Amorphous ionically conductive metal oxides and sol gel method of preparation

Abstract

Amorphous lithium lanthanum zirconium oxide (LLZO) is formed as an ionically-conductive electrolyte medium. The LLZO comprises by percentage of total number of atoms from about 0.1% to about 50% lithium, from about 0.1% to about 25% lanthanum, from about 0.1% to about 25% zirconium, from about 30% to about 70% oxygen and from 0.0% to about 25% carbon. At least one layer of amorphous LLZO may be formed through a sol-gel process wherein quantities of lanthanum methoxyethoxide, lithium butoxide and zirconium butoxide are dissolved in an alcohol-based solvent to form a mixture which is dispensed into a substantially planar configuration, transitioned through a gel phase, dried and cured to a substantially dry phase.

1 . An amorphous oxide-based compound having a general formula MwM′xM″yM′″z, wherein
 M comprises at least one alkali metal, 
 M′ comprises at least one element selected from the group consisting of barium, strontium, calcium, indium, magnesium, yttrium, scandium, chromium, aluminum, alkali metals, and lanthanides, 
 M″ comprises at least one element selected from the group consisting of zirconium, tantalum, niobium, antimony, tin, hafnium, bismuth, tungsten, silicon, selenium, gallium and germanium, and 
 M′″ comprises oxygen and optionally at least one element selected from the group consisting of sulfur, selenium, and halogens, 
 wherein w, x, y, and z are positive numbers, including various combinations of integers and fractions or decimals. 
 
     
     
         2 . The amorphous oxide-based compound of  claim 1 , wherein M comprises lithium, M′ comprises lanthanum, M″ comprises zirconium, and M′″ comprises oxygen. 
     
     
         3 . The amorphous oxide-based compound of  claim 1 , wherein by percentage of total number of atoms M comprises from about 0.1% to about 50%, M′ comprises from about 0.1% to about 25%, M″ comprises from about 0.1% to about 25%, and M′″ comprises from about 30% to about 70%. 
     
     
         4 . The amorphous oxide-based compound of  claim 1 , having a substantially planar configuration for an electrolyte medium. 
     
     
         5 . An electrolyte medium comprising at least one layer of amorphous lithium lanthanum zirconium oxide. 
     
     
         6 . The electrolyte medium of  claim 5 , wherein said amorphous lithium lanthanum zirconium oxide comprises by percentage of total number of atoms from about 0.1% to about 50% lithium, from about 0.1% to about 25% lanthanum, from about 0.1% to about 25% zirconium, from about 30% to about 70% oxygen and from 0.0% to about 25% carbon. 
     
     
         7 . A sol gel method for synthesizing an amorphous oxide-based compound comprising:
 producing a mixture by substantially dissolving in a solvent,   a first precursor solute comprising an alkali-metal compound,   a second precursor solute comprising a compound of at least one of barium, strontium, calcium, indium, magnesium, yttrium, scandium, chromium, aluminum, an alkali-metal and a lanthanide,   a third precursor solute comprising a compound of at least one of zirconium, tantalum, niobium, antimony, tin, hafnium, bismuth, tungsten, silicon, selenium, gallium and germanium, and   optionally a fourth precursor solute comprising a compound of at least one of oxygen, sulfur, selenium, and a halogen; and dispensing said mixture in a substantially planar configuration, transitioning through a gel phase, and drying and curing to a substantially dry phase.   
     
     
         8 . A method of synthesizing amorphous lithium lanthanum zirconium oxide comprising:
 producing a mixture by substantially dissolving in a solvent a first precursor solute comprising a compound of lithium, a second precursor solute comprising a compound of lanthanum, and a third precursor solute comprising a compound of zirconium; and   dispensing said mixture in a substantially planar configuration and drying and curing to a substantially dry phase.   
     
     
         9 . The method of  claim 8 , wherein said solvent comprises an alcohol-based solvent, said first precursor solute comprises lithium alkoxide, said second precursor solute comprises lanthanum alkoxide, and said third precursor solute comprises zirconium alkoxide. 
     
     
         10 . The method of  claim 9 , wherein said alcohol-based solvent comprises methoxyethanol. 
     
     
         11 . The method of  claim 9 , wherein said lithium alkoxide comprises lithium butoxide, said lanthanum alkoxide comprises lanthanum methoxyethoxide, and said zirconium alkoxide comprises zirconium butoxide. 
     
