Doped lithium lanthanum zirconium oxide

Abstract

The present application provides a reaction composition for forming a doped lithium lanthanum zirconium oxide comprising one or more lithium, lanthanum and / or zirconium species for forming a doped lithium lanthanum zirconium oxide, and at least one dopant provided as a polyoxometallate. The invention also provides a method for preparing the doped lithium lanthanum zirconium oxide.

Description

BACKGROUND

[0001] The present disclosure relates to doped lithium lanthanum zirconium oxides.

[0002] The present application relates to doped lithium lanthanum zirconium oxides. More particularly, but not exclusively, the present application relates to a method of making doped lithium lanthanum zirconium oxides. The present application also relates to doped lithium lanthanum zirconium oxides, compositions for forming doped lithium lanthanum zirconium oxides, and two-part reaction mixture compositions for forming doped lithium lanthanum zirconium oxides.

[0003] Doped lithiumated solid state electrolyte materials are typically prepared using solid state synthesis methods. This typically requires high temperature heating for long periods of time. These methods are energy intensive and can not be suitable for large scale production of the materials. Furthermore, in some cases, the produced materials require extensive processing. It is known that aqueous synthesis routes can be used to produce doped lithiumated solid state electrolyte materials, but these known routes often produce hazardous or unwanted waste, such as ammonium oxalate or choline hydroxide. Known synthesis routes sometimes use relatively unstable reagents or precursors, such as niobium pentachloride.

[0004] The present application aims to alleviate the above problems. Alternatively, or in addition, the present application aims to provide an improved method of making doped lithiumated solid state electrolyte materials, in particular, but not exclusively, doped lithium lanthanum zirconium oxides (sometimes referred to herein as LLZO). SUMMARY According to a first aspect of the present application, there is provided a method of making a doped lithium lanthanum zirconium oxide, the method comprising: forming the doped lithium lanthanum zirconium oxide from a polyoxometalate.

[0006] Applicants have found that doped lithium lanthanum zirconium oxides can be made using polyoxometalates. Examples of such methods have been shown to be effective, typically do not produce hazardous waste, and typically use relatively stable precursors.

[0007] The polyoxometalate optionally provides at least one dopant, and optionally a plurality of dopants. For the avoidance of doubt, the dopant(s) can be provided from one or more sources other than the polyoxometalate.

[0008] The skilled person will appreciate that the polyoxometalate structure is not retained in the doped lithium lanthanum zirconium oxide (“LLZO”). The polyoxometalate has been shown to be a suitable carrier for providing the dopant as part of the doped LLZO.

[0009] The dopant can be any suitable element other than lithium, lanthanum, zirconium, and oxygen, in amounts exceeding trace amounts in the doped lithium lanthanum zirconium oxide. For example, the dopant can be a metal or semimetal (such as boron or tellurium). For example, the dopant can be a halogen. For example, some of the oxygen can be replaced by a halogen. Such a doped material can comprise a lattice, optionally a crystalline lattice, in which certain species occupy lattice sites, and certain species occupy sites between the lattice sites (sites between the lattice sites, often referred to as "interstitial sites"). The one or more dopants can optically occupy sites between the lattice sites and / or occupy lattice sites. Optionally, the one or more species for incorporation into the solid state electrolyte material can comprise species for forming a lattice structure, thus optionally occupying lattice sites. The method is optionally performed in an aqueous liquid. For the avoidance of doubt, the method can comprise one or more dopants in addition to the dopant provided by the polyoxometalate.

[0010] The polyoxometalate is a polyatomic ion, typically but not always an anion, comprising three or more metal oxo anions connected together by shared oxygen atoms to form a closed three-dimensional framework. The polyoxometalate can optionally comprise a transition metal, a Group 13 species (such as boron (B), aluminum (Al), gallium (Ga), indium (In), thallium (Tl), or ruthenium (Nh)), a Group 15 species (such as arsenic (As), antimony (Sb), or bismuth (Bi)), or a Group 16 species (such as selenium (Se) or tellurium (Te)). The polyoxometalate can comprise one or more of niobium, molybdenum, tungsten, tellurium, tantalum, and aluminum. Each polyoxometalate ion comprises at least 3, optionally at least 4, optionally at least 5, optionally at least 6, and optionally at least 7 metal species. Each polyoxometalate ion can comprise no more than 300 metal species, optionally no more than 250, optionally no more than 200, optionally no more than 150, optionally no more than 100, optionally no more than 80, optionally no more than 60, optionally no more than 50, optionally no more than 40, optionally no more than 30, optionally no more than 20, optionally no more than 15, optionally no more than 14, optionally no more than 13, optionally no more than 12, optionally no more than 11, optionally no more than 10, optionally no more than 9, optionally no more than 8, optionally no more than 7 metal species. For the avoidance of doubt, what is meant here is the total number of metal atoms / ions in the polyoxometalate ion, not the number of different metal species in the ion.

[0011] For example, the polyoxometalate can have a Keggin structure, a Lindqvist structure, or an Anderson-Evans structure.

[0012] Optionally, the polyoxometalate comprises one or more of Nb, Te, Al, Ga, Sb, W, and Ta.

[0013] Optionally, the polyoxometalate can comprise one or more of [Nb6O 19 ] 8- , [Mo7O 24 ] 6- , [TeNb5O 19 ] 7- , [TeW6O 24 ] 6- , [Nb 6-x W x O 19 ] (8-x)- , [Nb3W3O 19 ] 5- , [Nb3Ta3O 19 ] -8 , [W 12 O 40 ] 8- , [W 12 O 42 ] 12- , and [Al 13 O4(OH) 24 ] 7+ wherein x is an integer from 1 to 5.

[0014] The method can comprise mixing at least two compositions, wherein at least one composition comprises a polyoxometalate. At least one composition optionally comprises a lanthanide species. At least one composition optionally comprises a zirconium species. At least one composition can optionally comprise one or more dopant species not provided by the polyoxometalate.

[0015] The method optionally comprises forming a composition (optionally a precipitate) comprising a lanthanide species, a zirconium species, and one or more dopant species derived from a polyoxometalate, optionally free of lithium species. As described above, the one or more dopant species can be initially provided as a polyoxometalate. The method can comprise forming the composition and then contacting the composition with one or more lithium species.

[0016] Forming a composition (optionally a precipitate) comprising a lanthanide species, a zirconium species, and one or more dopant species, optionally at a pH of at least 3.5, optionally at least 3.6, optionally at least 3.7, optionally at least 3.8, optionally at least 3.9, optionally at least 4.0, optionally at least 7, optionally at least 8, and optionally at least 9.

[0017] Forming a composition (optionally a precipitate) comprising a lanthanide species, a zirconium species, and one or more dopant species derived from a polyoxometalate can include mixing at least two precursor compositions, at least one of which comprises a polyoxometalate. At least one of the precursor compositions optionally comprises a lanthanide species. At least one of the precursor compositions optionally comprises a zirconium species. At least one of the precursor compositions can optionally comprise one or more dopants that are not provided by a polyoxometalate. Optionally, at least one of the precursor compositions is in solution form. Optionally, at least one of the precursor compositions is in suspension form. Optionally, at least two of the precursor compositions are in solution form. Optionally, at least one of the precursor compositions comprises a base, such as a hydroxide, carbonate, or bicarbonate. Optionally, at least one of the precursor compositions comprises lanthanide and zirconium species, and optionally comprises one or more dopants, optionally from a polyoxometalate. Optionally, at least one of the precursor compositions comprises lanthanide and zirconium species, but does not comprise a dopant, while another of the precursor compositions comprises one or more dopants, optionally from a polyoxometalate. Optionally, at least one of the precursor compositions comprises lanthanide and zirconium species, and one or more dopants, while another of the precursor compositions comprises one or more dopants, optionally from a polyoxometalate, and optionally a base. Optionally, at least one of the precursor compositions comprises lanthanide and zirconium species, and one or more dopants, while another of the precursor compositions comprises a base, but does not comprise a dopant. Optionally, one of the precursor compositions can be acidic.

