Solid state catholytes and electrolytes for energy storage devices
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. 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 from 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 5 to 17 atomic % of the catholyte material;
a sulfur element from 35 to 60 atomic % of the catholyte material; and
an oxygen element from greater than 0 to 15 atomic % of the catholyte material,
wherein the atomic amounts of silicon and tin are equal, and
wherein the catholyte material is characterized by primary CuKα XRD peaks at 2θ=30°±1°, 2θ=33°±1°, and 2θ=43°±1°.
2. 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.
3. 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.
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 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.
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 0 to 2.5), iron fluoride (FeF z , wherein z is from 0 to 3), or copper fluoride (CuF y , wherein y is from 0 to 2.5).
10. The device of claim 1 , wherein the catholyte material is Li a SiSnP b S c O d , wherein 2≦a≦10, 0.5≦b≦2.5, 4≦c≦12, and 0≦d≦3.4.
11. The device of claim 10 , wherein the catholyte material is Li 10 SiSnP 2 S 4 O d .
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 and an electrical conductivity less than 10 −5 S/cm.
15. The device of claim 14 , wherein the room temperature ionic conductivity ranges from 10 −4 to 10 −2 S/cm.
16. The device of claim 1 , wherein the catholyte material 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.
17. The device of claim 1 , further comprising a protective material overlying exposed regions of the active material to substantially maintain the sulfur element within the catholyte material.
18. The device of claim 1 , wherein the catholyte material is doped with a dopant and characterized by XRD peaks including 18-21°, 26-28°, 28-31°, 40-42°, and 46-48°.
19. 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.
20. 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.
21. The device of claim 17 , wherein the protective material overlying exposed regions of the active material is selected from the group consisting of AlF 3 , LiF, LiAlF 4 , LiPO 4 , Al 2 O 3 , TiO 2 , lithium titanate, lithium beta alumina, LiNbO 3 , LiCoO 2 , FeOF, and FeO x .