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

Patent metadata

Field	Value
Publication number	US-2017179522-A1
Application number	US-201715430375-A
Country	US
Kind code	A1
Filing date	Feb 10, 2017
Priority date	Oct 7, 2013
Publication date	Jun 22, 2017
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 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 5<A<8, 1.5<B<4, 0.1≦C≦2, O<D≦2; 1≦E≦2, 10<F≦13, and M′ is Al; and M″ is selected from Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, and Rb.

125 . The composition of claim 124 , wherein the composition is characterized by the empirical formula Li 7.0 La 3 (Zr t1 +Nb t2 )O 12 +0.35Al 2 O 3 ; wherein t1+t2=2 such that the molar ratio of La to the combined amount of (Zr+Nb) is 3:2.

126 . 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 6.5<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 Ta.

127 . The composition of claim 124 , wherein E is 1, 1.5, or 2.

128 . The composition of claim 124 , wherein the molar ratio of Garnet:Al 2 O 3 is between 1:0.1 and 1:0.65.

129 . The composition of claim 124 , wherein the molar ratio of Garnet:Al 2 O 3 is between 1:0.15 and 1:0.55.

130 . The composition of claim 124 , wherein the molar ratio of Garnet:Al 2 O 3 is between 1:0.25 and 1:0.45.

131 . The composition of claim 124 , wherein the subscript values represent elemental molar ratios of the precursor chemicals used to make the claimed composition.

132 . The composition of claim 124 , wherein the composition is a thin film having a film thickness of about 10 nm to about 100 μm.

133 . The composition of claim 132 , wherein the thickness is less than 20 μm and greater than 10 nm.

134 . The composition of claim 132 , wherein the film has grains having a d 50 diameter less than 10 μm.

135 . The composition of claim 132 , wherein the film has grains having a d 50 diameter less than 5 μm.

136 . The composition of claim 132 , wherein the film has grains having a d 50 diameter less than 2 μm.

137 . The composition of claim 132 , wherein the film has grains having a d 50 diameter less than 1 μm.

138 . An energy storage device comprising an electrolyte comprising the composition of claim 124 .

139 . An electrochemical device comprising a catholyte comprising the composition of claim 124 .

140 . A thin unsintered garnet film, comprising
lithium-stuffed garnet precursors or calcined garnet; at least one member selected from the group consisting of a binder, a solvent, a dispersant, and combinations thereof; wherein the garnet solid loading is at least 30% by volume (v/v); and wherein the film thickness is less than 100 μm.

141 . The thin unsintered garnet film of claim 140 , 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
M″ is selected from Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, or Rb.

142 . The thin unsintered garnet film of claim 140 , 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, and M′ is Al M″ is Ta.

143 . The thin unsintered garnet film of claim 140 , wherein the thin unsintered garnet film is adhered to a substrate.

144 . The thin unsintered garnet film of claim 143 , wherein the substrate is a polymer, a metal foil, a metal powder, a metal powder film, or a metal coating.

145 . The thin unsintered garnet film of claim 144 , wherein the metal is selected from Ni, Cu, Al, steel, alloys, or combinations thereof.

146 . The thin unsintered garnet film of claim 140 , wherein the solid loading is at least 35% v/v to 80% v/v.

147 . The thin unsintered garnet film of claim 140 , wherein the thin unsintered garnet film thickness is less than 50 μm and greater than 10 nm.

148 . The thin unsintered garnet film of claim 140 , wherein the thin unsintered garnet film is free standing.

149 . The thin unsintered garnet film of claim 140 ,
wherein the thin unsintered garnet film thickness is less than 50 μm and greater than 10 nm, and wherein the thin unsintered garnet film is optionally bonded to a current collector (CC) film on at least one side of the thin unsintered garnet film, wherein the CC comprises a metal or metal powder.

150 . The thin unsintered garnet film of claim 149 , wherein the CC film comprises a metal selected from the group consisting of Nickel (Ni), Copper (Cu), combinations thereof, and alloys thereof.

151 . The thin unsintered garnet film of claim 150 , wherein the thin unsintered garnet film is bonded to a CC on one side of the film.

152 . The thin unsintered garnet film of claim 150 , wherein the thin unsintered garnet film is bonded to a CC on two sides of the film.

153 . A trilayer comprising a metal foil or metal powder positioned between, and in contact with, two thin unsintered garnet films according to claim 150 .

154 . A bilayer comprising a metal foil or metal powder positioned in contact with a thin unsintered garnet film according to claim 150 .

Assignees

• Quantumscape Corp

Inventors

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

Classifications

• C04B2235/6567

  Treatment time · CPC title

• H01M10/0585

  of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators · CPC title

• C04B35/645

  Pressure sintering · CPC title

• C04B2235/3222

  Aluminates other than alumino-silicates, e.g. spinel (MgAl2O4) · CPC title

• C04B2235/666

  Applying a current during sintering, e.g. plasma sintering [SPS], electrical resistance heating or pulse electric current sintering [PECS] · CPC title