[0018] For example, a first precursor composition (optionally in solution form) can comprise one or more of Zr, La, and optionally one or more dopants. The first precursor composition can optionally be acidic. A second precursor composition (optionally in solution form, and also optionally in suspension form) can comprise one or more of a base, one or more dopants, and one or more of Zr and La. Such dopants can optionally be provided in the form of a polyoxometalate. Providing two such precursor compositions that can be mixed to form a precipitate is an effective method of making a composition (e.g., in the form of a precipitate) from which doped lithium lanthanum zirconium oxide can be made.

[0019] Optionally, a first precursor composition (optionally in solution form) can comprise one or more of Zr, La, and optionally one or more dopants. The first precursor composition can optionally be acidic. A second precursor composition (optionally in solution form, and also optionally in suspension form) can comprise one or more of a base and one or more dopants, but does not comprise one or more of Zr and La. Such dopants are optionally provided in the form of a polyoxometalate. Providing two such precursor compositions that can be mixed to form a precipitate is an effective method of making a composition (e.g., in the form of a precipitate) from which doped lithium lanthanum zirconium oxide can be made.

[0020] Optionally, the first precursor composition (optionally in solution form) may contain one or more of Zr and La, and optionally one or more dopants. Such dopants are optionally provided as polyoxometalates. The first composition may optionally be acidic. The second precursor composition (optionally in solution form, and also optionally in suspension form) may contain a base, but does not contain one or more dopants, nor one or more of Zr and La. Providing two such precursor compositions that can be mixed to form a precipitate is an efficient method for preparing compositions (e.g., in precipitate form) from which doped lithium lanthanum zirconium oxide can be prepared.

[0021] The method includes contacting the composition with a lithium substance (optionally lithium ions). Lithium ions can be provided by forming a solution containing lithium ions (e.g., by dissolving a lithium salt) and contacting the composition with the solution. Alternatively or additionally, the composition (e.g., in the form of a precipitate) will be present in a liquid, and the method may include dissolving a lithium salt in the liquid to provide lithium ions. The lithium salt may comprise any suitable lithium salt, such as lithium hydroxide, lithium nitrate, lithium halide, or lithium acetate.

[0022] The lithium material can be brought into contact with the composition by grinding (e.g., ball milling).

[0023] The lithium material can be brought into contact with the composition by freeze drying or spray drying.

[0024] The method may include forming a lithium-containing precipitate. The lithium-containing precipitate may be formed after, or simultaneously with, contact of a lithium material (optionally lithium ions) with a composition comprising zirconium, lanthanum, and one or more dopants. Forming the lithium-containing precipitate may include providing an anion source to which lithium can form an insoluble salt. For the avoidance of ambiguity, "providing" does not mean adding an anion source capable of forming an insoluble salt with lithium in a separate step. For example, a composition comprising zirconium, lanthanum, and one or more dopants may also include an anion source to which lithium can form an insoluble salt.

[0025] Forming a lithium-containing precipitate may optionally include: (i) contacting a composition comprising zirconium, lanthanum, and one or more dopants (optionally comprising a solid and optionally comprising a precipitate) with lithium ions, followed by providing an anion source capable of forming an insoluble salt with lithium; (ii) forming a composition comprising zirconium, lanthanum, one or more dopants, and an anion source capable of forming an insoluble salt with lithium (optionally comprising a solid and optionally comprising a precipitate), followed by providing lithium ions; or (iii) simultaneously contacting a composition comprising zirconium, lanthanum, and one or more dopants (optionally comprising a solid and optionally comprising a precipitate) with an anion source capable of forming an insoluble salt with lithium and lithium ions; or (iv) contacting a composition comprising zirconium, lanthanum, and one or more dopants (optionally comprising a solid and optionally comprising a precipitate) with an anion source capable of forming an insoluble salt with lithium, followed by providing lithium ions. In some cases, option (i) is preferred because it yields a higher desired product yield. Lithium ions can be provided by dissolving a soluble lithium salt in a liquid (such as a carrier liquid of the precipitate). Alternatively or additionally, lithium ions can also be provided by providing a lithium ion solution and contacting the solution with the precipitate.

[0026] The insoluble salt referred to here means that the salt is optionally insoluble in aqueous solution, and its insolubility is sufficient to precipitate it from the solution.

[0027] Anion sources that can form insoluble salts with lithium can include carbonate anion sources. Lithium carbonate is insoluble in many liquids, such as aqueous liquids. Carbonate anion sources can include one or more of carbonate ions, bicarbonate ions, and carbon dioxide. Carbon dioxide may be particularly effective because the solution from which lithium-containing precipitates are removed is a lithium carbonate solution, which can be reused without further purification. Therefore, this reduces lithium loss.

[0028] The method may include heating a lithium-containing precipitate to form a doped solid electrolyte material. This heating may optionally include calcining the lithium-containing precipitate. In this example, calcination includes heating to induce a phase transition. Heating the lithium-containing precipitate to form the doped solid electrolyte material may optionally include heating the lithium-containing precipitate to at least 500°C, optionally at least 600°C, optionally at least 700°C, optionally at least 800°C, optionally at least 900°C, and optionally at least 1000°C. Heating the lithium-containing precipitate to form the doped solid electrolyte material may optionally include heating the lithium-containing precipitate to no more than 1500°C, optionally no more than 1400°C, optionally no more than 1300°C, optionally no more than 1200°C, optionally no more than 1100°C, and optionally no more than 1000°C.

[0029] The method may include separating lithium-containing precipitates from ambient liquids, for example, by filtration and / or drying. For example, spray drying or freeze drying may be used.

[0030] The method may include drying a lithium-containing precipitate, optionally separating the lithium-containing precipitate from an ambient liquid. Drying the lithium-containing precipitate may include heating the lithium-containing precipitate to a temperature not exceeding 200°C, optionally not exceeding 180°C, optionally not exceeding 160°C, optionally not exceeding 140°C, optionally not exceeding 120°C, or optionally not exceeding 100°C. Drying the lithium-containing precipitate may include heating the lithium-containing precipitate to a temperature of at least 60°C, optionally at least 80°C, optionally at least 100°C, or optionally at least 120°C. Drying the lithium-containing precipitate may include exposing the lithium-containing precipitate to reduced pressure conditions.

[0031] Doped lithium-ion solid electrolyte materials may contain Li A La B Zr C O D Where A = 5.0-8.0, B = 2.5-3.0, C = 1.0-2.0, and D = 11-12. A is optionally at least 5.5, and optionally at least 5.8. A is optionally not exceeding 7.0, and optionally not exceeding 6.8. B is optionally at least 2.5, and optionally at least 2.8. C is optionally at least 1.3, and optionally at least 1.4. C is optionally not exceeding 1.8. D is optionally 12. To avoid ambiguity, the doped lithium-ion solid electrolyte material will contain dopants in addition to lithium, lanthanum, zirconium, and oxygen.

