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

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.

1 - 38 . (canceled) 
     
     
         39 . A method of making a lithium stuffed garnet doped with aluminum, the method comprising
 providing garnet precursors at a predetermined combination;   optionally drying the precursors for about 10 minutes to about 10 hours at about 80° C. to about 200° C.;   milling the combination for 5 to 10 hours;   calcining the combination in vessels at about 500° C. to about 1200° C. for about 4 to about 10 hours to form a garnet phase;   milling the formed garnet until the d 50  particle size is between 100 and 1000 nm;   mixing the milled formed garnet with a binder to form a slurry optionally comprising at least one member selected from the group consisting of a plasticizer, a dispersant, a surfactant, a binder mixture, a solvent, a solvent mixture, formed garnet, garnet chemical precursors, and combinations thereof;   optionally filtering the slurry;   providing green films of the slurry;   sintering the green film;   wherein sintering comprises:
 applying pressure to the film with setter plates; 
 heating the film under flowing gas between 140° C. and 1200° C. for about 15 minutes to about 6 hours. 
   
     
     
         40 . The method of  claim 39 , wherein the garnet precursor are selected from LiOH, Li 2 O, Li 2 CO 3 , La 2 O 3 , ZrO 2 , aluminum hydroxide, Al 2 O 3  and Al(NO 3 ) 3 .9H 2 O. 
     
     
         41 . The method of  claim 39 , wherein calcining the combination is in vessels at between 800 to 1000° C. for 6 hours or less. 
     
     
         42 . The method of  claim 39 , wherein the calcining comprises using Alumina vessels. 
     
     
         43 . The method of  claim 39 , wherein the milling the formed garnet is until the d 50  particle size is 400 nm. 
     
     
         44 . The method of any  claim 39 , wherein the mixing the milled forming garnet with a binder to form a slurry comprises about at least 4% to 50% w/w binder. 
     
     
         45 . (canceled) 
     
     
         46 . The method of  claim 39 , wherein the filtering the slurry comprises filtering with an 80 mesh sieve. 
     
     
         48 . The method of  claim 39 , wherein the applying pressure to the film with setter plates comprises applying a pressure of between 1 and 1000 pounds per square inch. 
     
     
         49 . The method of  claim 39 , wherein the setter plates are Pt setter plates. 
     
     
         50 . The method of  claim 39 , wherein the flowing gas is an Argon gas flowing at a flow rate of 315 sccm. 
     
     
         51 . The method of any  claim 39 , wherein the heating the slurry under flowing inert gas comprises separate dwells at 160° C. to 200° C. and 330° C. to 600° C. for 2 to 4 hours (hrs) each under a humidified Argon flow. 
     
     
         52 . The method of  claim 39 , wherein the milling the formed garnet is until the d 50  is between 200 and 450 nm. 
     
     
         53 - 91 . (canceled) 
     
     
         92 . A method for sintering a thin and free standing garnet film, comprising the following steps
 providing a green tape by casting a garnet slurry;   wherein the slurry comprises at least one member selected from the group consisting of
 garnet precursors, garnet, a binder, a solvent, a plasticizer, a surfactant, a dispersant, and combinations thereof. 
   sintering the green tape between setter plates;
 wherein the sintering is heat, spark plasma, or field assisted sintering; 
 and wherein sintering optionally includes applying pressure to the film with the setter plates. 
   
     
     
         93 . The method of  claim 92 , wherein the slurry comprises milled and calcined garnet. 
     
     
         94 . The method of  claim 92 , wherein the solid loading of the green tape is at least 30% v/v. 
     
     
         95 . The method of  claim 92 , wherein the solid loading of the green tape is at least 40% v/v. 
     
     
         96 . The method of  claim 92 , wherein the solid loading of the green tape is at least 50% v/v. 
     
     
         97 . The method of  claim 92 , wherein the solid loading of the green tape is at least 60% v/v. 
     
     
         98 . The method of  claim 92 , wherein the solid loading of the green tape is at least 65% v/v. 
     
     
         99 . The method of  claim 92 , wherein the film is sintered directly onto a metal. 
     
     
         100 . The method of  claim 99 , wherein the metal is a metal powder or a metal foil. 
     
     
         101 . The method of  claim 100 , wherein a metal powder is between and in contact with one side of the green tape and one setter plate. 
     
     
         102 . The method of  claim 100 , wherein a metal powder layer is positioned between and in contact with two green tapes, and wherein the green tapes are between and in contact with the setter plates. 
     
     
         103 . The method of  claim 99 , wherein the metal powder is Ni or Cu powder. 
     
     
         104 . The method of  claim 92 , wherein a source of Li is placed in proximity of the sintered film during sintering. 
     
     
         105 . The method of  claim 92 , wherein the setter plates are selected from YSZ, graphite, YSZ, Mg—SZ, zirconia, porous zirconia, SiO 2 , SiO 2  sand, LiAlO 2 , Li 2 O, LiLaO 2 , Li 6 Zr 2 O 7 , Al 2 O 3 , Al 2 O 3  powder, Al 2 O 3  paper, nickel, nickel powder, garnet ceramics, garnet powder, a sacrificial garnet film, Li 2 ZrO 3 . 
     
     
         106 . (canceled) 
     
     
         107 . The method of  claim 105 , wherein a zirconia setter plate contacts the metal powder. 
     
     
         108 - 123 . (canceled) 
     
     
         124 . The method of  claim 39  wherein the flowing gas is at a controlled humidity and oxygen partial pressure. 
     
     
         125 . The method of  claim 39  wherein calcining the combination comprises calcining between 800-1000° C. for 10 hours or less and then calcining again between 800-1000° C. for 10 hours or less.