Solid state catholytes and electrolytes for energy storage devices

• US 9,553,332 B2
• Filed: 09/09/2015
• Issued: 01/24/2017
• Est. Priority Date: 05/15/2013
• Status: Active Grant

• Current Assignee: Quantumscape Battery Incorporated
• Original Assignee: Quantumscape Corporation
• Inventors: Chao, Cheng Chieh, Chen, Zhebo, Holme, Tim, Mayer, Marie A., Riley, Gilbert N. Jr.
• Primary Examiner(s): HARRIS, GARY D
• Application Number:
  US14/849,468
• Publication Number:
  US 20150380766A1
• Time in Patent Office: 503 Days
• Field of Search: 429/322
• US Class Current: 1/1
• CPC Class Codes: C01B 33/00 Silicon; Compounds thereof C01B6/00, C01B21/00, C01B23/00 take precedence; persilicates C01B15/14; carbides C01B32/956
• CPC Class Codes: C01P 2006/40 Electric properties
• CPC Class Codes: C04B 2235/3203 Lithium oxide or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/428 Silicon
• CPC Class Codes: C04B 2235/446 Sulfides, tellurides or selenides
• CPC Class Codes: C04B 2235/447 Phosphates or phosphites calcium phosphates C04B2235/3212, e.g. orthophosphate, hypophosphite
• CPC Class Codes: C04B 35/547 based on sulfides or selenides or tellurides
• CPC Class Codes: C04B 35/6261 Milling
• CPC Class Codes: C04B 35/6262 of calcined, sintered clinker or ceramics
• CPC Class Codes: C04B 35/62645 Thermal treatment of powders or mixtures thereof other than sintering
• 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 10/056 characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
• CPC Class Codes: H01M 10/0562 Solid materials
• CPC Class Codes: H01M 2220/20 Batteries in motive systems, e.g. vehicle, ship, plane
• CPC Class Codes: H01M 2220/30 Batteries in portable systems, e.g. mobile phone, laptop
• CPC Class Codes: H01M 2300/0068 inorganic
• CPC Class Codes: H01M 2300/0071 Oxides
• CPC Class Codes: H01M 2300/0074 Ion conductive at high temperature
• 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 4/136 Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
• CPC Class Codes: H01M 4/366 : as layered products
• 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 4/582 : Halogenides
• CPC Class Codes: H01M 4/5825 : Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• CPC Class Codes: H01M 4/62 : Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
• CPC Class Codes: H01M 4/624 : Electric conductive fillers
• CPC Class Codes: H01M 50/46 : Separators, membranes or diaphragms characterised by their combination with electrodes
• 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

The present invention provides an energy storage device comprising a cathode region having an active region which expands or contracts from a first volume to a second volume during a period of a charge and discharge. The device has a a solid state catholyte material which includes lithium, phosphorus, sulfur, and silicon elements. The device has a protective material formed overlying exposed regions of the cathode material to substantially maintain the sulfur species within the catholyte material. Also included is a novel oxygen doped configuration of Li_aSiP_bS_c containing material.

Claims

1. An energy storage device comprising a cathode region, the cathode region comprising:

an active material region comprising an active material that expands or contracts from a first volume to a second volume during a period of charge and discharge;

a solid state catholyte material spatially confined in spatial regions not occupied by the active material region, wherein the solid state catholyte material comprises;

a lithium element;

a silicon element;

a phosphorous element;

a sulfur element; and

an oxygen element,

wherein the solid state catholyte material is polycrystalline and characterized by a primary CuKα

XRD peak at 2θ

=31°

±

1°

, 2θ

=33°

±

1°

, or 2θ

=43°

±

1°

, and wherein the oxygen element has a ratio to the sulfur element of 1;

2 or less.

2. The device of claim 1, wherein the oxygen element is less than 10 atomic percent of the solid state catholyte material.

3. The device of claim 1, wherein the active material region is greater than about 50 percent by volume of the cathode region, and wherein the solid state catholyte material is less than about 30 percent by volume of the cathode region.

4. The device of claim 1, wherein the active material region is greater than about 45 percent by volume of the cathode region, and wherein the solid state catholyte material is less than about 30 percent by volume of the cathode region.