[0032] The following statements relating to the method of the first aspect of this application preferably relate to doped lithium lanthanum zirconium oxide. One or more dopants comprise one or more of alkali metals, alkaline earth metals, transition metals (e.g., Group 4, 5, or 6 substances), Group 13 substances, Group 15 substances, Group 16 substances, rare earth substances, and lanthanides. This is especially true when the doped lithium-ionized solid electrolyte material is doped lithium lanthanum zirconium oxide.

[0033] Doped lithium lanthanum zirconium oxide has the formula Li A La B Zr C O D X EWhere A = 5.0-8.0, B = 2.5-3.0, C = 1.0-2.0, D = 11-12, and X is one or more dopants, and E is the total amount of dopants. E is optionally at least 0.01, optionally at least 0.05, optionally at least 0.1, optionally at least 0.15, optionally at least 0.2, optionally at least 0.25, optionally at least 0.3. E is optionally not more than 1.0, optionally not more than 0.9, optionally not more than 0.8, optionally not more than 0.75.

[0034] One or more dopants may optionally include one or more of transition metals, Group 6 substances, Group 13 substances, Group 15 substances, and Group 16 substances.

[0035] One or more dopants may optionally include one or more of alkali metals, alkaline earth metals, Group 4 substances, Group 6 substances, lanthanides, and rare earth substances.

[0036] One or more dopants may optionally include one or more of transition metals, Group 6 substances, Group 13 substances, Group 15 substances, and Group 16 substances, and may also include one or more of alkali metals, alkaline earth metals, Group 4 substances, Group 6 substances, lanthanides, and rare earth substances.

[0037] Optionally, the doped lithium lanthanum zirconium oxide may have the formula Li A La B Zr C O D X1 E1 X2 E2Where A, B, C, and D are defined above, and X1 represents one or more dopants, each dopant comprising a transition metal (optionally Group 4, 5, or 6) (optionally Ta and / or Nb, and / or Group 6 (optionally W and / or Mo)), a Group 13 (optionally Ga and / or Al), a Group 15 (optionally Sb), or a Group 16 (optionally Te), and E1 represents the total amount of such dopants. X2 represents one or more dopants, each of which is not a transition metal, a Group 13, a Group 15, or a Group 16, and E2 represents the total amount of such dopants. E1 is optionally at least 0.01, optionally at least 0.05, optionally at least 0.1, optionally at least 0.15, optionally at least 0.2, optionally at least 0.25, optionally at least 0.3. E1 is optionally not more than 0.8, optionally not more than 0.7, optionally not more than 0.6. E2 is optionally at least 0.01, optionally at least 0.05, optionally at least 0.08, optionally at least 0.1, optionally at least 0.2. E2 is optionally not more than 0.5, optionally not more than 0.4, optionally not more than 0.3. X2 optionally represents one or more dopants, each dopant comprising an alkali metal (optionally Rb), an alkaline earth metal (optionally selected from Ca, Ba, Mg, and Sr), a lanthanide (optionally Ce), and a rare earth material (optionally Y and / or Sc). X2 optionally represents one or more dopants, each dopant comprising an alkali metal, an alkaline earth metal, a lanthanide, or a rare earth material.

[0038] For example, X1 can represent one or more of Nb, Te, Al, Ga, Sb, W, and Ta.

[0039] For example, X2 can represent one or more of Hf, Ti, Sr, Ca, Ba, Mg, Ce, Sc, Y, and Rb.

[0040] One or more dopants may optionally include one or more of Mo, Nb, Te, Al, Ga, Sb, W, and Ta. Such dopants have been found to be advantageous for LLZO materials.

[0041] One or more dopants may optionally include one or more of Hf, Ti, Sr, Ca, Ba, Mg, Ce, Sc, Y, and Rb. Such dopants are beneficial to LLZO materials and may optionally be used in combination with other dopants such as one or more of Nb, Mo, Te, Al, Ga, Sb, W, and Ta.

[0042] According to a second aspect of this application, a doped lithium lanthanum zirconium oxide prepared according to the method of the first aspect of this application is also provided. The doped lithium lanthanum zirconium oxide of the second aspect of this application may include the features described above related to the method of the first aspect of this application.

[0043] According to a third aspect of this application, a reactive composition for forming doped lithium lanthanum zirconium oxide is provided, comprising: One or more lithium, lanthanum and / or zirconium materials used to form the doped lithium lanthanum zirconium oxide, and at least one dopant provided as a polyoxometalate.

[0044] The applicant has found it advantageous to provide one or more polyoxometalate dopants. The reaction composition may optionally contain reaction and / or decomposition products of one or more polyoxometalates, such as one or more metal oxides.

[0045] The reaction composition of the third aspect of this application may include one or more features of the method of the first aspect of this application. For example, the reaction composition may include an anion source, with which lithium can form a precipitate. For example, the reaction composition may include a carbonate ion source, such as carbonate ions, bicarbonate ions, or carbon dioxide.

[0046] Optionally, the reaction composition may comprise one or more lanthanum and / or zirconium materials for forming the doped lithium lanthanum zirconium oxide, and optionally at least one dopant (optionally provided as a polyoxometalate but not containing lithium material) for forming the doped lithium lanthanum zirconium oxide. The reaction composition may comprise a solid (optionally a precipitate) which optionally provides one or more lanthanum and / or zirconium materials for forming the doped lithium lanthanum zirconium oxide. In this respect, such a composition may be formed prior to the addition of lithium material. The reaction composition may optionally comprise one or more lanthanum and / or zirconium materials for forming the doped lithium lanthanum zirconium oxide, and optionally at least one dopant (optionally provided as a polyoxometalate) and lithium material.

[0047] The pH of the reaction composition may be at least 3.5, optionally at least 4.0, optionally at least 4.5, optionally at least 5.0. The pH of the reaction composition may optionally not exceed 8.0, optionally not exceed 7.5, optionally not exceed 7.0, optionally not exceed 6.5, optionally not exceed 6.0, optionally not exceed 5.5, and optionally not exceed 5.0. This may occur, for example, when the reaction composition contains one or more lanthanum and / or zirconium materials for forming the doped lithium lanthanum zirconium oxide, and optionally contains at least one dopant (optionally provided as a polyoxometalate, but not containing lithium material). The one or more dopants may be substantially the same as those described in the method of the first aspect of this application.

[0048] The method of the first aspect of this application can be used to prepare the composition of the third aspect of this application. In this regard, this application can provide a method for preparing a reactive composition according to the third aspect of this application, the method comprising mixing at least two compositions, wherein at least one composition comprises a polyoxometalate, at least one composition comprises a lanthanide, and at least one composition comprises a zirconium. The composition may have one or more of the features described above related to the method of the first aspect of this application.

[0049] According to a fourth aspect of this application, a multipart reactive composition for forming doped lithium lanthanum zirconium oxide is provided, comprising: The first part comprises one or more lithium, lanthanum and / or zirconium materials for forming the doped lithium lanthanum zirconium oxide, optionally a base, and optionally a dopant provided as a polyoxometalate. Optionally, the second part may contain a base if no base is provided in the first part, or a dopant provided in the form of a polyoxometalate if no polyoxometalate is provided in the first part; and Optionally, the third part contains a lithium substance (optionally lithium ions, optionally a lithium ion solution, if the lithium substance is not provided in the first or second part).

