Ceramic garnet based ionically conducting material

Patent metadata

Field	Value
Publication number	US-10818965-B2
Application number	US-201715646327-A
Country	US
Kind code	B2
Filing date	Jul 11, 2017
Priority date	Jul 11, 2016
Publication date	Oct 27, 2020
Grant date	Oct 27, 2020

Abstract

Disclosed is a ceramic material having a formula of LiwAxM2Re3-yOz, 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.

First claim

What is claimed is:

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.

Assignees

• Univ Michigan Regents

Inventors

• Sakamoto Jeffrey
• Thompson Travis

Classifications

• Y02E60/13

  Energy storage using capacitors · CPC title

• C04B2235/3244

  Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof · CPC title

• C04B2235/32

  Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides · CPC title

• C04B35/645

  Pressure sintering · CPC title

• H01M4/382

  Lithium (H01M4/405 takes precedence) · CPC title