Lithium-stuffed garnet electrolytes with secondary phase inclusions

Patent metadata

Field	Value
Publication number	US-2023050593-A1
Application number	US-202217961195-A
Country	US
Kind code	A1
Filing date	Oct 6, 2022
Priority date	Jun 23, 2017
Publication date	Feb 16, 2023
Grant date	—

Abstract

The instant disclosure sets forth multiphase lithium-stuffed garnet electrolytes having secondary phase inclusions, wherein these secondary phase inclusions are material(s) which is/are not a cubic phase lithium-stuffed garnet but which is/are entrapped or enclosed within a lithium-stuffed garnet. When the secondary phase inclusions described herein are included in a lithium-stuffed garnet at 30-0.1 volume %, the inclusions stabilize the multiphase matrix and allow for improved sintering of the lithium-stuffed garnet. The electrolytes described herein, which include lithium-stuffed garnet with secondary phase inclusions, have an improved sinterability and density compared to phase pure cubic lithium-stuffed garnet having the formula Li 7 La 3 Zr 2 O 12 .

First claim

What is claimed is:

1 - 99 . (canceled)

100 . A powder comprising:
a primary phase selected from lithium-stuffed garnet; and a secondary phase selected from Li x Al y O z wherein 1≤x≤5, 1≤y≤5, and 2≤z≤8; LiZr 2 O 3 ; La 2 Zr 2 O 7 ; La 2 O 3 ; Li x Zr y O z wherein 2≤x≤8, 0≤y≤1, and 1≤z≤6; LaAlO 3 ; La 2 (Li 0.5 Al 0.5 )O 4 ; LiLaO 2 ; and combinations thereof.

101 . The powder of claim 100 , wherein the primary phase comprises cubic lithium-stuffed garnet.

102 . The powder of claim 101 , wherein the primary phase lithium-stuffed garnet is characterized by the formula Li A La B Al C M″ D Zn E O F , wherein 5<A<8, 1.5<B<4, 0.1<C<2, 0≤D<2; 1<E<3, 10<F<13, and M″ is selected from the group consisting of Mo, W, Nb, Y, Ta, Ga, Sb, Ca, Ba, Sr, Ce, Hf, and Rb.

103 . The powder of claim 101 , wherein M″ is selected from the group consisting of Mo, W, Nb, Y, Ta, and Ga.

104 . The powder of claim 100 , wherein the secondary phase d 50 grain size is from 1 μm to 10 μm.

105 . The powder of claim 100 , wherein the primary phase lithium-stuffed garnet d 50 grain size is from 0.5 μm to 10 μm.

106 . The powder of claim 100 , wherein the d 90 grain size of the primary phase, secondary phase, or both, is from 1 μm to 5 μm.

107 . The powder of claim 100 , wherein the powder is present in a pellet.

108 . The powder of claim 100 , wherein the powder is present in a green film.

109 . The powder of claim 100 , wherein the secondary phase in the powder comprises 0.1-25 vol % of LiAlO 2 , 0.1-15 vol % of Li 2 ZrO 3 , 0.1-15 vol % of LaAlO 3 , or a combination thereof, as measured by XRD.

110 . The powder of claim 100 , wherein the powder comprises pyrochlore at less than 20 vol % as measured by XRD after an electrolyte is heated at 850° C. for 2 hours.

111 . The powder of claim 100 , wherein the powder comprises crystalline domains of lithium-stuffed garnet, wherein the median crystalline domain has a d 50 median crystalline domain size of 0.5 nm to 10 μm in diameter.

112 . The powder of claim 100 , wherein the secondary phase comprises tetragonal garnet.

113 . The powder of claim 100 , wherein the secondary phase comprises La 2 Zr 2 O 7 , LiAlO 2 , LaAlO 3 , tetragonal garnet, Li 2 ZrO 3 , or combinations thereof.