[0050] Multipart reaction compositions may include the features described above in relation to the methods of the first aspect of this application and / or the reaction compositions of the third aspect of this application.

[0051] For example, a multipart reactive composition for forming doped lithium lanthanum zirconium oxide may comprise: The first part comprises one or more lanthanum and / or zirconium materials for forming a doped lithium lanthanum zirconium oxide; The second part comprises a base and a dopant provided in the form of a polyoxometalate; and The third part contains a lithium substance (optionally lithium ions) provided as a lithium ion solution.

[0052] Of course, it should be understood that features described in one aspect of this application may be incorporated into other aspects of this application. For example, the method of this application may include any features described in the apparatus of this application, and vice versa.

[0053] The implementation scheme of this application is described below only by way of examples. Invention Details The reagents used in the following examples were sourced from the following sources: ZrOCl2·8H2O: Thermo Scientific A12342; La2O3: ACROS Organics 199160010; La(NO3)3·6H2O: VWR 24958.238; 37% HCl: VWR 20252-335; Na2CO3: Tata; K2CO3: VWR 26724.360; Nb2O5: Alfa Aesar 11365-35; Nb2O5·xH2O: CBMM; KOH: VWR 26668.365; K8[Nb6O] 19 [:Nb2O5 or Nb2O5.xH2O is stirred in KOH solution at 90-180℃ until it hardly dissolves, then the remaining solid is removed by filtration to obtain a clear pale blue solution; LiOH.H2O: Alfa Aesar 43171-36; NH4HCO3: Merck 1.01131.5000; ((NH4)2Zr(OH)2(CO3)2 solution: Sigma Aldrich 464597.250; 40% (TBA)OH solution: VWR 85738.180; 69% HNO3: VWR 20425.322; (ZrO2)2.CO2.xH2O: Alfa Aesar 43245.36; (NH4)6[Mo7O 24 ].4H2O: VWR 21276.185; LiNO3: VWR25029.268; Te(OH)6: Alfa Aesar 14197.09; Na2WO4.2H2O: HC Starck; Cs2CO3: provided by Dakram; Ta2O5: Alfa Aesar 14709.18; HfOCl2.8H2O: Alfa Aesar 11833.14; TiOSO4 solution: SigmaAldrich 495379-1L; SrCl2.6H2O: Alfa Aesar 12494.36; CaCl2.2H2O: ACROS Organics207780025; BaCl2.2H2O: VWR 21709.364; MgCl2.6H2O: Sigma Aldrich M9272-500G; CeCl3.7H2O: Alfa Aesar A12947.30; ScCl3.6H2O: Alfa Aesar 11218.03; YCl3.6H2O: ACROSOrganics 199180500; Al(NO3)3.9H2O: Alfa Aesar 12360.A1; (NH4) 10H2W 12 O 42 ].xH2O: HCStarck; (NH4)6[H2W 12 O 40 ].xH2O: HC Starck; CO2: Air Liquide; K8Ta6O 19 .16H2O - Heat tantalum powder and KOH together to 450°C until melted. Then extract the melt into a minimal amount of water to prepare a clear, colorless solution; Rb2CO3: Sigma Aldrich 8.43858.0010; WO3.2H2O - Slowly add to a 20% HCl solution at room temperature and stir for 4 hours. Filter out the resulting yellow precipitate and air dry.

[0055] Example 1 - MC06-081 –Li 6.4 La3Zr 1.4 Nb 0.6 O 12 Solution A was prepared as follows: 128.9 g of 37% HCl and 66.6 g of ZrOCl2·8H2O were dissolved in 200 ml of deionized water. After complete dissolution, 71.1 g of La2O3 was added and stirred until dissolved. The solution was then diluted with deionized water to 1.5 L.

[0056] Solution B was prepared by the following method: 75.8 g of K8Nb6O 19 Solution (30.7% K8Nb6O) 19 Dilute 15H2O (4.34% KOH) with deionized water to 500 ml, then add 107.2 g K2CO3. Stir the mixture until completely dissolved.

[0057] Add solution A to solution B at room temperature over 1 hour. Let the mixture age for 40 minutes. Separate the resulting white precipitate by filtration and wash until the conductivity of the filtrate is less than 500 µS.

[0058] The filter cake was then resuspended in a solution of 64.8 g LiOH·H₂O in 500 ml of deionized water and stirred until resuspended. A solution of 61.0 g NH₄HCO₃ in 300 ml of deionized water was added to the suspended filter cake over 45 minutes. The suspension was then separated by filtration and dried at 110 °C. The dried solid was heated to 900 °C for 10 hours to obtain Li. 6.4 La3Zr 1.4 Nb 0.6 O 12XRD analysis confirmed that the crystal structure is cubic. No impurities were found. This example demonstrates that doped LLZO can be prepared by forming a precipitate containing lanthanum, zirconium, and niobium, contacting the precipitate with lithium ions, and then adding a carbonate ion source, with no visible impurities. Niobium is provided in the form of a polyoxometalate, in this example, [Nb6O]. 19 ] 8- .

[0059] Example 2 – CO02-104 – Li 6.4 La3Zr 1.4 Nb 0.6 O 12 7.42 g of Nb₂O₅·xH₂O was added to 16.87 g of 40% TBA-OH solution and diluted to 50 mL. TBA is (C₄H₁₈)₄N₂O. + The suspension was refluxed at 100°C for 5.5 hours and then cooled to room temperature. The remaining solids were removed by vacuum filtration to obtain a solution containing (TBA)6Nb. 10 O 28 The solution.

[0060] Solution A was prepared as follows: 12.7 g of 37% HCl and 6.59 g of ZrOCl2·8H2O were dissolved in 30 mL of deionized water. After dissolution, 7.00 g of La2O3 was added and stirred until dissolved. The solution was then diluted to 150 mL.

[0061] Composition B was prepared by the following method: 74.13 g of (TBA)6Nb 10 O 28 The solution (3.28%) is (TBA)6Nb 10 O 28 (1.21% TBA-OH) was diluted to 100 mL with deionized water. 8.54 g of Na2CO3 was added and stirred to dissolve, resulting in the formation of a white precipitate.

[0062] Solution A is added to composition B within 1 hour. The resulting white precipitate is aged for one hour, then separated and washed by vacuum filtration.

[0063] The filter cake was resuspended in 50 mL of deionized water, and 6.19 g of LiOH·H₂O was added and dissolved. Separately, 5.83 g of NH₄HCO₃ was dissolved in 27 mL of deionized water and added to the suspended filter cake over 40 minutes. The white suspension was separated by vacuum filtration and dried at 110 °C. The dried solid was calcined at 900 °C for 10 hours. The prepared material was pure cubic LLZO. This example demonstrates that doped LLZO can be produced using decaniobate (in this example, [Nb]). 10 O 28 ] 6- )preparation.

[0064] Example 3 - CO02-115A –Li 6.4 La3Zr 1.4 Nb 0.6 O 12 Solution A was prepared as follows: 12.7 g of 37% HCl and 6.59 g of ZrOCl2·8H2O were dissolved in 30 mL of deionized water. After dissolution, 7.00 g of La2O3 was added and stirred until dissolved. The solution was then diluted to 150 mL.

[0065] Solution B was prepared by the following method: 8.66 g of K8Nb6O 19 .15H2O (19.4% is K8Nb6O) 19 0.15H₂O (0.87% KOH) was diluted to 50 mL with deionized water. 12.4 g of NH₄HCO₃ was added to the solution and stirred to dissolve. Note that solution B uses bicarbonate ions, while Examples 1 and 2 use carbonate ions.

