IP Library › Granted Patent US 10,818,965
Granted Patent B2
US 10,818,965 · App. 15/646,327 · Granted Oct 27, 2020

Ceramic garnet based ionically conducting material

Inventors: Jeffrey Sakamoto (Ann Arbor, MI); Travis Thompson (Ann Arbor, MI)
Assignee: The Regents of the University of Michigan
H01M10/0562C04B35/50C04B35/6261C04B35/645H01M4/04H01M4/624H01M10/0525C04B2235/32C04B2235/3203C04B2235/3206C04B2235/3208C04B2235/3213C04B2235/3215C04B2235/3217C04B2235/3227C04B2235/3244C04B2235/3251C04B2235/3256C04B2235/3258C04B2235/3284C04B2235/3286C04B2235/3287C04B2235/3293C04B2235/3294C04B2235/3409C04B2235/3418C04B2235/44C04B2235/442C04B2235/443C04B2235/763C04B2235/765H01M4/382H01M12/08H01M2300/0077Y02E60/128Y02T10/7011
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Quick Facts
Patent No.
US 10,818,965
App. No.
15/646,327
Granted
Oct 27, 2020
Kind
B2
Abstract

Disclosed is a ceramic material having a formula of Li w A x M 2 Re 3-y O z , wherein w is 5-7.5; wherein A is selected from B, Al, Ga, In, Zn, Cd, Y, Sc, Mg, Ca, Sr, Ba, and any combination thereof; wherein x is 0-2; wherein M is selected from Zr, Hf, Nb, Ta, Mo, W, Sn, Ge, Si, Sb, Se, Te, and any combination thereof; wherein Re is selected from lanthanide elements, actinide elements, and any combination thereof; wherein y is 0.01-0.75; wherein z is 10.875-13.125; and wherein the material has a garnet-type or garnet-like crystal structure. The ceramic garnet based material is ionically conducting and can be used as a solid state electrolyte for an electrochemical device such as a battery or supercapacitor.

Claims (61)

1. A battery comprising a cathode, an anode, and a solid-state electrolyte comprising a ceramic material having a formula of Li w A x M 2 Re 3-y O z

wherein w is 5-7.5,

wherein A is selected from B, Al, Ga, In, Zn, Cd, Y, Sc, Mg, Ca, Sr, Ba, and any combination thereof,

wherein x is 0-2,

wherein M is selected from Zr, Hf, Nb, Ta, Mo, W, Sn, Ge, Si, Sb, Se, Te, and any combination thereof,

wherein Re is selected from lanthanide elements, actinide elements, and any combination thereof,

wherein y is 0.01-0.75,

wherein z is 10.875-13.125, and

wherein the material has a garnet-type or garnet-like crystal structure, and

wherein the ceramic material is charge neutral, and

wherein the Re site is deficient relative to an LLZO (Li 7 La 3 Zr 2 O 12 ) reference formulation, and

wherein z is selected to be different from the LLZO (Li 7 La 3 Zr 2 O 12 ) reference formulation.

2. The battery of claim 1 wherein:

the ceramic material has space groups Ia 3 d (no. 230).

3. The battery of claim 1 wherein:

the ceramic material has space groups /4 1 / acd (no. 142).

4. The battery of claim 1 wherein:

the ceramic material has space groups Ia 3 d (no. 230), and

the ceramic material has space groups /4 1 / acd (no. 142).

5. The battery of claim 1 wherein:

the ceramic material at least partially has a tetragonal crystal structure.

6. The battery of claim 1 wherein:

the ceramic material has a total ionic conductivity greater than 10 −5 S/cm.

7. The battery of claim 1 wherein:

the ceramic material has a total lithium ionic conductivity greater than 10 −5 S/cm.

8. The battery of claim 1 wherein:

the ceramic material has an activation energy for ion conduction of less than 0.5 eV, and

the activation energy is measured from a plot of LN (σT) [LN(S-K/m)] vs. 1000/T[1/K].

9. The battery of claim 1 wherein:

the ceramic material has an activation energy for lithium ion conduction of less than 0.2 eV at temperatures less than 40° C., and

the activation energy is measured from a plot of LN (σT) [LN(S-K/m)] vs. 1000/T[1/K].

10. The battery of claim 1 wherein:

the ceramic material has an activation energy for lithium ion conduction of less than 0.1 eV at temperatures less than 40° C.

11. The battery of claim 1 wherein:

A is Al,

x is greater than zero,

M is Zr, and

Re is lanthanum.

12. The battery of claim 11 wherein:

w is 6-7,

x is 0.2-0.3,

y is 0.01-0.5, and

z is 11.5-12.5.

13. The battery of claim 1 wherein:

the ceramic material has the formula: Li 6.58 Al 0.25 Zr 2 La 2.7 O 11.715.

14. The battery of claim 1 , wherein:

the cathode comprises a lithium host material selected from the group consisting of lithium metal oxides wherein the metal is one or more aluminum, cobalt, iron, manganese, nickel and vanadium, and lithium-containing phosphates having a general formula LiMPO 4 wherein M is one or more of cobalt, iron, manganese, and nickel.

15. The battery of claim 1 wherein:

the anode comprises a lithium host material is selected from the group consisting of graphite, lithium titanium oxides, hard carbon, tin/cobalt alloy, and silicon/carbon.

16. The battery of claim 1 wherein:

the anode comprises a lithium metal.

17. The battery of claim 1 wherein:

the electrochemical device includes a lithium metal anode and a cathode comprising sulfur.

18. The battery of claim 1 wherein:

the electrochemical device includes a lithium metal anode and a cathode comprising an air electrode.

19. The battery of claim 1 wherein:

the solid-state electrolyte comprises a solid solution of the ceramic material of claim 1 and an additional material having a garnet-type or garnet-like crystal structure.

20. The battery of claim 19 wherein:

the additional material comprises Li 5 La 3 Ta 2 O 12 (LLTO) and/or Li 5 La 3 Nb 2 O 12 (LLNO).

21. The battery of claim 1 wherein:

not enough Li is present to balance the Re site deficiency and a cubic phase is still dominant.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 8, 2020
From: SAKAMOTO, JEFFREY; THOMPSON, TRAVIS
To: THE REGENTS OF THE UNIVERSITY OF MICHIGAN
Reel/Frame 053146/0238 →
Continuity (2)
Provisional Application 62360770 · Jul 11, 2016
Related Publication 20180013171A1 · Jan 11, 2018