     
         12 . The method of  claim 11 , wherein said lanthanum methoxyethoxide comprises an amount of said lanthanum methoxyethoxide pre-dissolved in an amount of said alcohol-based solvent to produce a lanthanum methoxyethoxide solution comprising about 12% by weight of said lanthanum methoxyethoxide. 
     
     
         13 . The method of  claim 11 , wherein said zirconium butoxide comprises an amount of said zirconium butoxide pre-dissolved in an amount of butanol to produce a zirconium butoxide solution comprising about 80% by weight of said zirconium butoxide. 
     
     
         14 . The method of  claim 8 , wherein said mixture is dispensed into a substantially planar configuration by one of spin coating, casting, dip coating, spray coating, screen printing and ink-jet printing. 
     
     
         15 . The method of  claim 11 , wherein said lanthanum methoxyethoxide comprises an amount of said lanthanum methoxyethoxide pre-dissolved in an amount of said alcohol-based solvent to produce a lanthanum methoxyethoxide solution comprising about 12% by weight of said lanthanum methoxyethoxide; and wherein said zirconium butoxide comprises an amount of said zirconium butoxide pre-dissolved in an amount of butanol to produce a zirconium butoxide solution comprising about 80% by weight of said zirconium butoxide. 
     
     
         16 . The method of  claim 8 , wherein the mixture further comprises a polymer. 
     
     
         17 . The method of  claim 16 , wherein said solvent comprises an alcohol-based solvent, said first precursor solute comprises lithium alkoxide, said second precursor solute comprises lanthanum alkoxide, and said third precursor solute comprises zirconium alkoxide. 
     
     
         18 . The method of  claim 17 , wherein said alcohol-based solvent comprises methoxyethanol and said polymer comprises polyvinyl pyrrolidone. 
     
     
         19 . The method of  claim 17 , wherein said lithium alkoxide comprises lithium butoxide, said lanthanum alkoxide comprises lanthanum methoxyethoxide, and said zirconium alkoxide comprises zirconium butoxide. 
     
     
         20 . The method of  claim 19 , wherein said lanthanum methoxyethoxide comprises an amount of said lanthanum methoxyethoxide pre-dissolved in an amount of said alcohol-based solvent to produce a lanthanum methoxyethoxide solution comprising about 12% by weight of said lanthanum methoxyethoxide. 
     
     
         21 . The method of  claim 19 , wherein said zirconium butoxide comprises an amount of said zirconium butoxide pre-dissolved in an amount of butanol to produce a zirconium butoxide solution comprising about 80% by weight of said zirconium butoxide. 
     
     
         22 . The method of  claim 16 , wherein said polymer comprises an amount of said polymer pre-dissolved in an amount of said alcohol-based solvent to produce a polymer solution. 
     
     
         23 . The method of  claim 7 , wherein said mixture is dispensed into a substantially planar configuration by one of spin coating, casting, dip coating, spray coating, screen printing and ink-jet printing. 
     
     
         24 . The method of  claim 19 , wherein said lanthanum methoxyethoxide comprises an amount of said lanthanum methoxyethoxide pre-dissolved in an amount of said alcohol-based solvent to produce a lanthanum methoxyethoxide solution comprising about 12% by weight of said lanthanum methoxyethoxide;
 wherein said zirconium butoxide comprises an amount of said zirconium butoxide pre-dissolved in an amount of butanol to produce a zirconium butoxide solution comprising about 80% by weight said zirconium butoxide; and   wherein said polymer comprises an amount of said polymer pre-dissolved in an amount of said alcohol-based solvent to produce a polymer solution.   
     
     
         25 . The method of  claim 24 , wherein said alcohol-based solvent comprises methoxyethanol and said polymer comprises polyvinyl pyrrolidone. 
     
     
         26 . The method of  claim 7 , wherein the step of drying and curing said mixture comprises exposing and heating said mixture in an environment comprising air and ozone, wherein a concentration of said ozone in said air is greater than 0.05 parts per million. 
     
     
         27 . The method of  claim 26 , wherein the step of drying and curing said mixture further comprises:
 exposing said mixture to said environment comprising air and ozone for about one hour; and   then heating said mixture in said environment comprising air and ozone at about 80° C. for about 30 minutes.   
     
     
         28 . The method of  claim 27 , wherein the steps of exposing and heating said mixture in an environment comprising air and ozone are followed by the step of heating said mixture in air. 
     