[0066] Solution A is added to solution B within 1 hour. The resulting white precipitate is aged for 1 hour, then separated and washed by vacuum filtration.

[0067] The filter cake was resuspended in 50 mL of deionized water and diluted to 100 mL. 6.19 g of LiOH·H₂O was added and dissolved. Separately, 5.83 g of NH₄HCO₃ was dissolved in 27 mL of deionized water and added to the suspended filter cake over 40 minutes. The white suspension was separated by vacuum filtration and dried at 110 °C. The dried solid was then calcined at 900 °C for 12 hours. The prepared material was cubic LLZO containing small amounts of La₂O₃ and La₂Zr₂O₇ impurities. These impurities are presumably due to insufficient mixing during the experiment. Niobium was provided as a polyoxometalate, in this case [Nb₆O₃]. 19 ] 8- .

[0068] Example 4 - MC07-058C –Li 6.4 La3Zr 1.4 Nb 0.6 O 12 Solution A was prepared as follows: 12.2 g of 37% HCl and 6.32 g of ZrOCl2·8H2O were dissolved in 20 mL of deionized water. After complete dissolution, 6.72 g of La2O3 was added and stirred until dissolved. The solution was then diluted to 100 mL with deionized water.

[0069] Composition B was prepared by the following method: 9.35 g of K8Nb6O 19 Solution (21.3% K8Nb6O) 19 (Based on 0.15H2O, 3.87% is KOH) was diluted to 100 ml with deionized water, then 3.86 g Na2CO3 and 4.08 g KOH were added. The mixture was stirred until completely dissolved. A precipitate slowly formed after standing. Note that composition B uses both carbonate anions and potassium hydroxide.

[0070] Solution A was added to composition B over 1 hour at room temperature. The resulting white precipitate was separated by centrifugation and washed, then resuspended in a solution of 6.01 g LiOH·H₂O in 40 ml deionized water. The suspension was stirred until homogeneous. Over 40 minutes, a solution of 5.66 g NH₄HCO₃ in 28 ml deionized water was added to the suspended filter cake. The solid was then separated by filtration and dried at 110 °C. The dried solid was heated to 900 °C for 10 hours to obtain Li. 6.4 La3Zr 1.4 Nb 0.6 O 12 XRD analysis confirmed a cubic crystal structure. No impurities were formed. Niobium was provided as a polyoxometalate, in this case [Nb6O]. 19 ] 8- .

[0071] Example 5 - MC07-060C –Li 6.4 La3Zr 1.4 Nb 0.6 O 12 Solution A was prepared as follows: 12.2 g of 37% HCl and 6.33 g of ZrOCl2·8H2O were dissolved in 20 mL of deionized water. After complete dissolution, 6.72 g of La2O3 was added and stirred until dissolved. The solution was then diluted to 100 mL with deionized water.

[0072] Solution B was prepared by the following method: 9.34 g of K8Nb6O 19 Solution (21.3% K8Nb6O) 19 Dilute 15H₂O (3.87% KOH) with deionized water to 100 mL, then add 8.19 g KOH. Stir the mixture until completely dissolved. Note that potassium hydroxide was used in solution B.

[0073] Solution A was added to solution B over 1 hour at room temperature. The resulting white precipitate was separated by centrifugation and washing, then resuspended in a solution of 6.01 g LiOH·H₂O in 40 ml deionized water. The suspension was stirred until homogeneous. Over 40 minutes, a solution of 5.66 g NH₄HCO₃ in 28 ml deionized water was added to the suspended filter cake. The solid was then separated by filtration and dried at 110 °C. The dried solid was heated to 900 °C for 10 hours to obtain Li. 6.4 La3Zr 1.4 Nb 0.6 O 12 XRD analysis confirmed a cubic crystal structure. No impurities were found. Niobium was provided as a polyoxometalate, in this case [Nb6O]. 19 ] 8 .

[0074] Example 6 - CO02-122A –Li 6.4 La3Zr 1.4 Nb 0.6 O 12 Solution A was prepared as follows: 3.73 g of 69% HNO3 was diluted with 4.85 mL of deionized water to obtain a 30% solution. 6.24 g of [ZrO2]2·CO2·xH2O (40.37% ZrO2) was added, and the slurry was heated to 50°C to dissolve the solid, yielding a ZrO(NO3)2 solution. Then, 18.6 g of La(NO3)3·6H2O was dissolved in the solution and stirred. Note that zirconium nitrate and lanthanum nitrate were used.

[0075] Solution B was prepared by the following method: 7.89 g of K8Nb6O 19 Solution (21.3% K8Nb6O) 19 15H2O (3.87% KOH) was diluted to 50 mL with deionized water. Then, 8.31 g of Na2CO3 was dissolved in the solution and stirred.

[0076] At room temperature, solution A was added to solution B over 1 hour. The resulting white precipitate was separated by centrifugation and washed, then slurried again in 50 mL of deionized water. 6.19 g of LiOH·H2O was dissolved in the slurry. Separately, 5.83 g of NH4HCO3 was dissolved in 27 mL of deionized water and stirred. Under stirring, the NH4HCO3 solution was added to the slurry over 40 minutes. The precipitate was separated by filtration and then dried in an oven at 110 °C. The dried solid was calcined at 900 °C for 12 hours. XRD analysis confirmed that the crystal structure was cubic, containing a small amount of La2Zr2O7. Niobium was provided in the form of a polyoxometalate, in this case [Nb6O 19 ] 8- .

[0077] Example 7 - MC07-066C Li 6.4 La3Zr 1.4 Nb 0.6 O 12 Solution A was prepared by dissolving 12.2 g of 37% HCl and 6.72 g of La2O3 in 20 ml of deionized water. The solution was then diluted with deionized water to 100 mL.

[0078] Solution B was prepared as follows: 13.09 g of ammonium zirconium carbonate solution (zirconium content 13.6%) was diluted to 100 ml with deionized water, and then 4.63 g of K₂CO₃ was added. The mixture was stirred until completely dissolved, and then 9.33 g of K₈Nb₆O₃ was added. 19 Solution (21.3% K8Nb6O) 19 (15H₂O, 3.87% KOH). The solution remains clear and colorless. Note that ammonium zirconium carbonate was used in solution B.

[0079] Solution A was added to solution B over 1 hour at room temperature. The resulting white precipitate was separated by centrifugation and washed, then resuspended in a solution of 6.01 g LiOH·H₂O in 40 ml deionized water. The suspension was stirred until homogeneous. Over 40 minutes, a solution of 5.66 g NH₄HCO₃ in 28 ml deionized water was added to the suspended filter cake. The solid was then separated by filtration and dried at 110 °C. The dried solid was heated to 900 °C for 10 hours to obtain Li. 6.4 La3Zr 1.4 Nb 0.6 O 12 XRD analysis confirmed a cubic crystal structure with a small amount of La₂Zr₂O₇ impurities. Niobium was provided as a polyoxometalate, in this case [Nb₆O₂].19 ] 8 .

[0080] Example 8 - MC07-012A – Li 6.4 La3Zr 1.7 Mo 0.3 O 12 Solution A was prepared as follows: 12.2 g of 37% HCl and 7.68 g of ZrOCl2·8H2O were dissolved in 20 ml of deionized water. After complete dissolution, 6.72 g of La2O3 was added and stirred until dissolved. The solution was then diluted with water to 100 ml.

