Lithium battery structures employing composite layers, and fabrication methods to produce composite layers

• US 9,252,455 B1
• Filed: 08/12/2011
• Issued: 02/02/2016
• Est. Priority Date: 04/14/2010
• Status: Expired due to Fees

• Current Assignee: HRL Laboratories LLC (The Boeing Co.)
• Original Assignee: HRL Laboratories LLC (The Boeing Co.)
• Inventors: Liu, Ping, Hicks-Garner, Jocelyn, Gross, Adam F., Liu, Jun
• Primary Examiner(s): Ryan, Patrick
• Assistant Examiner(s): GRESO, AARON J
• Application Number:
  US13/208,341
• Time in Patent Office: 1,635 Days
• Field of Search: 429/144, 429/122, 429/188
• US Class Current: 1/1
• CPC Class Codes: H01M 10/052 Li-accumulators
• 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 12/08 composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
• CPC Class Codes: H01M 2300/0071 Oxides
• CPC Class Codes: H01M 4/366 as layered products
• CPC Class Codes: H01M 4/382 Lithium H01M4/405 takes precedence
• CPC Class Codes: H01M 50/417 Polyolefins
• CPC Class Codes: H01M 50/431 Inorganic material
• CPC Class Codes: H01M 50/434 Ceramics
• CPC Class Codes: H01M 50/449 having a layered structure
• CPC Class Codes: H01M 50/451 comprising layers of only organic material and layers containing inorganic material
• CPC Class Codes: H01M 50/457 comprising three or more layers
• CPC Class Codes: H01M 50/497 Ionic conductivity
• 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

Abstract

This invention provides lithium-based batteries that include one or more inorganic barrier layers disposed between the anode and the cathode. The inorganic barrier layer is a lithium-ion conductor and is non-permeable to lithium-containing compounds, such as lithium polysulfides or lithium dendrites. The inorganic barrier layer may be in direct contact with the anode or cathode, or electrically isolated from the anode and cathode. The principles disclosed herein solve the problem of maintaining electrical isolation of the anode and cathode, while providing efficient lithium-ion conduction without crossover of other lithium species that would otherwise limit the power performance of the battery.

Claims

1. A lithium-based battery comprising:

(a) an anode for supplying or receiving lithium ions;

(b) a cathode for receiving or supplying said lithium ions;

(c) a liquid electrolyte for transporting said lithium ions between said anode and said cathode;

(d) a separator for electrically isolating said anode and said cathode, wherein said separator is permeable to said lithium ions;

(e) a substrate layer disposed between said anode and said cathode; and

(f) a structurally rigid and continuous inorganic barrier layer coated onto said substrate layer, wherein said inorganic barrier layer is a lithium-ion conductor and is non-permeable to lithium dendrites produced by a lithium reaction at said cathode, wherein said inorganic barrier layer has a lithium-ion conductivity from about 10<sup>−

5</sup> S/cm to about 10<sup>−

2</sup> S/cm at a temperature from −

50°

C. to 80°

C., and wherein said inorganic barrier layer has an electronic conductivity from about 10<sup>−

2</sup> S/cm to about 10² S/cm at a temperature from −

50°

C. to 80°

C.

2. The battery of claim 1, wherein said inorganic barrier layer is in direct contact with said cathode.

3. The battery of claim 1, wherein said inorganic barrier layer is in direct contact with said anode.

4. The battery of claim 1, wherein said inorganic barrier layer is electrically isolated from said anode.

5. The battery of claim 4, wherein said inorganic barrier layer is electrically isolated from said anode and from said cathode.

6. The battery of claim 1, wherein said substrate layer is a porous polymer.

7. The battery of claim 1, wherein said substrate layer is in direct contact with said separator.

8. The battery of claim 1, wherein said substrate layer is in direct contact with said cathode.

9. The battery of claim 1, said battery further comprising a second inorganic barrier layer disposed between said anode and said cathode, wherein said second inorganic barrier layer is a lithium-ion conductor.

10. The battery of claim 9, wherein said second inorganic barrier layer is electrically isolated from said anode and from said cathode.

11. The battery of claim 9, wherein each of said inorganic barrier layer and said second inorganic barrier layer is electrically isolated from said anode and from said cathode.

12. The battery of claim 11, wherein said substrate layer is coated on one side with said inorganic barrier layer and is coated on the opposite side with said second inorganic barrier layer.

13. The battery of claim 1, wherein said inorganic barrier layer comprises one or more compounds selected from the group consisting of VO_x (x≦

2.5), MnO_x (x≦

2), Li_xMn₂O₄ (0≦

x≦

2), Li_xCoO₂ (0≦

x≦

1), Li_xTiO₂ (0≦

x≦

1), Li_3+xTi₅O₁₂ (0≦

x≦

4), Li_xTiS₂ (0≦

x≦

1), Li_xNiO₂ (0≦

x≦

1), Li_xV₂O_y (0≦

x≦

5, 4≦

y≦

5), Li_xWO₃ (0≦

x≦

0.5), Li_xNb₂O₅ (0≦

x≦

3), Li_xFePO₄ (0≦

x≦

1), Li_xCoPO₄ (0≦

x≦

1), Li_xVPO₄ (0≦

x≦

1), and combinations thereof.

14. A lithium-ion battery comprising:

(a) an anode for supplying or receiving lithium ions;

(b) a cathode for receiving or supplying said lithium ions;

(c) a liquid electrolyte for transporting said lithium ions between said anode and said cathode;

(d) a separator for electrically isolating said anode and said cathode, wherein said separator is permeable to said lithium ions;

(e) a substrate layer disposed between said anode and said cathode; and

(f) a structurally rigid and continuous inorganic barrier layer coated onto said substrate layer, wherein said inorganic barrier layer is a lithium-ion conductor and is non-permeable to lithium dendrites produced by a lithium reaction at said cathode, wherein said inorganic barrier layer has a lithium-ion conductivity from about 10<sup>−

5</sup> S/cm to about 10<sup>−

2</sup> S/cm at a temperature from −

50°

C. to 80°

C., and wherein said inorganic barrier layer has an electronic conductivity from about 10<sup>−

2</sup> S/cm to about 10² S/cm at a temperature from −

50°

C. to 80°

C.