5. The device of claim 1, further comprising a polymer material configured within a vicinity of the solid state catholyte material.

6. The device of claim 1, wherein the solid state catholyte material comprises a plurality of particles.

7. The device of claim 1, wherein the active material region comprises clusters having a median diameter ranging from about 2 μ

m to about 10 μ

m.

8. The device of claim 1, wherein the solid state catholyte material comprises a plurality of particles interconnected via a necking arrangement, and wherein the particle diameter to neck ratio dimension ranges from 1% to 80% and wherein the cathode region has a porosity of less than 30% of a total volume of the cathode region.

9. The device of claim 1, wherein the active material comprises iron and fluorine.

10. The device of claim 1, wherein the active material is selected from NCA (nickel cobalt aluminum oxide), LMNO (lithium manganese nickel oxide), LCO (lithium cobalt oxide), nickel fluoride (NiF_x, wherein x is from 0 to 2.5), iron fluoride (FeF_z, wherein z is from 0 to 3), and copper fluoride (CuF_y, wherein y is from 0 to 2.5).

11. The device of claim 1, wherein the solid state catholyte material is selected from Li_aSiP_bS_cO_d wherein 2≦

a≦

10, 0.5≦

b≦

2.5, 4≦

c≦

12, and d≦

3.

12. The device of claim 11, wherein a is 6, b is 1.5, and c is 7, and d is 1.

13. The device of claim 1, wherein the oxygen element has a ratio to the sulfur element of 1:

10 or less.

14. The device of claim 1, wherein the active material region is greater than 50 percent by volume of the cathode region.

15. The device of claim 1, wherein the solid state catholyte material has a room temperature ionic conductivity ranging from 10⁻

5 to 5×

10<sup>−

2</sup> S/cm and an electrical conductivity less than 10<sup>−

5</sup> S/cm.

16. The device of claim 15, wherein the room temperature ionic conductivity ranges from 10⁻

4 to 10<sup>−

2</sup> S/cm.

17. The device of claim 1, wherein the solid state catholyte material is characterized by:

a room temperature ionic conductivity ranging from 10<sup>−

5</sup> S/cm to 10<sup>−

2</sup> S/cm; and

an electrical conductivity less than 10<sup>−

5</sup> S/cm.

18. The device of claim 1, wherein the solid state catholyte is characterized by:

a room temperature ionic conductivity ranging from 10<sup>−

5</sup> S/cm to 10<sup>−

2</sup> S/cm;

an electrical conductivity less than 10<sup>−

5</sup> S/cm; and

a first major CuKα

XRD peak between about 41 to 45°

2θ

, a second major CuKα

XRD peak between about 30 to 35°

2θ

, and a third major CuKα

XRD peak between 51-54°

2θ

.

19. The device of claim 1, wherein the solid state catholyte material is selected from Li_aSiP_bS_cO_d, wherein 2≦

a≦

10, 0.5≦

b≦

2.5, 4≦

c≦

12, and d≦

3, and wherein any impurities are less than 10 atomic percent.

20. The device of claim 1, wherein the solid state catholyte material is characterized by primary Raman peaks at 418±

10 cm<sup>−

1</sup>, 383±

10 cm<sup>−

1</sup>, 286 ±

10 cm<sup>−

1</sup>, and 1614±

10 cm<sup>−

1</sup> when measured by a Renishaw inVia Raman microscope.

21. The device of claim 1, wherein the solid state catholyte material is characterized by a ⁷Li NMR peak shift at 1.18 ₁₃ ppm.

22. The device of claim 1, wherein the solid state catholyte material is characterized by at least one ³¹P NMR peak shift ranging from 86-88 ppm, 92-94 ppm, or 73-78 ppm.

23. The device of claim 11, wherein a is 4, b is 0.9, c is 4 and d is 0.5.

24. The device of claim 1, comprising a protective material overlaying exposed regions of the active material to substantially maintain the sulfur element within the solid state catholyte material, wherein the protective material is selected from AlF₃, LiF, LiAlF₄, LiPO₄, Al₂O₃, TiO₂, lithium titanate, lithium beta alumina, LiNbO₃, LiCoO₂, FeOF, and FeOx.