Garnet materials for li secondary batteries and methods of making and using garnet materials

Patent metadata

Field	Value
Publication number	US-2022344704-A1
Application number	US-202217709390-A
Country	US
Kind code	A1
Filing date	Mar 30, 2022
Priority date	Oct 7, 2013
Publication date	Oct 27, 2022
Grant date	—

Abstract

Set forth herein are garnet material compositions, e.g., lithium-stuffed garnets and lithium-stuffed garnets doped with alumina, which are suitable for use as electrolytes and catholytes in solid state battery applications. Also set forth herein are lithium-stuffed garnet thin films having fine grains therein. Disclosed herein are novel and inventive methods of making and using lithium-stuffed garnets as catholytes, electrolytes and/or anolytes for all solid state lithium rechargeable batteries. Also disclosed herein are novel electrochemical devices which incorporate these garnet catholytes, electrolytes and/or anolytes. Also set forth herein are methods for preparing novel structures, including dense thin (<50 um) free standing membranes of an ionically conducting material for use as a catholyte, electrolyte, and, or, anolyte, in an electrochemical device, a battery component (positive or negative electrode materials), or a complete solid state electrochemical energy storage device. Also, the methods set forth herein disclose novel sintering techniques, e.g., for heating and/or field assisted (FAST) sintering, for solid state energy storage devices and the components thereof.

First claim

1 .- 123 . (canceled)

124 . A composition comprising:
a nanostructured lithium stuffed garnet-based powder; wherein the lithium-stuffed garnet-based powder is characterized by one of the following formula: Li A La B M′ C M″ D Zr E O F , Li A La B M′ C M″ D Ta E O F , Li A La B M′ C M″ D Nb E O F , wherein 4<A<8.5, 1.5<B<4, 0≤C≤2, 0≤D≤2; 0≤E<2, 10<F≤13, and M′ and M″ are each, independently in each instance selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta; Li a La b Zr c Al d Me″ e O f , wherein 5<a<7.7; 2<b<4; 0≤c≤2.5; 0≤d≤2; 0≤e<2, 10≤f<13 and Me″ is a metal selected from Nb, Ta, V, W, Mo, or Sb; Li A La B M′ C M″ D Zr E O F , wherein the molar ratio of Al 2 O 3 :lithium-stuffed garnet is between 0.05 and 0.7; or Li g La 3 Zr 2 O 12 .Al 2 O 3 , wherein 5.5<g<8.5 and the molar ratio of Al 2 O 3 :lithium-stuffed garnet is between 0.05 and 1.0, wherein the lithium-stuffed garnet-based powder comprises crystalline domains of lithium-stuffed garnet having a median crystalline domain diameter of 0.5 nm to 10 μm.

125 . The composition of claim 124 , wherein the lithium-stuffed garnet-based powder is characterized by Li A La B M′ C M″ D Zr E O F , Li A La B M′ c M″ D Ta E O F , Li A La B M′ c M″ D Nb E O F , wherein 4<A<8.5, 1.5<B<4, 0≤C≤2, 0≤D≤2; 0≤E<2, 10<F≤13, and M′ and M″ are each, independently in each instance selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta.

126 . The composition of claim 124 , wherein the lithium-stuffed garnet-based powder is characterized by Li a La b Zr c Al d Me″ e O f , wherein 5<a<7.7; 2<b<4; 0≤c≤2.5; 0≤d≤2; 0≤e<2, 10<f<13 and Me″ is a metal selected from Nb, Ta, V, W, Mo, or Sb.

127 . The composition of claim 124 , wherein the lithium-stuffed garnet-based powder is characterized by Li A La B M′ c M″ D Zr E O F , wherein the molar ratio of Al 2 O 3 :lithium-stuffed garnet is between 0.05 and 0.7.

128 . The composition of claim 124 , wherein the lithium-stuffed garnet-based powder is characterized by Li g La 3 Zr 2 O 12 —Al 2 O 3 , wherein 5.5<g<8.5 and the molar ratio of Al 2 O 3 :lithium-stuffed garnet is between 0.05 and 1.0.

129 . The composition of claim 124 , wherein the median crystalline domain diameter is 20 nm, 23 nm, 25.5 nm, 28.5 nm, 30 nm, 40 nm, 50 nm, 65 nm, 80 nm, 100 nm, 200 nm, or combinations thereof.

130 . A lithium-stuffed garnet film comprising the composition of claim 124 , wherein the lithium-stuffed garnet thin film has a thickness of 1 μm to 150 μm.

131 . The lithium-stuffed garnet film comprising the composition of claim 130 , wherein the thickness of the lithium-stuffed garnet thin film is less than 50 μm.

132 . The lithium-stuffed garnet film comprising the composition of claim 130 , wherein the thickness of the lithium-stuffed garnet thin film is less than 30 μm.

133 . The lithium-stuffed garnet film comprising the composition of claim 130 , wherein the lithium-stuffed garnet thin film has a surface roughness of less than 5 μm.

134 . A method of preparing lithium-stuffed garnet-based powder, the method comprising:
providing garnet material precursor, wherein the garnet material precursor is LiOH, La 2 O 3 , ZrO 2 , Nb 2 O 5 , Ta 2 O 5 , Al-nitrate, or combinations thereof; calcining the garnet material precursors to produce calcined garnet material; and milling the calcined garnet material to reduce a mean primary particle size of the calcined garnet material precursors to produce lithium-stuffed garnet-based powder.

135 . The method of claim 134 , further comprising sintering the lithium-stuffed garnet-based powder at a temperature of 600° C. to 1400° C.

136 . The method of claim 134 , wherein the lithium-stuffed garnet-based powder comprises crystalline domains of lithium-stuffed garnet powder having a median crystalline domain diameter is 0.5 nm to 10 μm.

137 . The method of claim 134 , further comprising milling the lithium-stuffed garnet-based powder to produce a lithium-stuffed garnet-based powder having a d 50 particle size of 100 nm.

138 . The method of claim 134 , further comprising milling the lithium-stuffed garnet-based powder to produce a lithium-stuffed garnet-based powder having a d 50 particle size of 200 nm.

139 . The method of claim 134 , further comprising milling the lithium-stuffed garnet-based powder to produce a lithium-stuffed garnet-based powder having a d 50 particle size of 350 nm.

140 . The method of claim 134 , wherein the milling step is selected from ball milling, horizontal milling, attritor milling, immersion milling, or combinations thereof.

Assignees

• Quantumscape Battery Inc

Inventors

• Karpenko Oleh
• Donnelly Niall
• Holme Tim
• Hudson Will
• Iyer Sriram
• Choi Dong Hee Anna
• Singh Mohit
• Winoto Adrian

Classifications

• C01P2006/40

  Electric properties · CPC title

• C04B35/6261

  Milling · CPC title

• H01M10/056

  characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes · CPC title

• C04B2235/3227

  Lanthanum oxide or oxide-forming salts thereof · CPC title

• C04B2235/6567

  Treatment time · CPC title