconium oxide
• CPC Class Codes: H01M 4/0404 by coating on electrode collectors
• CPC Class Codes: H01M 4/0426 Sputtering
• CPC Class Codes: H01M 4/0428 Chemical vapour deposition
• 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 4/483 for non-aqueous cells H01M4/485 takes precedence
• CPC Class Codes: H01M 4/521 of iron for aqueous cells
• 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 4/8657 layered
• CPC Class Codes: H01M 4/88 Processes of manufacture
• CPC Class Codes: H01M 8/1246 the electrolyte consisting of oxides
• CPC Class Codes: H01M 8/1253 the electrolyte containing zirconium oxide
• CPC Class Codes: H01M 8/126 the electrolyte containing cerium oxide
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries
• CPC Class Codes: Y02E 60/13 : Energy storage using capacitors
• CPC Class Codes: Y02E 60/50 : Fuel cells
• CPC Class Codes: Y02P 70/50 : Manufacturing or production processes characterised by the final manufactured product

Abstract

Described are solid-state electrochemical energy storage devices and methods of making solid-state electrochemical energy storage devices in which components of the batteries are truly solid-state and do not comprise a gel. Nor do they rely on lithium-containing electrolytes. Electrolytes useful with the solid-state electrochemical energy storage described herein include, for example, ceramic electrolytes exhibiting a crystal structure including voids or crystallographic defects that permit conduction or migration of oxygen ions across a layer of the ceramic electrolyte. Disclosed methods of making solid-state electrochemical energy storage devices include multi-stage deposition processes, in which an electrode is deposited in a first stage and an electrolyte is deposited in a second stage.

Claims

1. A Faradaic solid-state energy storage device comprising:

a first electrode,

wherein the first electrode has a first thickness greater than 1 nm and less than or equal to 80 nm, and

wherein the first electrode comprises a first redox-supporting transition metal, an oxide of the first redox-supporting transition metal, or a combination of the first redox-supporting transition metal and the oxide of the first redox-supporting transition metal;

a solid electrolyte positioned in direct contact with the first electrode,

wherein the solid electrolyte has a second thickness greater than 1 nm and less than or equal to 500 nm, and

wherein the solid electrolyte comprises a solid-state, oxygen ion conducting ceramic electrolyte, wherein the solid-state, oxygen ion conducting ceramic electrolyte has a crystal structure including vacancies that permit conduction or migration of oxygen ions through the crystal structure; and

a second electrode positioned in direct contact with the solid electrolyte,

wherein the second electrode has a third thickness greater than 1 nm and less than or equal to 80 nm, and

wherein the second electrode comprises a second redox-supporting transition metal, an oxide of the second redox-supporting transition metal, or a combination of the second redox-supporting transition metal and the oxide of the second redox-supporting transition metal.

2. The Faradaic solid-state energy storage device of claim 1, wherein the first electrode is dispersed on a first electrically conductive supporting substrate, or wherein the second electrode is dispersed on a second electrically conductive supporting substrate, or both.

3. The Faradaic solid-state energy storage device of claim 1, wherein the first electrode, the second electrode, and the solid electrolyte are independently fabricated using a controllable deposition method including one or more techniques selected from the group consisting of:

atomic layer deposition, magnetron sputtering, sputter deposition, molecular beam epitaxy, pulsed deposition, and chemical vapor deposition.

4. The Faradaic solid-state energy storage device of claim 1, wherein the first thickness and the third thickness are independently between 10 nm and 80 nm and wherein the second thickness is between 15 nm and 500 nm.

5. The Faradaic solid-state energy storage device of claim 1, wherein the first redox-supporting transition metal, the second redox-supporting transition metal, or both the first redox-supporting transition metal and the second redox-supporting transition metal comprise a transition metal having two non-zero oxidation states.

6. The Faradaic solid-state energy storage device of claim 1, wherein the first redox-supporting transition metal and the second redox-supporting transition metal have different oxidation states.

7. The Faradaic solid-state energy storage device of claim 1, wherein the first redox-supporting transition metal and the second redox-supporting transition metal are independently Co, or Ni.

8. The Faradaic solid-state energy storage device of claim 1, wherein the first redox-supporting transition metal comprises ruthenium, wherein the second redox-supporting transition metal comprises ruthenium, or wherein both the first redox-supporting transition metal and the second redox-supporting transition metal comprise ruthenium.

9. The Faradaic solid-state energy storage device of claim 1, wherein the first redox-supporting transition metal and the second redox-supporting transtion metal exhibit between 3 and 6 positive oxidation states.

10. The Faradaic solid-state energy storage device of claim 1, wherein the solid electrolyte has a temperature of between 50°

C. and 600°

C., and wherein the solid electrolyte permits conduction or migration of oxygen ions through the solid electrolyte for participation in redox reactions at the first electrode and the second electrode.

11. The Faradaic solid-state energy storage device of claim 1, further comprising:

a second solid electrolyte positioned in direct contact with the second electrode,

wherein the second solid electrolyte has a fourth thickness greater than 1 nm and less than or equal to 500 nm, and

wherein the second solid electrolyte comprises a second solid-state, oxygen ion conducting ceramic electrolyte, wherein the second solid-state, oxygen ion conducting ceramic electrolyte has the crystal structure including vacancies that permit conduction or migration of oxygen ions through the crystal structure; and

a third electrode positioned in direct contact with the second solid electrolyte,

wherein the third electrode has a fifth thickness greater than 1 nm and less than or equal to 80 nm, and

wherein the third electrode comprises a third redox-supporting transition metal, an oxide of the third redox-supporting transition metal, or a combination of the third redox-supporting transition metal and the oxide of the third redox-supporting transition metal.

