Solid state catholyte or electrolyte for battery using LiaMPbSc (M=Si, Ge, and/or Sn)

Patent metadata

Field	Value
Publication number	US-10535878-B2
Application number	US-201815986675-A
Country	US
Kind code	B2
Filing date	May 22, 2018
Priority date	May 15, 2013
Publication date	Jan 14, 2020
Grant date	Jan 14, 2020

Abstract

The present invention provides an energy storage device comprising a cathode region or other element. The device has a major active region comprising a plurality of first active regions spatially disposed within the cathode region. The major active region expands or contracts from a first volume to a second volume during a period of a charge and discharge. The device has a catholyte material spatially confined within a spatial region of the cathode region and spatially disposed within spatial regions not occupied by the first active regions. In an example, the catholyte material comprises a lithium, germanium, phosphorous, and sulfur (“LGPS”) containing material configured in a polycrystalline state. The device has an oxygen species configured within the LGPS containing material, the oxygen species having a ratio to the sulfur species of 1:2 and less to form a LGPSO material. 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 dopant configuration of the Li a MP b S c (LMPS) [M=Si, Ge, and/or Sn] containing material.

First claim

What is claimed:

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 catholyte material spatially confined in spatial regions not occupied by the active material region, wherein the catholyte material comprises:
a lithium element from greater than 30 to 50 atomic % of the catholyte material;
a silicon element from greater than 0 to 10 atomic % of the catholyte material;
a tin element from greater than 0 to 10 atomic % of the catholyte material;
a phosphorous element from greater than 5 to 15 atomic % of the catholyte material;
a sulfur element from greater than 30 to 55 atomic % of the catholyte material; and
an oxygen element from greater than 0 to 15 atomic % of the catholyte material,
wherein the Si/(Si+Sn) stoichiometry is from 0.25 to 0.75; and
wherein the catholyte material is characterized by a primary CuKα XRD peak at 2θ=30°±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; and

optionally, a protective material overlaying exposed regions of the active material to substantially maintain the sulfur element within the catholyte material.

2. The device of claim 1 , wherein the oxygen element is less than 10 atomic percent of the material and greater than 0 atomic %.

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 catholyte material is less than about 30 percent by volume of the cathode region.

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

5. The device of claim 1 , wherein the catholyte material comprises a plurality of particles.

6. The device of claim 1 , wherein the active material region comprises clusters having a median diameter ranging from about 2 μm to about 10 μm.

7. The device of claim 1 , wherein the catholyte material comprises a plurality of polycrystalline particles interconnected via a necking arrangement, and wherein the particle diameter to neck ratio dimension ranges from 1% to 100% and wherein the cathode region has a porosity of less than 30% of a total volume of the cathode region.

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

9. 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 1 to 2.5), and iron fluoride (FeF z , wherein z is from 1 to 3).

10. The device of claim 1 , wherein the catholyte material is selected from Li a (SiSn)P b S c wherein 2<a<10, 0.5<b<2.5, 4<c<12, and comprises an oxygen element from greater than 0 to 15 atomic % of the catholyte material.

11. The device of claim 10 , wherein a is 6, b is 1.5, c is 7, and comprises an oxygen element from greater than 0 to 15 atomic % of the catholyte material.

12. The device of claim 1 , wherein the oxygen element has a ratio to the sulfur element of 1:10 or less.

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

14. The device of claim 1 , wherein the catholyte material has a room temperature ionic conductivity ranging from 10 −5 to 5×10 −2 S/cm.

15. The device of claim 14 , wherein the catholyte material has a room temperature ionic conductivity ranging from 10 −5 to 5×10 −2 S/cm and an electrical conductivity less than 10 −5 S/cm.

16. The device of claim 1 , wherein the catholyte material is characterized by primary Raman peaks at 418±10 cm −1 , 383±10 cm −1 , 286±10 cm −1 , and 1614±10 cm −1 when measured by a Renishaw inVia Raman microscope.

17. The device of claim 1 , wherein the catholyte material is characterized by a 7 Li NMR peak shift at 0.732 ppm, 0.812 ppm, 0.955 ppm, or 1.176 ppm.

18. The device of claim 1 , wherein the catholyte material is characterized by at least one 31 P NMR peak shift ranging from 86-88 ppm, 92-94 ppm, 73-78 ppm, or 108-109.5 ppm.

19. The device of claim 1 , wherein the catholyte material is LMPSO material doped with a dopant and characterized by a plurality of different XRPD peaks in a plurality of ranges including 18-21°, 26-28°, 28-31°, and 46-48°.

Assignees

• Quantumscape Corp

Inventors

• Chao Cheng-Chieh
• Chen Zhebo
• Holme Tim
• Mayer Marie A
• Riley Jr Gilbert N

Classifications

• C04B2235/447

  Phosphates or phosphites, e.g. orthophosphate or hypophosphite · CPC title

• C04B2235/446

  Sulfides, tellurides or selenides · CPC title

• C04B2235/428

  Silicon · CPC title

• C04B2235/3203

  Lithium oxide or oxide-forming salts thereof · CPC title

• C04B35/62645

  Thermal treatment of powders or mixtures thereof other than sintering · CPC title