[0081] Solution B was prepared by the following method: 9.44 g of KOH and 0.73 g of (NH4)6Mo7O 24 Dissolve .4H2O in 100ml of water. Stir the mixture until completely dissolved.

[0082] At room temperature, solution A is added to solution B over 1 hour. The resulting white precipitate is separated by centrifugation and washed.

[0083] The filter cake was then resuspended in a solution of 6.68 g LiNO3 in 50 ml of deionized water and stirred until resuspended. The suspension was prepared to a volume of 100 ml. The suspension was then frozen and lyophilized. The dried solid was heated to 900 °C for 10 hours to obtain Li. 6.4 La3Zr 1.7 Mo 0.3 O 12 XRD analysis confirmed that the crystal structure is cubic. This example demonstrates the use of polyoxometalate anions, doped with Mo dopant (in this example, [Mo7O]). 24 ] 6- (Instead of Nb dopant)

[0084] Example 9 - MC07-025 –Li 6.4 La3Zr 1.48 Nb 0.43 Te 0.09 O 12 K7[TeNb5O 19 It is prepared by the following method: 0.32 g Te(OH)6 is added to a mixture containing 1.35 g K8[Nb6O] 19 Add 0.07 g of KOH to an 8.53 g solution. Prepare a suspension to approximately 10 ml, then stir and heat slowly until a clear, colorless solution is formed. After cooling, seal the solution in a small vial and let it stand for 3 days before use.

[0085] Solution A was prepared as follows: 14.2 g of 37% HCl and 7.83 g of ZrOCl2·8H2O were dissolved in 20 ml of deionized water. After complete dissolution, 7.38 g of La2O3 was added and stirred until dissolved. The solution was then diluted to 100 ml with deionized water.

[0086] Solution B is prepared by the following method: All of the K7[TeNb5O] prepared above is used... 19 Add the solution and 9.72 g Na2CO3 to 100 ml of water and dissolve until a clear, colorless solution is obtained.

[0087] At room temperature, solution A was added to solution B over 1 hour. The resulting white precipitate was separated by centrifugation and then resuspended in a solution of 7.57 g LiOH·H₂O in 90 ml of deionized water, stirred until resuspended. The suspension was prepared to 150 ml. Over 40 minutes, a solution of 7.13 g NH₄HCO₃ in 33 ml of deionized water was added to the suspended filter cake. The suspension was then separated by filtration and dried at 110 °C. The dried solid was heated to 900 °C for 10 hours to obtain Li. 6.4 La3Zr 1.48 Nb 0.43 Te 0.09 O 12 XRD analysis confirmed a cubic crystal structure. The presence of La₂O₃ impurities is likely due to excessive feed. Niobium and tellurium are provided as polyoxometalates, in this case [TeNb₅O₂]. 19 ] 7- .

[0088] Example 10 - MC07-027 –Li 6.4 La3Zr 1.7 W 0.257 Te 0.043 O 12 Na6[TeW6O 24 The Na₂WO₄·2H₂O was prepared according to the method described herein. 5.00 g of Na₂WO₄·2H₂O and 0.60 g of Te(OH)₆ were dissolved in water, and the solution was diluted to 100 ml. The pH was adjusted to 4.95 with a 10% hydrochloric acid solution. The solution was heated to approximately 90°C until the solution volume was approximately 40 ml. The solution was allowed to cool and stand. Large Na₆[TeW₆O]₂ was formed. 24 ].22H2O crystals were recovered by decantation and dried in air.

[0089] Solution A was prepared as follows: 12.2 g of 37% HCl and 7.68 g of ZrOCl2·8H2O were dissolved in 20 ml of deionized water. After complete dissolution, 6.72 g of La2O3 was added and stirred until dissolved. The solution was then diluted with water to 100 ml.

[0090] Solution B was prepared by the following method: 8.89 g of Na₂CO₃ and 1.27 g of Na₆[TeW₆O₃] were mixed. 24 ].22H2O was dissolved in 100 ml of water to obtain a clear, colorless solution.

[0091] At room temperature, solution A was added to solution B over 1 hour. The resulting white precipitate was separated by centrifugation.

[0092] The filter cake was then resuspended in a solution of 6.67 g LiNO3 in 90 ml of deionized water and stirred until resuspended. The suspension was diluted with water to 100 ml and stirred for 30 minutes. The suspension was sieved to remove agglomerates, then frozen and lyophilized. The dried solid was heated to 900 °C for 10 hours to obtain Li. 6.4 La3Zr 1.7 W 0.257 Te 0.043 O 12 XRD analysis confirmed a cubic crystal structure (containing a small amount of La₂Zr₂O₇ impurities). Tungsten and tellurium were provided as polyoxometalates, in this case [TeW₆O₃]. 24 ] 6 .

[0093] Example 11 - MC07-028 –Li 6.4 La3Z 1.6 W 0.2 Nb 0.2 O 12 Nominal K5[Nb3W3O 19 Manufactured according to the method described herein. 25.58 g contains 4.04 g K8[Nb6O] 19 A solution of 0.22 g KOH was added to 80 mL of water and heated to approximately 60°C. Then, 5.52 g WO3·2H2O and 20 mL of water were added. The suspension was heated and stirred until the yellow color disappeared and the mixture became a white turbidity. The mixture was cooled and stored. This mixture will contain substances with the general formula [Nb...]. 6-x W x O 19 ] (8-x)- The Lindqvist ion, where x is 0 to 5. Most ions have x = 2, 3, and 4.

[0094] Solution A was prepared as follows: 12.2 g of 37% HCl and 7.23 g of ZrOCl2·8H2O were dissolved in 20 ml of deionized water. After complete dissolution, 6.72 g of La2O3 was added and stirred until dissolved. The solution was then diluted with water to 100 ml.

[0095] Composition B was prepared by the following method: 8.69 g of Na2CO3 and 21.53 g of K5[Nb3W3O], nominally containing 1.22 g of K5[Nb3W3O], were added. 19 Dissolve the solution of [Na₂CO₃] in 80 ml of water. Stir the mixture until Na₂CO₃ is completely dissolved. 19 It is still slightly cloudy.

[0096] At room temperature, solution A is added to composition B over 1 hour. The resulting white precipitate is separated by centrifugation and washed.

[0097] The filter cake was then resuspended in a solution of 6.67 g LiNO3 in 90 ml of deionized water and stirred until resuspended. The suspension was prepared to a volume of 150 ml and stirred for 30 minutes. The suspension was sieved to remove agglomerates, then frozen and lyophilized. The dried solid was heated to 900 °C for 10 hours to obtain Li. 6.4 La3Z 1.6 W 0.2 Nb 0.2 O 12 XRD analysis confirmed a cubic crystal structure with a small amount of La₂O₃ impurities. Tungsten and niobium were provided as polyoxometalates, in this case [Nb₃W₃O₄]. 19 ] 5- .

[0098] Example 12 - MC07-058B –Li 6.4 La3Zr 1.4 Ta 0.3 Nb 0.3 O 12 Nominal Cs8[Nb 3.11 Ta 2.89 O 19 The mixture was prepared by manually mixing 30.11 g Cs₂CO₃, 7.71 g Ta₂O₅, and 5.00 g Nb₂O₅, and then heating to 900 °C for 10 hours. The cooled melt was extracted with water to obtain a pale blue, slightly turbid solution with a total mass of 110.5 g. This mixture will contain substances with the general formula [Nb₂O₅]. 6-x Ta x O 19 ] 8-The Lindqvist ion, where x is 0 to 6. Most ions have x = 2, 3, and 4.