12. The Faradaic solid-state energy storage device of claim 1, wherein the first redox-supporting transition metal comprises manganese, wherein the second redox-supporting transition metal comprises manganese, or wherein both the first redox-supporting transition metal and the second redox-supporting transition metal comprise manganese.

13. The Faradaic solid-state energy storage device of claim 1, wherein the first electrode has a first oxidation state and the second electrode has a second oxidation state, and wherien a difference between the first oxidation state and the second oxidation state provides a stored electrical energy density of between 10 J/cm³ and 750 J/cm³.

14. The Faradaic solid-state energy storage device of claim 1, wherein the solid-state, oxygen ion conducting ceramic comprises yttria-stabilized zirconia (YSZ) having the crystal structure including vacancies that permit conduction or migration of oxygen ions through the crystal structure.

15. A method of making a Faradaic solid-state energy storage device, the method comprising:

depositing a first electrode on a substrate,

wherein the first electrode has a first thickness greater than 1 nm and less than or equal to 80 nm,

wherein the first electrode comprises a first redox-supporting transition metal, an oxide of the first redox-supporting transition metal, or a combination of the first redox-supporting transition metal and the oxide of the first redox-supporting transition metal, and

wherein depositing the first electrode includes depositing using a first controllable deposition method;

depositing a solid electrolyte on the first electrode,

wherein the solid electrolyte has a second thickness greater than 1 nm and less than or equal to 500 nm,

wherein the solid electrolyte comprises a solid-state, oxygen ion conducting ceramic electrolyte, wherein the solid-state, oxygen ion conducting ceramic has a crystal structure including vacancies that permit conduction or migration of oxygen ions through the crystal structure, and

wherein depositing the solid electrolyte includes depositing using a second controllable deposition method; and

depositing a second electrode on the solid electrolyte,

wherein the second electrode has a third thickness greater than 1 nm and less than or equal to 80 nm,

wherein the second electrode comprises a second redox-supporting transition metal, an oxide of the second redox-supporting transition metal, or a combination of the second redox-supporting transition metal and the oxide of the second redox-supporting transition metal, and

wherein depositing the second electrode includes depositing using a third controllable deposition method.

16. The method of claim 15, further comprising:

depositing a second solid electrolyte on the second electrode,

wherein the second solid electrolyte has a fourth thickness greater than 1 nm and less than or equal to 500 nm,

wherein the second solid electrolyte comprises a second solid-state, oxygen ion conducting ceramic electrolyte, wherein the second solid-state, oxygen ion conducting ceramic electrolyte has a crystal structure including vacancies that permit conduction or migration of oxygen ions through the crystal structure, and

wherein depositing the second solid electrolyte includes depositing using a fourth controllable deposition method; and

depositing a third electrode on the second solid electrolyte,

wherein the third electrode has a fifth thickness greater than 1 nm and less than or equal to 80 nm,

wherein the third electrode comprises a third redox-supporting transition metal, an oxide of the third redox-supporting transition metal, or a combination of the third redox-supporting transition metal and the oxide of the third redox-supporting transition metal, and

wherein depositing the third electrode includes depositing using a fifth controllable deposition method.

17. The method of claim 15, wherein the first redox-supporting transition metal and the second redox-supporting transition metal independently comprise ruthenium, manganese, cobalt, or nickel, and wherein the solid-state, oxygen ion conducting ceramic electrolyte comprises yttria-stabilized zirconium (YSZ) having the crystal structure including vacancies that permit conduction or migration of oxygen ions through the crystal structure.

18. The method of claim 15, further comprising initiating redox reactions at the first electrode and the second electode to reversibly establish stored electrical energy having a density of between 10 J/cm³ and 750 J/cm³.

19. A Faradaic solid-state energy storage device comprising:

a first electrode,

wherein the first electrode has a first thickness greater than 1 nm and less than or equal to 80nm, and

wherein the first electrode comprises a cobalt oxide or a nickel oxide;

a solid electrolyte positioned in direct contact with the first electrode,

wherein the solid electrolyte has a second thickness greater than 1 nm and less than or equal to 500 nm, and

wherein the solid electrolyte comprises a solid-state, oxygen ion conducting yttrium stabilized zirconium (YSZ) electrolyte, wherein the solid-state, oxygen ion conducting YSZ electrolyte has a crystal structure including vacancies that permit conduction or migration of oxygen ions through the YSZ;

a second electrode positioned in direct contact with the solid electrolyte,

wherein the second electrode has a third thickness greater than 1 nm and less than or equal to 80nm, and

wherein the second electrode comprises cobalt oxide or nickel oxide;

a plurality of additional solid electrolytes, each of the plurality of additional solid electrolytes positioned in direct contact with one or two electrodes,

wherein the plurality of additional solid electrolytes each independently have thicknesses greater than 1 nm and less than or equal to 500 nm, and

wherein the plurality of additional solid electrolytes comprise the solid-state, oxygen ion conducting ceramic electrolyte; and

a plurality of additional electrodes, each of the plurality of additional electrodes positioned in direct contact with one or two of the plurality of additional solid electrolytes,

wherein the plurality of additional electrodes each independently have thicknesses greater than 1 nm and less than or equal to 80 nm, and

wherein the plurality of additional electrodes each independently comprise cobalt oxide or nickel oxide.

20. The Faradaic solid-state energy storage device of claim 19, wherein oxidation states of the cobalt oxide or the nickel oxide alternate from electrode to electrode.