Garnet-lithium titanate composite electrolyte

Patent metadata

Field	Value
Publication number	US-2021347697-A1
Application number	US-202117308646-A
Country	US
Kind code	A1
Filing date	May 5, 2021
Priority date	May 8, 2020
Publication date	Nov 11, 2021
Grant date	—

Abstract

A sintered composite ceramic includes: a lithium-garnet major phase; and a lithium-rich minor phase, such that the lithium-rich minor phase has LixTiO(x+4)/2, with 0.66≤x≤4. The sintered composite ceramic may exhibit a relative density of at least 90% of a theoretical maximum density of the ceramic, an ionic conductivity of at least 0.35 mS·cm−1, or a critical current density (CCD) of at least 1.0 mA·cm−2.

First claim

What is claimed is:

1 . A sintered composite ceramic, comprising:
a lithium-garnet major phase; and a lithium-rich minor phase, wherein the lithium-rich minor phase comprises Li x TiO (x+4)/2 , with 0.66≤x≤4.

2 . The sintered composite ceramic of claim 1 , wherein the lithium-garnet major phase comprises at least one of:
(i) Li 7-3a La 3 Zr 2 L a O 12 , with L=Al, Ga or Fe and 0<a<0.33; (ii) Li 7 La 3-b Zr 2 M b O 12 , with M=Bi or Y and 0<b<1; (iii) Li 7-c La 3 (Zr 2-c ,N c )O 12 , with N=In, Si, Ge, Sn, V, W, Te, Nb, or Ta and 0<c<1, or a combination thereof.

3 . The sintered composite ceramic of claim 1 , wherein a mass ratio of lithium-garnet major phase to lithium-rich minor phase is in a range of 100:2 to 100:8.

4 . The sintered composite ceramic of claim 1 , wherein the ceramic has a relative density of at least 90% of a theoretical maximum density of the ceramic.

5 . The sintered composite ceramic of claim 1 , wherein the ceramic has an ionic conductivity of at least 0.35 mS·cm −1 .

6 . The sintered composite ceramic of claim 1 , wherein the ceramic has a critical current density (CCD) of at least 1.0 mA·cm −2 .

7 . The sintered composite ceramic of claim 1 , wherein the ceramic has a critical current density (CCD) of at least 1.5 mA·cm −2 .

8 . A sintered composite ceramic, comprising:
a lithium-garnet major phase; and a lithium-rich minor phase, wherein the lithium-rich minor phase comprises at least one of: Li 2 TiO 3 , Li 4 Ti 5 O 12 , Li 2 Ti 3 O 7 , Li 4 TiO 4 , or a combination thereof.

9 . The sintered composite ceramic of claim 8 , wherein the lithium-garnet major phase comprises at least one of:
(i) Li 7-3a La 3 Zr 2 L a O 12 , with L=Al, Ga or Fe and 0<a<0.33; (ii) Li 7 La 3-b Zr 2 M b O 12 , with M=Bi or Y and 0<b<1; (iii) Li 7-c La 3 (Zr 2-c ,N c )O 12 , with N=In, Si, Ge, Sn, V, W, Te, Nb, or Ta and 0<c<1, or a combination thereof.

10 . The sintered composite ceramic of claim 8 , wherein a mass ratio of lithium-garnet major phase to lithium-rich minor phase is in a range of 100:2 to 100:8.

11 . A battery, comprising:
at least one lithium electrode; and an electrolyte in contact with the at least one lithium electrode, wherein the electrolyte is a lithium-garnet composite electrolyte comprising the sintered composite ceramic of claim 1 .

12 . A method of making the composite ceramic, comprising:
a first mixing of inorganic source materials to form a mixture, including a lithium source compound and at least one transition metal compound; a first milling of the mixture to reduce the particle size of the precursors; calcining the milled mixture to form a garnet oxide at from 800 to 1200° C.; a second mixing of the milled and calcined garnet oxide with at least one minor phase additive to form a second mixture; a second milling of the second mixture to reduce the particle size of constituents of the second mixture; compacting the second milled second mixture into a green pellet; and sintering the green pellet at a temperature ranging from 1000° C. to 1300° C., wherein the minor phase additive comprises Li x TiO (x+4)/2 , with 0.66≤x≤4.

13 . The method of claim 12 , wherein at least one of the lithium source compound or the minor phase additive is present in a stoichiometric excess.

14 . The method of claim 12 , wherein a mass ratio of the milled and calcined garnet oxide to the at least one minor phase additive is in a range of 100:2 to 100:8.

15 . The method of claim 12 , wherein no mother powder is applied with the green pellet in the sintering step.

16 . The method of claim 12 , wherein mother powder is applied with the green pellet in the sintering step.

17 . A sintered composite ceramic, comprising:
a lithium-garnet major phase; and a lithium-rich minor phase, wherein a mass ratio of lithium-garnet major phase to lithium-rich minor phase is in a range of 100:2 to 100:8, and wherein the ceramic comprises at least one of:
(i) a relative density of at least 90% of a theoretical maximum density of the ceramic,
(ii) an ionic conductivity of at least 0.35 mS·cm −1 , and
(iii) a critical current density (CCD) of at least 1.0 mA·cm −2 .

18 . The sintered composite ceramic of claim 17 , wherein the ceramic has a critical current density (CCD) of at least 1.5 mA·cm −2 .

Assignees

• Corning Inc
• Shanghai Inst Ceramics Cas

Inventors

• Badding Michael Edward
• Jin Jun
• Song Zhen
• Su Jianmeng
• Wen Zhaoyin
• Xiu Tongping
• Zheng Chujun

Classifications

• H01M2300/0085

  Immobilising or gelification of electrolyte · CPC title

• H01M10/0562

  Solid materials · CPC title

• C04B2235/3293

  Tin oxides, stannates or oxide forming salts thereof, e.g. indium tin oxide [ITO] · CPC title

• C04B2235/3286

  Gallium oxides, gallates, indium oxides, indates, thallium oxides, thallates or oxide forming salts thereof, e.g. zinc gallate · CPC title

• C04B2235/3203

  Lithium oxide or oxide-forming salts thereof · CPC title