[0099] Solution A was prepared as follows: 12.2 g of 37% HCl and 6.33 g of ZrOCl2·8H2O were dissolved in 20 ml of deionized water. After complete dissolution, 6.72 g of La2O3 was added and stirred until dissolved. The solution was then diluted with water to 100 ml.

[0100] Composition B was prepared by the following method: 23.26 g of Cs₂CO₃ and 12.12 g of a compound nominally containing 2.89 g of Cs₈[Nb] were mixed. 3.11 Ta 2.89 O 19 A solution of 1.56 g Cs₂CO₃ was dissolved in 90 ml of water. The mixture was stirred until Cs₂CO₃ was completely dissolved—Cs₈[Nb₃Ta₃O₃] 19 It is still slightly cloudy.

[0101] At room temperature, solution A was added to composition B over 1 hour. The resulting white precipitate was separated by centrifugation and washed, then resuspended in a solution of 6.01 g LiOH·H₂O in 40 ml of deionized water, and stirred until resuspended. The suspension was prepared to 100 ml. Over 40 minutes, a solution of 5.66 g NH₄HCO₃ in 28 ml of deionized water was added to the suspended filter cake. The suspension was then separated by filtration and dried at 110 °C. The dried solid was heated to 900 °C for 10 hours to obtain Li. 6.4 La3Zr 1.4 Nb 0.3 Ta 0.3 O 12 XRD analysis confirmed a cubic crystal structure. No impurities were found. Tantalum and niobium are provided as polyoxometalates, nominally [Nb3Ta3O] in this case. 19 ] -8 .

[0102] Example 13 - CO02-79B Li 6.4 La3Zr 1.3 Nb 0.6 Hf 0.1 O 12 Preparation Solution A was prepared as follows: 13.2 g of 37% HCl and 6.77 g of ZrOCl2·8H2O were dissolved in 30 mL of deionized water. After dissolution, 7.23 g of La2O3 was added and stirred to dissolve. The solution was then diluted to 150 mL, and 0.61 g of HfOCl2·8H2O was added and stirred to dissolve.

[0103] Solution B was prepared by the following method: 7.45 g of K8Nb6O 19 .15H2O solution (19.4% K8Nb6O) 19 Dilute 0.15H2O (0.87% KOH) to 50 mL. Add 8.82 g Na2CO3 to the solution and stir to dissolve.

[0104] Solution A was added to solution B within 1 hour and 40 minutes. The resulting white precipitate was aged for 1 hour, and then separated and washed by vacuum filtration.

[0105] The filter cake was resuspended in 50 mL of deionized water, and 5.83 g of LiOH·H₂O was added and dissolved. Separately, 5.49 g of NH₄HCO₃ was dissolved in 27 mL of deionized water and added to the suspended filter cake over 40 minutes. The white suspension was separated by vacuum filtration and dried at 110 °C. The dried solid was calcined at 900 °C for 12 hours. The prepared material is cubic LLZO containing a small amount of La₂O₃. Niobium is provided in the form of a polyoxometalate, in this example, [Nb₆O₃]. 19 ] 8 .

[0106] Example 14 - CO02-82A –Li 6.4 La3Zr 1.3 Nb 0.6 Ti 0.1 O 12 Preparation Solution A was prepared as follows: 13.3 g of 37% HCl and 6.39 g of ZrOCl2·8H2O were dissolved in 30 mL of deionized water. After dissolution, 7.34 g of La2O3 was added and stirred to dissolve. The solution was then diluted to 150 mL, and 1.60 g of TiOSO4 solution (15 wt% TiOSO4, 50 wt% H2SO4) was added and stirred to dissolve.

[0107] Solution B was prepared by the following method: 9.08 g of K8Nb6O 19 .15H2O solution (19.4% K8Nb6O) 19Dilute the solution (0.15H2O, 0.87% KOH) to 50 mL. Add 10.50 g of Na2CO3 to the solution and stir to dissolve.

[0108] Solution A was added to solution B within 1 hour and 40 minutes. The resulting white precipitate was aged for 1 hour, and then separated and washed by vacuum filtration.

[0109] The filter cake was resuspended in 50 mL of deionized water, and 5.90 g of LiOH·H₂O was added and dissolved. Separately, 5.56 g of NH₄HCO₃ was dissolved in 27 mL of deionized water and added to the suspended filter cake over 40 minutes. The white suspension was separated by vacuum filtration and dried at 110 °C. The dried solid was calcined at 900 °C for 12 hours. The prepared material was cubic LLZO containing a small amount of La₂O₃. Niobium was provided in the form of a polyoxometalate, in this example, [Nb₆O₃]. 19 ] 8 .

[0110] Example 15 - CO02-29 –Li 6.5 La 2.9 Sr 0.1 Zr 1.4 Nb 0.6 O 12 Preparation Solution A was prepared as follows: 12.9 g of 37% HCl and 6.88 g of ZrOCl2·8H2O were dissolved in 30 mL of deionized water. After dissolution, 7.10 g of La2O3 was added and stirred to dissolve. The solution was then diluted to 150 mL, and 0.40 g of SrCl2·6H2O was added and stirred to dissolve.

[0111] Composition B was prepared by the following method: 10.19 g of K8Nb6O 19 .15H2O solution (21.3% K8Nb6O) 19 15H₂O (3.87% KOH) was diluted to 50 mL with deionized water. 8.34 g of Na₂CO₃ was added and stirred to dissolve, resulting in the formation of a white precipitate.

[0112] Solution A was added to composition B over a period of 1 hour and 40 minutes. The resulting white precipitate was aged for one hour, and then separated and washed by vacuum filtration.

[0113] The filter cake was resuspended in 50 mL of deionized water, and 5.97 g of LiOH·H₂O was added and dissolved. Separately, 5.41 g of NH₄HCO₃ was dissolved in 22 mL of deionized water and added to the suspended filter cake over 40 minutes. The white suspension was separated by vacuum filtration and dried at 110 °C. The dried solid was calcined at 900 °C for 10 hours. The prepared material was pure cubic LLZO. Niobium was provided in the form of a polyoxometalate, in this example [Nb₆O₃]. 19 ] 8- .

[0114] Example 16 - CO02-33 –Li 6.5 La 2.9 Ca 0.1 Zr 1.4 Nb 0.6 O 12 Preparation Solution A was prepared as follows: 13.0 g of 37% HCl and 7.02 g of ZrOCl2·8H2O were dissolved in 30 mL of deionized water. After dissolution, 7.14 g of La2O3 was added and stirred to dissolve. The solution was then diluted to 150 mL, and 0.22 g of CaCl2·2H2O was added and stirred to dissolve.

[0115] Composition B was prepared by the following method: 10.25 g of K8Nb6O 19 .15H2O solution (21.3% K8Nb6O) 19 15H₂O (3.87% KOH) was diluted to 50 mL with deionized water. 8.39 g of Na₂CO₃ was added and stirred to dissolve, resulting in the formation of a white precipitate.

[0116] Solution A was added to composition B over a period of 1 hour and 40 minutes. The resulting white precipitate was aged for 1 hour, and then separated and washed by vacuum filtration.