     
         29 . The method of  claim 28 , wherein the step of drying and curing said mixture further comprises heating said mixture in air at about 300° C. for about 30 minutes. 
     
     
         30 . The method of  claim 7 , wherein the step of drying and curing said mixture comprises exposing and heating said mixture in an environment comprising air and ozone, wherein a concentration of said ozone in said air is greater than 0.05 parts per million. 
     
     
         31 . The method of  claim 30 , wherein the step of drying and curing said mixture further comprises:
 exposing said mixture to said environment comprising air and ozone for about one hour; and   then heating said mixture in said environment comprising air and ozone at about 80° C. for about 30 minutes.   
     
     
         32 . The method of  claim 30 , wherein the steps of exposing and heating said mixture in an environment comprising air and ozone are followed by the step of heating said mixture in air. 
     
     
         33 . The method of  claim 32 , wherein the step of drying and curing said mixture further comprises:
 exposing said mixture to said environment comprising air and ozone for about one hour;   then heating said mixture in said environment comprising air and ozone at about 80° C. for about 30 minutes; and   then heating said mixture in air at about 300° C. for about 30 minutes.   
     
     
         34 . The method of  claim 16 , wherein the step of drying and curing said mixture comprises exposing and heating said mixture in an environment comprising air and ozone, wherein a concentration of said ozone in said air is greater than 0.05 parts per million. 
     
     
         35 . The method of  claim 34 , wherein the step of drying and curing said mixture further comprises:
 exposing said mixture to said environment comprising air and ozone for about one hour; and   then heating said mixture in said environment comprising air and ozone at about 80° C. for about 30 minutes.   
     
     
         36 . The method of  claim 34 , wherein the steps of exposing and heating said mixture in an environment comprising air and ozone are followed by the step of heating said mixture in air. 
     
     
         37 . The method of  claim 36 , wherein the step of drying and curing said mixture further comprises:
 exposing said mixture to said environment comprising air and ozone for about one hour;   then heating said mixture in said environment comprising air and ozone at about 80° C. for about 30 minutes; and   then heating said mixture in air at about 300° C. for about 30 minutes.   
     
     
         38 . An amorphous oxide-based compound having a general formula MwCM′xM″yM′″z, wherein
 C comprises carbon, 
 M comprises at least one alkali metal, 
 M′ comprises at least one element selected from the group consisting of barium, strontium, calcium, indium, magnesium, yttrium, scandium, chromium, aluminum, alkali metals, and lanthanides, 
 M″ comprises at least one element selected from the group consisting of zirconium, tantalum, niobium, antimony, tin, hafnium, bismuth, tungsten, silicon, selenium, gallium and germanium, and 
 M′″ comprises oxygen and optionally at least one element selected from the group consisting of sulfur, selenium, and halogens, 
 wherein w, x, y, and z are positive numbers, including various combinations of integers and fractions or decimals. 
 
     
     
         39 . The amorphous oxide-based compound of  claim 38 , wherein M comprises lithium, M′ comprises lanthanum, M″ comprises zirconium and M′″ comprises oxygen. 
     
     
         40 . The amorphous oxide-based compound of  claim 38 , wherein by percentage of total number of atoms M comprises from about 0.1% to about 50%, carbon comprises up to about 25%, M′ comprises from about 0.1% to about 25%, M″ comprises from about 0.1% to about 25%, and M′″ comprises from about 30% to about 70%. 
     
     
         41 . The amorphous oxide-based compound of  claim 38 , having a substantially planar configuration for an electrolyte medium. 
     
     
         42 . An electrolyte medium comprising at least one layer of amorphous lithium carbon lanthanum zirconium oxide. 
     
     
         43 . The electrolyte medium of  claim 42 , wherein said amorphous lithium carbon lanthanum zirconium oxide comprises by percentage of total number of atoms from about 0.1% to about 50% lithium, up to about 25% carbon, from about 0.1% to about 25% lanthanum, from about 0.1% to about 25% zirconium, and from about 30% to about 70% oxygen. 
     
     
         44 . A method of synthesizing amorphous lithium carbon lanthanum zirconium oxide comprising:
 producing a mixture by substantially dissolving in a solvent,   a first precursor solute comprising a compound of lithium,   a second precursor solute comprising a compound of lanthanum, and   a third precursor solute comprising a compound of zirconium; and   dispensing said mixture in a substantially planar configuration and drying and curing to a substantially dry phase.   
     
