Lithium-stuffed garnet electrolytes with secondary phase inclusions

Patent metadata

Field	Value
Publication number	US-2024405264-A1
Application number	US-202418734585-A
Country	US
Kind code	A1
Filing date	Jun 5, 2024
Priority date	Jun 23, 2017
Publication date	Dec 5, 2024
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

1 .- 99 . (canceled)

100 . A bilayer comprising:
a metal foil or metal powder bonded to one side of a sintered lithium-stuffed garnet thin film, wherein the sintered lithium-stuffed garnet thin film comprises: a primary cubic phase lithium-stuffed garnet characterized by the chemical formula Li A La B M′ C M″ D Zr 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, and Ta; and a secondary phase inclusion; wherein:
the primary cubic phase lithium-stuffed garnet is present in the sintered lithium-stuffed garnet thin film at about 70 volume percent to 99.9 volume percent with respect to the volume of the sintered lithium-stuffed garnet thin film; and
the secondary phase inclusion is present in the sintered lithium-stuffed garnet thin film at about 0.1 volume percent to 30 volume percent with respect to the volume of the sintered lithium-stuffed garnet thin film,
wherein the secondary phase inclusion includes at least two materials selected from the groups consisting of:
(i) tetragonal phase garnet; Li a Zr b O c , wherein 1≤a≤8, 1≤b≤2, and 1≤c≤7, and wherein subscripts a, b, and c are selected so that Li a Zr b O c is charge neutral; Li g Al n O i , wherein 1≤g≤5, 1≤h≤5, and 25i≤8, and wherein subscripts g, h, i are selected so that Li g Al n O i is charge neutral; and
(ii) La 2 Zr 2 O 7 ; La 2 O 3 ; LaAlO 3 ; La 2 (Li 0.5 Al 0.5 )O 4 ; LiLaO 2 ; LiZr 2 O 3 ;
and combinations thereof.

101 . The bilayer of claim 100 , wherein the thickness of the sintered lithium-stuffed garnet thin film is between 10 nm and 100 μm.

102 . The bilayer of claim 100 , wherein the sintered lithium-stuffed garnet thin film has an area of at least 25 cm 2 .

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

104 . The bilayer of claim 100 , wherein the secondary phase inclusion d 50 grain size is less than 10 μm.

105 . The bilayer of claim 100 , wherein the secondary phase inclusion comprises at least three materials selected from the group consisting of: tetragonal phase garnet; La 2 Zr 2 O 7 ; La 2 O 3 ; LaAlO 3 ; La 2 (Li 0.5 Al 0.5 )O 4 ; LiLaO 2 ; Li a Zr b O c , wherein 1≤a≤8, 1≤b≤2, and 1≤c≤7, and wherein subscripts a, b, and c are selected so that Li a Zr b O c is charge neutral; and Li g Al h O i , wherein 1≤g≤5, 1≤h≤5, and 2≤i≤8, and wherein subscripts g, h, i are selected so that Li g Al h O i is charge neutral.

106 . The bilayer of claim 105 , wherein the secondary phase inclusion comprises LiZr 2 O 3 .

107 . The bilayer of claim 100 , wherein the secondary phase inclusion comprises at least four materials selected from the group consisting of: tetragonal phase garnet; Li a Zr b O c , wherein 1≤a≤8, 1≤b≤2, and 1≤c≤7, and wherein subscripts a, b, and c are selected so that Li a Zr b O c is charge neutral; and Li g Al h O i , wherein 1≤g≤5, 1≤h≤5, and 2≤i≤8, and wherein subscripts g, h, i are selected so that Li g Al h O i is charge neutral.

108 . The bilayer of claim 100 , wherein the secondary phase inclusion comprises La 2 Zr 2 O 7 , La 2 O 3 , LaAlO 3 , La 2 (Li 0.5 Al 0.5 )O 4 , LiLaO 2 , LiZr 2 O 3 , or combinations thereof.

109 . The bilayer of claim 100 , wherein the total amount of secondary phase inclusion is 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 vol %.

110 . The bilayer of claim 100 , wherein the secondary phase inclusion comprises La 2 Zr 2 O 7 ; tetragonal garnet; Li a Zr b O c , wherein 1≤a≤8, 1≤b≤2, and 1≤c≤7, and wherein subscripts a, b, and c are selected so that Li a Zr b O c is charge neutral.

