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

Patent metadata

Field	Value
Publication number	US-2017346135-A1
Application number	US-201715480475-A
Country	US
Kind code	A1
Filing date	Apr 6, 2017
Priority date	Oct 7, 2013
Publication date	Nov 30, 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 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.

125 . The thin unsintered garnet 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.

126 . The thin unsintered garnet 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.

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

128 . The thin unsintered garnet 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.

129 . The thin unsintered garnet film of claim 128 , wherein the metal is selected from the group consisting of Ni, Cu, Al, steel, alloys, and combinations thereof.

130 . The thin unsintered garnet film of claim 124 , wherein the solid loading is at least 35% v/v to 80% v/v.

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

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

133 . The thin unsintered garnet 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 garnet 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; the CC comprises a metal or metal powder; and the CC film comprises a metal selected from the group consisting of Nickel (Ni), Copper (Cu), combinations thereof, and alloys thereof.

135 . The thin unsintered garnet film of claim 134 , wherein the thin unsintered garnet film is bonded to a CC on one side of the film.

136 . The thin unsintered garnet film of claim 134 , wherein the thin unsintered garnet film is bonded to a CC on two sides of the film.

137 . A trilayer comprising a metal foil or metal powder positioned between, and in contact with, two thin unsintered garnet films according to claim 134 .

138 . A bilayer comprising a metal foil or metal powder positioned in contact with a thin unsintered garnet film according to claim 134 .

Assignees

• Quantumscape Corp

Inventors

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

Classifications

• C04B35/6262

  of calcined, sintered clinker or ceramics · CPC title

• C04B35/645

  Pressure sintering · CPC title

• C04B2235/6025

  Tape casting, e.g. with a doctor blade · CPC title

• C04B2235/3294

  Antimony oxides, antimonates, antimonites or oxide forming salts thereof, indium antimonate · CPC title

• C04B2235/3217

  Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina · CPC title