     
         45 . The method of  claim 44 , wherein the step of drying and curing said mixture comprises exposing and heating said mixture in an environment comprising air and ozone, wherein a concentration of said ozone in said air is greater than 0.05 parts per million. 
     
     
         46 . The method of  claim 45 , wherein the step of drying and curing said mixture further comprises:
 exposing said mixture to said environment comprising air and ozone for about one hour; and   then heating said mixture in said environment comprising air and ozone at about 80° C. for about 30 minutes.   
     
     
         47 . The method of  claim 45 , wherein the steps of exposing and heating said mixture in an environment comprising air and ozone are followed by the step of heating said mixture in air. 
     
     
         48 . The method of  claim 47 , wherein the step of drying and curing said mixture further comprises:
 exposing said mixture to said environment comprising air and ozone for about one hour;   then heating said mixture in said environment comprising air and ozone at about 80° C. for about 30 minutes; and   then heating said mixture in air at about 300° C. for about 30 minutes.   
     
     
         49 . The method of  claim 44 , wherein said solvent comprises an alcohol-based solvent, said first precursor solute comprises lithium alkoxide, said second precursor solute comprises lanthanum alkoxide, and said third precursor solute comprises zirconium alkoxide. 
     
     
         50 . The method of  claim 49 , wherein said alcohol-based solvent comprises methoxyethanol. 
     
     
         51 . The method of  claim 49 , wherein said lithium alkoxide comprises lithium butoxide, said lanthanum alkoxide comprises lanthanum methoxyethoxide, and said zirconium alkoxide comprises zirconium butoxide. 
     
     
         52 . The method of  claim 51 , wherein said lanthanum methoxyethoxide comprises an amount of said lanthanum methoxyethoxide pre-dissolved in an amount of said alcohol-based solvent to produce a lanthanum methoxyethoxide solution comprising about 12% by weight of said lanthanum methoxyethoxide. 
     
     
         53 . The method of  claim 51 , wherein said zirconium butoxide comprises an amount of said zirconium butoxide pre-dissolved in an amount of butanol to produce a zirconium butoxide solution comprising about 80% by weight of said zirconium butoxide. 
     
     
         54 . The method of  claim 51 , wherein said lanthanum methoxyethoxide comprises an amount of said lanthanum methoxyethoxide pre-dissolved in an amount of said alcohol-based solvent to produce a lanthanum methoxyethoxide solution comprising about 12% by weight of said lanthanum methoxyethoxide; and wherein said zirconium butoxide comprises an amount of said zirconium butoxide pre-dissolved in an amount of butanol to produce a zirconium butoxide solution comprising about 80% by weight of said zirconium butoxide. 
     
     
         55 . The method of  claim 44 , wherein said mixture is dispensed into a substantially planar configuration by one of spin coating, casting, dip coating, spray coating, screen printing and ink-jet printing. 
     
     
         56 . The method of  claim 44 , wherein the mixture further comprises a polymer. 
     
     
         57 . The method of  claim 56 , wherein the step of drying and curing said mixture comprises exposing and heating said mixture in an environment comprising air and ozone, wherein a concentration of said ozone in said air is greater than 0.05 parts per million. 
     
     
         58 . The method of  claim 57 , wherein the step of drying and curing said mixture further comprises:
 exposing said mixture to said environment comprising air and ozone for about one hour; and   then heating said mixture in said environment comprising air and ozone at about 80° C. for about 30 minutes.   
     
     
         59 . The method of  claim 57 , wherein the steps of exposing and heating said mixture in an environment comprising air and ozone are followed by the step of heating said mixture in air. 
     
     
         60 . The method of  claim 59 , wherein the step of drying and curing said mixture further comprises:
 exposing said mixture to said environment comprising air and ozone for about one hour;   then heating said mixture in said environment comprising air and ozone at about 80° C. for about 30 minutes; and   then heating said mixture in air at about 300° C. for about 30 minutes.   
     
     
         61 . The method of  claim 56 , wherein said solvent comprises an alcohol-based solvent, said first precursor solute comprises lithium alkoxide, said second precursor solute comprises lanthanum alkoxide, and said third precursor solute comprises zirconium alkoxide. 
     
     
         62 . The method of  claim 61 , wherein said alcohol-based solvent comprises methoxyethanol and said polymer comprises polyvinyl pyrrolidone. 
     
