Garnet-type lithium-ion solid-state conductor

Patent metadata

Field	Value
Publication number	US-11444318-B2
Application number	US-201916541255-A
Country	US
Kind code	B2
Filing date	Aug 15, 2019
Priority date	Jan 11, 2019
Publication date	Sep 13, 2022
Grant date	Sep 13, 2022

Abstract

Disclosed is a solid state electrolyte comprising a compound of Formula 1Li7−a*α−(b−4)*β−xMaαLa3Hf2−βMbβO12−x−δXx  (1)whereinMa is a cationic element having a valence of a+;Mb is a cationic element having a valence of b+; andX is an anion having a valence of −1,wherein, when Ma includes H, 0≤α≤5, otherwise 0≤α≤0.75, and wherein 0≤β≤1.5, 0≤x≤1.5, and (a*α+(b−4)β+x)>0, 0≤δ≤1.

First claim

What is claimed is:

1. A solid state electrolyte comprising a compound of Formula 1
Li 7−a*α−(b−4)*β−x M a α La 3 Hf 2−β M b β O 12−x−δ X x   (1)

wherein
M a is a cationic element having a valence of a+;
M b is a cationic element having a valence of b+; and
X is an anion having a valence of −1,
wherein, when M a comprises H, 0<α≤5, otherwise 0<α≤0.75, and
wherein 0≤β≤1.5, 0<x≤1.5, and (a*α+(b−4)β+x)>0, 0≤δ≤1.

2. The solid state electrolyte of claim 1 , wherein a Li crystallographic site comprises M a disposed thereon.

3. The solid state electrolyte of claim 1 , wherein M a is a monovalent element, a divalent element, a trivalent element, or a tetravalent element.

4. The solid state electrolyte of claim 2 , wherein a is 1 and M a is monovalent and is H, Na, K, Rb, or a combination thereof.

5. The solid state electrolyte of claim 2 , wherein a is 2 and M a is divalent and is Be, Mg, Ca, Sr, Ba, or a combination thereof.

6. The solid state electrolyte of claim 2 , wherein a is 3, and M a is trivalent and is B, Al, Ga, In, Sc, Y, La, Ce, Pr, Nd, or a combination thereof.

7. The solid state electrolyte of claim 2 , wherein a is 4, and M a is tetravalent and is Zr, Ti, Sn, Si, Ge, Pb, or a combination thereof.

8. The solid state electrolyte of claim 1 , wherein a Hf crystallographic site comprises M b disposed thereon.

9. The solid state electrolyte of claim 1 , wherein M b is a divalent element, a trivalent element, a tetravalent element, or a pentavalent element.

10. The solid state electrolyte of claim 9 , wherein b is 2 and M b is divalent and is Be, Mg, Ca, Sr, Ba, or a combination thereof.

11. The solid state electrolyte of claim 9 , wherein b is 3 and M b is trivalent and is B, Al, Ga, In, Sc, Y, La, Ce, Pr, Nd, or a combination thereof.

12. The solid state electrolyte of claim 9 , wherein b is 4 and M b is tetravalent and is Zr, Ti, Sn, Si, Ge, Pb, or a combination thereof.

13. The solid state electrolyte of claim 9 , wherein b is 5 and M b is pentavalent and is V, Ta, Nb, or a combination thereof.

14. The solid state electrolyte of claim 9 , wherein b is 6 and M b is hexavalent and is Cr, Mo, W, or a combination thereof.

15. The solid state electrolyte of claim 1 , wherein M a and M b are different.

16. The solid state electrolyte of claim 1 , wherein X is F.

17. The solid state electrolyte of claim 1 , wherein M b is Zr, and wherein the solid state electrolyte is in the form of a particle wherein a ratio of a concentration of Hf to Zr on a surface of the particle is greater than a ratio of a concentration of Hf to Zr in a center of the particle.

18. The solid state electrolyte of claim 1 , wherein M b is Zr, and wherein the solid state electrolyte is in the form of a particle wherein a concentration of Hf increases in a direction from a center of the particle to a surface of the particle.

19. A particle comprising:
the solid state electrolyte of claim 1 ; and
a liquid electrolyte within a pore of the particle.

20. A solid state electrolyte comprising:
a core comprising a first solid state electrolyte; and
a shell comprising the compound of claim 1 on the core,

wherein the first solid state electrolyte and the compound of Formula 1 are different.

21. A porous separator for a battery, the separator comprising:
a porous substrate, and
the compound of claim 1 on the substrate.

22. A protected negative electrode, the electrode comprising lithium metal and the solid state electrolyte of claim 1 directly on the lithium metal.

23. A positive active material for a lithium battery, the positive active material comprising:
a lithium transition metal oxide; and
the solid state electrolyte of claim 1 on the lithium transition metal oxide.

24. A battery comprising:
a positive electrode;
a negative electrode; and
the solid state electrolyte of claim 1 between the positive electrode and the negative electrode.

25. A solid state electrolyte comprising a compound of the formula
Li 7−a*α−(b−4)*β−x M a α La 3 Hf 2−β M b β O 12−x−δ F x

wherein
M a is a cationic element having a valence of a+;
M b is a cationic element having a valence of b+; and
wherein, when M a comprises H, 0<α≤5, otherwise 0<α≤0.75, and
wherein 0≤β≤1.5, 0<x≤1.5, and (a*α+(b−4)β+x)>0, 0≤δ≤1.

Assignees

• Samsung Electronics Co Ltd

Inventors

• Wang Yan
• Miara Lincoln
• Ma Sang Bok

Classifications

• H01M50/497

  Ionic conductivity · CPC title

• H01M50/443

  Particulate material · CPC title

• H01M50/451

  comprising layers of only organic material and layers containing inorganic material · CPC title

• C04B2235/3208

  Calcium oxide or oxide-forming salts thereof, e.g. lime · CPC title

• C04B35/505

  based on yttrium oxide · CPC title