111 . The bilayer of claim 100 , wherein the secondary phase inclusion in the sintered lithium-stuffed garnet thin film comprises LiAlO 2 present in the sintered lithium-stuffed garnet thin film at about 0.1-25 vol %.

112 . The bilayer of claim 100 , wherein the secondary phase inclusion in the sintered lithium-stuffed garnet thin film comprises LiAlO 2 present in the sintered lithium-stuffed garnet thin film at about 0.1-25 vol %, Li 2 ZrO 3 present in the sintered lithium-stuffed garnet thin film at about 0.1-15 vol % and LaAlO3 present in the sintered lithium-stuffed garnet thin film at about 0.1-15 vol %, as measured by quantitative XRD.

113 . The bilayer of claim 100 , wherein the secondary phase inclusion in the sintered lithium-stuffed garnet thin film comprises LiAlO 2 present in the sintered lithium-stuffed garnet thin film at about 3-8 vol %, Li 2 ZrO 3 present in the sintered lithium-stuffed garnet thin film at about 1-10 vol % and LaAlO 3 present in the sintered lithium-stuffed garnet thin film at about 1-8 vol %, as measured by quantitative XRD.

114 . The bilayer of claim 100 , where the sintered lithium-stuffed garnet thin film has a total porosity of less than 5 vol % as determined by SEM.

115 . A process of making a composition, wherein the compositions comprises:
a primary cubic phase lithium-stuffed garnet characterized by the chemical formula Li A La B M′ C M″ D Zr 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, and Ta; and a secondary phase inclusion; wherein:
the primary cubic phase lithium-stuffed garnet is present at about 70 volume percent to 99.9 volume percent with respect to the volume of the composition; and
the secondary phase inclusion is present at about 0.1 volume percent to 30 volume percent-with respect to the volume of the composition, wherein the secondary phase inclusion includes at least two materials selected from the group consisting of:
(i) tetragonal phase garnet; Li a Zr b O c , wherein 1≤a≤8, 1≤b≤2, and 1≤c≤7, and wherein subscripts a, b, and c are selected so that Li a Zr b O c is charge neutral; Li g Al h O i , wherein 1≤g≤5, 1≤h≤5, and 2≤i≤8, and wherein subscripts g, h, i are selected so that Li g Al h O i is charge neutral; and
(ii) La 2 Zr 2 O 7 ; La 2 O 3 ; LaAlO 3 ; La 2 (Li 0.5 Al 0.5 )O 4 ; LiLaO 2 ;
and combinations thereof.

the process comprising the following steps:
(a) providing a mixture of lithium-stuffed garnet chemical precursors, wherein an amount of Al in the mixture exceeds a solubility limit of Al in the primary cubic phase lithium-stuffed garnet; and
(b) calcining the mixture by heating it to at least 800° C.

116 . The process of claim 115 , wherein the lithium-stuffed garnet chemical precursors are selected from: lithium hydroxide, lithium oxide, zirconium oxide, zirconium nitrate, zirconium acetate, lanthanum oxide, lanthanum nitrate, lanthanum acetate, aluminum oxide, aluminum, aluminum nitrate, aluminum nitrate nonahydrate, aluminum (oxy) hydroxide, gallium oxide, corundum, niobium oxide, tantalum oxide, and combinations thereof.

117 . The process of claim 115 , wherein the secondary phase inclusion in the sintered lithium-stuffed garnet thin film comprises tetragonal garnet.

118 . The process of claim 115 , wherein the secondary phase inclusion in the sintered lithium-stuffed garnet thin film comprises Li a Zr b O c , wherein 1≤a≤8, 1≤b≤2, and 1≤c≤7, and wherein subscripts a, b, and c are selected so that Li a Zr b O c is charge neutral.

119 . The composition of claim 115 , wherein the secondary phase inclusion in the

Assignees

• Quantumscape Battery Inc

Inventors

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

Classifications

• H01M2300/0071

  Oxides · CPC title

• H01M2220/20

  Batteries in motive systems, e.g. vehicle, ship, plane · 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

• C01P2002/74

  by peak-intensities or a ratio thereof only · CPC title