     
         63 . The method of  claim 61 , wherein said lithium alkoxide comprises lithium butoxide, said lanthanum alkoxide comprises lanthanum methoxyethoxide, and said zirconium alkoxide comprises zirconium butoxide. 
     
     
         64 . The method of  claim 63 , wherein said lanthanum methoxyethoxide comprises an amount of said lanthanum methoxyethoxide pre-dissolved in an amount of said alcohol-based solvent to produce a lanthanum methoxyethoxide solution comprising about 12% by weight of said lanthanum methoxyethoxide. 
     
     
         65 . The method of  claim 63 , wherein said zirconium butoxide comprises an amount of said zirconium butoxide pre-dissolved in an amount of butanol to produce a zirconium butoxide solution comprising about 80% by weight of said zirconium butoxide. 
     
     
         66 . The method of  claim 56 , wherein said polymer comprises an amount of said polymer pre-dissolved in an amount of said alcohol-based solvent to produce a polymer solution. 
     
     
         67 . The method of  claim 63 , wherein said lanthanum methoxyethoxide comprises an amount of said lanthanum methoxyethoxide pre-dissolved in an amount of said alcohol-based solvent to produce a lanthanum methoxyethoxide solution comprising about 12% by weight of said lanthanum methoxyethoxide;
 wherein said zirconium butoxide comprises an amount of said zirconium butoxide pre-dissolved in an amount of butanol to produce a zirconium butoxide solution comprising about 80% by weight of said zirconium butoxide; and   wherein said polymer comprises an amount of said polymer pre-dissolved in an amount of said alcohol-based solvent to produce a polymer solution.   
     
     
         68 . The method of  claim 67 , wherein said alcohol-based solvent comprises methoxyethanol and said polymer comprises polyvinyl pyrrolidone. 
     
     
         69 . The method of  claim 56 , wherein said mixture is dispensed into a substantially planar configuration by one of spin coating, casting, dip coating, spray coating, screen printing, and ink-jet printing. 
     
     
         70 . The method of  claim 8 , wherein said solvent comprises an alcohol-based solvent, and wherein at least one of said first precursor solute, said second precursor solute, and said third precursor solute comprises a metal β-diketonate. 
     
     
         71 . The method of  claim 70 , wherein the metal β-diketonate comprises a metal acetyl acetonate. 
     
     
         72 . The method of  claim 16 , wherein said solvent comprises an alcohol-based solvent, and wherein at least one of said first precursor solute, said second precursor solute, and said third precursor solute comprises a metal β-diketonate. 
     
     
         73 . The method of  claim 72 , wherein the metal β-diketonate comprises a metal acetyl acetonate. 
     
     
         74 . The method of  claim 44 , wherein said solvent comprises an alcohol-based solvent, and wherein at least one of said first precursor solute, said second precursor solute, and said third precursor solute comprises a metal β-diketonate. 
     
     
         75 . The method of  claim 74 , wherein the metal β-diketonate comprises a metal acetyl acetonate. 
     
     
         76 . The method of  claim 56 , wherein said solvent comprises an alcohol-based solvent, and wherein at least one of said first precursor solute, said second precursor solute, and said third precursor solute comprises a metal β-diketonate. 
     
     
         77 . The method of  claim 76 , wherein the metal β-diketonate comprises a metal acetyl acetonate. 
     
     
         78 . The method of  claim 7 , wherein the mixture further comprises at least one gelling, drying, and/or curing control agent. 
     
     
         79 . The method of  claim 78 , wherein the at least one gelling, drying, and/or curing control agent is selected from the group consisting of acetylacetone, acetic acid, ethanol, and an ethanol/water mixture. 
     
     
         80 . The method of  claim 8 , wherein the mixture further comprises at least one gelling, drying, and/or curing control agent. 
     
     
         81 . The method of  claim 80 , wherein the at least one gelling, drying, and/or curing control agent is selected from the group consisting of acetylacetone, acetic acid, ethanol, and an ethanol/water mixture. 
     
     
         82 . The method of  claim 44 , wherein the mixture further comprises at least one gelling, drying, and/or curing control agent. 
     
     
         83 . The method of  claim 82 , wherein the at least one gelling, drying, and/or curing control agent is selected from the group consisting of acetylacetone, acetic acid, ethanol, and an ethanol/water mixture.