114 . The powder of claim 100 , wherein the secondary phase comprises Li x Al y O z wherein 1≤x≤5, 1≤y≤5, and 2≤z≤8, and LiZr 2 O 3 .

115 . The powder of claim 100 , wherein the secondary phase comprises Li x Al y O z wherein 1≤x≤5, 1≤y≤5, and 2≤z≤8, and La 2 Zr 2 O 7 .

116 . The powder of claim 100 , wherein the secondary phase comprises Li x Al y O z wherein 1≤x≤5, 1≤y≤5, and 2≤z≤8, and Li x Zr y O z wherein 2≤x≤8, 0≤y≤1, and 1≤z≤6.

117 . The powder of claim 100 , wherein the secondary phase comprises Li x Al y O z wherein 1≤x≤5, 1≤y≤5, and 2≤z≤8, and LaAlO 3 .

118 . The powder of claim 100 , wherein the secondary phase comprises Li x Al y O z wherein 1≤x≤5, 1≤y≤5, and 2≤z≤8, and tetragonal garnet.

119 . The powder of claim 100 , wherein the secondary phase comprises Li x Al y O z wherein 1≤x≤5, 1≤y≤5, and 2≤z≤8, and La 2 (Li 0.5 Al 0.5 )O 4 .

120 . The powder of claim 100 , wherein the secondary phase comprises Li x Al y O z wherein 1≤x≤5, 1≤y≤5, and 2≤z≤8, and LiLaO 2 .

121 . The powder of claim 100 , wherein the secondary phase comprises LiZr 2 O 3 and La 2 Zr 2 O 7 .

122 . The powder of claim 100 , wherein the secondary phase comprises LiZr 2 O 3 and La 2 O 3 .

123 . The powder of claim 100 , wherein the secondary phase comprises LiZr 2 O 3 and Li x Zr y O z wherein 2≤x≤8, 0≤y≤1, and 1≤z≤6.

124 . The powder of claim 100 , wherein the secondary phase comprises LiZr 2 O 3 and La 2 (Li 0.5 Al 0.5 )O 4 .

125 . The powder of claim 100 , wherein the secondary phase comprises LiZr 2 O 3 and LiLaO 2 .

126 . The powder of claim 100 , wherein the secondary phase comprises LiZr 2 O 3 and tetragonal garnet.

127 . The powder of claim 100 , wherein the powder is characterized by a median particle size of 100 nm to 10 μm.

128 . The powder of claim 100 , wherein the powder is characterized by a median particle size is 800 nm to 2 μm.

129 . The powder of claim 100 , wherein the primary phase lithium-stuffed garnet d 50 grain size is larger than the secondary phase inclusion d 50 grain size.

130 . The powder of claim 100 , wherein the secondary phase inclusions include at least two, three, or four types of secondary phase inclusions.

131 . The powder of claim 100 , wherein the secondary phase inclusions are homogeneously distributed over a volume of 10000 μm 3 or more.

132 . The powder of claim 100 , wherein the density of the powder is 4.6-5.2 g/cm 3 as measured by the Archimedes method.

133 . The powder of claim 100 , wherein the powder has a total porosity of less than 5 vol % as determined by SEM.

134 . A method of making a slurry comprising combining the powder of claim 100 with non-aqueous solvent and binder.

Assignees

• Quantumscape Battery Inc

Inventors

• Beck Larry
• Chao Cheng-Chieh
• Cheng Lei
• Donnelly Niall
• Gardner William H
• Holme Tim
• Hudson Will
• Iyer Sriram
• Karpenko Oleh
• Li Yang
• Xu Gengfu

Classifications

• C01G25/006

  Compounds containing zirconium, with or without oxygen or hydrogen, and containing two or more other elements · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• C01P2004/61

  Micrometer sized, i.e. from 1-100 micrometer · CPC title

• H01M2300/002

  Inorganic electrolyte · CPC title

• H01M10/0562 Primary

  Solid materials · CPC title