Solid state catholyte or electrolyte for battery using Li
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.
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;
a member selected from the group consisting of a silicon element, tin element, germanium element, and combinations thereof;
a phosphorous element;
a sulfur element; and
an oxygen element,
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 to form a LGPSO, LSPSO, or LTPSO material; and
optionally, a protective material overlying 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 20 atomic percent of the LGPSO, LSPSO, or LTPSO 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 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 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 catholyte material.
6. The device of claim 1 , wherein the 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 μm to about 10 μm.
8. The device of claim 1 , wherein the 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 greater than 100% to form a polycrystalline structure having 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 catholyte material is selected from Li a SiP b S c O d and Li a GeP b S c O d , wherein 2≤a≤10, 0.5≤b≤2.5, 4≤c≤12, and d≤3.
12. The device of claim 1 , wherein the catholyte material is Li a GeP b S c O d , wherein 2≤a≤10, 0.5≤b≤2.5, 4≤c≤12, and d≤3.4.
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 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 15 , wherein the room temperature ionic conductivity ranges from 10 −4 to 10 −2 S/cm.
17. The device of claim 1 , wherein the catholyte material is the LSPSO material and is characterized by:
a room temperature ionic conductivity ranging from 10 −5 S/cm to 10 −2 S/cm; and
an electrical conductivity less than 10 −5 S/cm.
18. The device of claim 1 , wherein the catholyte is the LSPSO material and is characterized by:
a room temperature ionic conductivity ranging from 10 −5 S/cm to 10 −2 S/cm;
an electrical conductivity less than 10 −5 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 catholyte material is Li a SiP b S c O 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 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.
21. The device of claim 1 , wherein the catholyte material is the LSPSO material doped with a tin element to form an LSTPSO alloy material, wherein the lithium element ranges from 30 to 50 at %, wherein the silicon element ranges from 0 to 15 at %, wherein the tin element ranges from 0 to 15 at %, wherein the phosphorous element ranges from 5 to 17 at %, wherein the sulfur element ranges from 30-55 at %, and wherein the oxygen element ranges from 0-15 at % of the catholyte material.
22. The device of claim 1 , wherein the catholyte material is the LMPSO material doped with a dopant and characterized by a plurality of different XRD peaks in a plurality of ranges including 18-21°, 26-28°, 28-31°, 40-42°, and 46-48°.
23. The device of claim 1 , wherein the catholyte material is characterized by at least one 7 Li NMR peak shift ranging from 0.5-1.5 ppm.
24. The device of claim 1 , wherein the catholyte material is characterized by at least one 31 P NMR peak shifts ranging from 86-88 ppm, 92-94 ppm, 73-78 ppm, or 108-109.5 ppm.