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

Patent metadata

Field	Value
Publication number	US-2019103630-A1
Application number	US-201816102606-A
Country	US
Kind code	A1
Filing date	Aug 13, 2018
Priority date	Oct 7, 2013
Publication date	Apr 4, 2019
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 . A composition comprising a lithium stuffed garnet and Al 2 O 3 , wherein the lithium-stuffed garnet is characterized by the empirical 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 M′ and M″ are, independently in each instance, either absent or are each independently selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta; and wherein the molar ratio of Garnet:Al 2 O 3 is between 0.05 and 0.7.

2 .- 123 . (canceled)

124 . A thin unsintered film, comprising:
lithium-stuffed garnet precursor powders or calcined lithium-stuffed garnet powder; and at least one member selected from the group consisting of a binder, a solvent, a dispersant, and combinations thereof; wherein the solid loading of the lithium-stuffed garnet precursor powders or the calcined lithium-stuffed garnet powder is at least 40% by volume (v/v); wherein the film thickness is less than 100 μm; and wherein the median grain size of the lithium-stuffed garnet precursor powders or the calcined lithium-stuffed garnet powder is between 0.1 μm and 10 μm.

125 . The thin unsintered film of claim 124 , wherein the solid loading of the lithium-stuffed garnet precursor powders or the calcined lithium-stuffed garnet powder is at least 45% by volume (v/v).

126 . The thin unsintered film of claim 124 , wherein the solid loading of the lithium-stuffed garnet precursor powders or the calcined lithium-stuffed garnet powder is at least 45%, 50%, 55%, 60%, 65%, 70%, 75%, or 80% by volume (v/v).

127 . The thin unsintered film of claim 124 , wherein the lithium-stuffed garnet is characterized by the empirical formula Li A La B M′ C M″ D Zr E O F , wherein 5<A<8, 1.5<B<4, 0.1≤C≤2, 0<D≤2; 1≤E≤2, 10<F≤13, and
M′ is Al; and
M″ is selected from the group consisting of Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, and Rb.

128 . The thin unsintered film of claim 124 , wherein the lithium-stuffed garnet is characterized by the empirical formula
Li A La B M′ C M″ D Zr E O F , wherein 6.5<A<8, 1.5<B<4, 0.1≤C≤2, 0<D≤2; 1≤E≤2, 10<F≤13, M′ is Al; and M″ is Ta.

129 . The thin unsintered film of claim 124 , wherein the thin unsintered garnet film is adhered to a substrate.

130 . The thin unsintered film of claim 127 , wherein the substrate is selected from the group consisting of a polymer, a metal foil, a metal powder, a metal powder film, or a metal coating.

131 . The thin unsintered film of claim 130 , wherein the metal is selected from the group consisting of Ni, Cu, Al, steel, alloys, and combinations thereof.

132 . The thin unsintered film of claim 124 , wherein the solid loading is at least 40% v/v to 80% v/v.

133 . The thin unsintered film of claim 124 , wherein the thin unsintered garnet film thickness is less than 50 μm and greater than 10 nm.

134 . The thin unsintered film of claim 124 , wherein the thin unsintered garnet film is free standing.

135 . The thin unsintered film of claim 133 , wherein:
the thin unsintered garnet film is bonded to a current collector (CC) film on at least one side of the thin unsintered garnet film; and the CC film comprises a metal or metal powder, wherein the metal is selected from the group consisting of Nickel (Ni), Copper (Cu), combinations thereof, and alloys thereof.

136 . The thin unsintered film of claim 135 , wherein the thin unsintered garnet film is bonded to a CC film on one side of the film.

137 . The thin unsintered film of claim 135 , wherein the thin unsintered garnet film is bonded to a CC film on two sides of the film.

138 . A bilayer comprising a metal foil or metal powder positioned in contact with a thin unsintered film according to claim 124 .

139 . A trilayer comprising a metal foil or metal powder and two unsintered films according to claim 124 , wherein the metal foil or metal powder is positioned between and in contact with the two thin unsintered films according to claim 124 .

140 . The thin unsintered film of claim 124 , wherein the film thickness is 10 μm to 100 μm.

141 . A thin unsintered film, comprising:
lithium-stuffed garnet precursor powders or calcined lithium-stuffed garnet powder; and at least one member selected from the group consisting of a binder, a solvent, a dispersant, and combinations thereof; wherein the solid loading of the lithium-stuffed garnet precursor powders or the calcined lithium-stuffed garnet powder is at least 40% by mass (w/w); wherein the film thickness is less than 100 μm; and wherein the median grain size of the lithium-stuffed garnet precursor powders or the calcined lithium-stuffed garnet powder is between 0.1 μm and 10 μm.

142 . The thin unsintered film of claim 141 , wherein the solid loading of the lithium-stuffed garnet precursor powders or the calcined lithium-stuffed garnet powder is at least 45% by mass (w/w).

143 . The thin unsintered film of claim 141 , wherein the solid loading of the lithium-stuffed garnet precursor powders or the calcined lithium-stuffed garnet powder is at least 45%, 50%, 55%, 60%, 65%, 70%, 75%, or 80% by mass (w/w).

144 . The thin unsintered film of claim 141 , wherein the lithium-stuffed garnet is characterized by the empirical formula Li A La B M′ C M″ D Zr E O F , wherein 5<A<8, 1.5<B<4, 0.1≤C≤2, 0<D≤2; 1≤E≤2, 10<F≤13, and
M′ is Al; and
M″ is selected from the group consisting of Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, and Rb.

145 . The thin unsintered film of claim 141 , wherein the lithium-stuffed garnet is characterized by the empirical formula
Li A La B M′ C M″ D Zr E O F , wherein 6.5<A<8, 1.5<B<4, 0.1≤C≤2, 0<D≤2; 1≤E≤2, 10<F≤13, M′ is Al; and M″ is Ta.

146 . The thin unsintered film of claim 141 , wherein the thin unsintered garnet film is adhered to a substrate.

147 . The thin unsintered film of claim 146 , wherein the substrate is selected from the group consisting of a polymer, a metal foil, a metal powder, a metal powder film, or a metal coating.

148 . The thin unsintered film of claim 147 , wherein the metal is selected from the group consisting of Ni, Cu, Al, steel, alloys, and combinations thereof.

149 . The thin unsintered film of claim 141 , wherein the solid loading is at least 40% v/v to 80% v/v.

150 . The thin unsintered film of claim 141 , wherein the thin unsintered garnet film thickness is less than 50 μm and greater than 10 nm.

151 . The thin unsintered film of claim 141 , wherein the thin unsintered garnet film is free standing.

152 . The thin unsintered film of claim 150 , wherein:
the thin unsintered garnet film is bonded to a current collector (CC) film on at least one side of the thin unsintered garnet film; and the CC film comprises a metal or metal powder, wherein the metal is selected from the group consisting of Nickel (Ni), Copper (Cu), combinations thereof, and alloys thereof.

153 . The thin unsintered film of claim 152 , wherein the thin unsintered garnet film is bonded to a CC film on one side of the film.

154 . The thin unsintered film of claim 152 , wherein the thin unsintered garnet film is bonded to a CC film on two sides of the film.

155 . A bilayer comprising a metal foil or metal powder positioned in contact with a thin unsintered film according to claim 141 .

156 . A trilayer comp

Assignees

• Quantumscape Corp

Inventors

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

Classifications

• H01M4/366

  as layered products · CPC title

• C04B2235/786

  Micrometer sized grains, i.e. from 1 to 100 micron · CPC title

• C04B41/009

  characterised by the material treated · CPC title

• H01M2300/0091

  in the form of mixtures · CPC title

• H01M4/8657

  layered · CPC title