[0117] The filter cake was resuspended in 50 mL of deionized water, and 6.00 g of LiOH·H₂O was added and dissolved. Separately, 5.65 g of NH₄HCO₃ was dissolved in 27 mL of deionized water and added to the suspended filter cake over 40 minutes. The white suspension was separated by vacuum filtration and dried at 110 °C. The dried solid was calcined at 900 °C for 10 hours. The prepared material was pure cubic LLZO. Niobium was provided in the form of a polyoxometalate, in this example [Nb₆O₃]. 19 ] 8 .

[0118] Example 17 - CO02-39 –Li 6.75La 2.75 Ca 0.25 Zr 1.4 Nb 0.5 O 12 Preparation Solution A was prepared as follows: 12.5 g of 37% HCl and 7.53 g of ZrOCl2·8H2O were dissolved in 30 mL of deionized water. After dissolution, 6.88 g of La2O3 was added and stirred to dissolve. The solution was then diluted to 150 mL, and 0.56 g of CaCl2·2H2O was added and stirred to dissolve.

[0119] Composition B was prepared by the following method: 8.68 g of K8Nb6O 19 .15H2O solution (21.3% K8Nb6O) 19 15H₂O (3.87% KOH) was diluted to 50 mL with deionized water. 8.70 g of Na₂CO₃ was added and stirred to dissolve, resulting in the formation of a white precipitate.

[0120] Solution A was added to composition B over a period of 1 hour and 40 minutes. The resulting white precipitate was aged for 1 hour, and then separated and washed by vacuum filtration.

[0121] The filter cake was resuspended in 50 mL of deionized water, and 6.25 g of LiOH·H₂O was added and dissolved. Separately, 5.89 g of NH₄HCO₃ was dissolved in 28 mL of deionized water and added to the suspended filter cake over 40 minutes. The white suspension was separated by vacuum filtration and dried at 110 °C. The dried solid was calcined at 900 °C for 10 hours. The prepared material was pure cubic LLZO. Niobium was provided in the form of a polyoxometalate, in this example [Nb₆O₃]. 19 ] 8- .

[0122] Example 18 - CO02-47 –Li 6.5 La 2.9 Ba 0.1 Zr 1.4 Nb 0.6 O 12 Preparation Solution A was prepared as follows: 12.8 g of 37% HCl and 6.94 g of ZrOCl2·8H2O were dissolved in 30 mL of deionized water. After dissolution, 7.05 g of La2O3 was added and stirred to dissolve. The solution was then diluted to 150 mL, and 0.36 g of BaCl2·2H2O was added and stirred to dissolve.

[0123] Composition B was prepared by the following method: 11.11 g of K8Nb6O 19 .15H2O solution (19.4% K8Nb6O) 19 0.15H2O (0.87% KOH) was diluted to 50 mL with deionized water. 8.57 g of Na2CO3 was added and stirred to dissolve, resulting in the formation of a white precipitate.

[0124] Solution A was added to composition B over a period of 1 hour and 40 minutes. The resulting white precipitate was aged for 1 hour, and then separated and washed by vacuum filtration.

[0125] The filter cake was resuspended in 50 mL of deionized water, and 5.95 g of LiOH·H₂O was added and dissolved. Separately, 5.60 g of NH₄HCO₃ was dissolved in 27 mL of deionized water and added to the suspended filter cake over 40 minutes. The white suspension was separated by vacuum filtration and dried at 110 °C. The dried solid was calcined at 900 °C for 10 hours. The prepared material was pure cubic LLZO. Niobium was provided in the form of a polyoxometalate, in this example [Nb₆O₃]. 19 ] 8- .

[0126] Example 19 - CO02-76A –Li 6.5 La 2.9 Mg 0.1 Zr 1.4 Nb 0.6 O 12 Preparation Solution A was prepared as follows: 13.0 g of 37% HCl and 6.95 g of ZrOCl2·8H2O were dissolved in 30 mL of deionized water. After dissolution, 7.17 g of La2O3 was added and stirred to dissolve. The solution was then diluted to 150 mL, and 0.31 g of MgCl2·6H2O was added and stirred to dissolve.

[0127] Solution B was prepared by dissolving 8.77 g of Na₂CO₃ in 50 ml of deionized water. 2.19 g of K₈Nb₆O₃ was then added. 19 Add .15H2O to the solution and stir to dissolve.

[0128] Solution A was added to solution B within 1 hour and 40 minutes. The resulting white precipitate was aged for 1 hour, and then separated and washed by vacuum filtration.

[0129] The filter cake was resuspended in 50 mL of deionized water, and 6.02 g of LiOH·H₂O was added and dissolved. Separately, 5.77 g of NH₄HCO₃ was dissolved in 27 mL of deionized water and added to the suspended filter cake over 40 minutes. The white suspension was separated by vacuum filtration and dried at 110 °C. The dried solid was calcined at 900 °C for 12 hours. The prepared material was cubic LLZO containing a small amount of Li₂CO₃. Niobium was provided in the form of a polyoxometalate, in this example, [Nb₆O₃]. 19 ] 8 .

[0130] Example 20 - CO02-76B –Li 6.5 La 2.9 Ce 0.1 Zr 1.4 Nb 0.6 O 12 Preparation Solution A was prepared as follows: 12.8 g of 37% HCl and 6.84 g of ZrOCl2·8H2O were dissolved in 30 mL of deionized water. After dissolution, 7.06 g of La2O3 was added and stirred to dissolve. The solution was then diluted to 150 mL, and 0.56 g of CeCl3·7H2O was added and stirred to dissolve.

[0131] Solution B was prepared by dissolving 8.71 g of Na₂CO₃ in 50 ml of deionized water. 2.16 g of K₈Nb₆O₃ was then added. 19 Add .15H2O to the solution and stir to dissolve.

[0132] Solution A was added to solution B within 1 hour and 40 minutes. The resulting white precipitate was aged for 1 hour, and then separated and washed by vacuum filtration.

[0133] The filter cake was resuspended in 50 mL of deionized water, and 5.88 g of LiOH·H₂O was added and dissolved. Separately, 5.53 g of NH₄HCO₃ was dissolved in 26 mL of deionized water and added to the suspended filter cake over 40 minutes. The white suspension was separated by vacuum filtration and dried at 110 °C. The dried solid was calcined at 900 °C for 12 hours. The prepared material was pure cubic LLZO. Niobium was provided in the form of a polyoxometalate, in this example [Nb₆O₃]. 19 ] 8- .

[0134] Example 21 - CO02-79C –Li 6.5 La3Zr 1.3 Nb 0.6 Sc0.1 O 12 Preparation Solution A was prepared as follows: 13.4 g of 37% HCl and 6.38 g of ZrOCl2·8H2O were dissolved in 30 mL of deionized water. After dissolution, 7.34 g of La2O3 was added and stirred to dissolve. The solution was then diluted to 150 mL, and 0.39 g of ScCl3·6H2O was added and stirred to dissolve.

[0135] Solution B was prepared by the following method: 9.08 g of K8Nb6O 19 .15H2O solution (19.4% K8Nb6O) 19 Dilute the solution (0.15H2O, 0.87% KOH) to 50 mL. Add 8.76 g of Na2CO3 to the solution and stir to dissolve.

[0136] Solution A was added to solution B within 1 hour and 40 minutes. The resulting white precipitate was aged for 1 hour, and then separated and washed by vacuum filtration.

[0137] The filter cake was resuspended in 50 mL of deionized water, and 5.97 g of LiOH·H₂O was added and dissolved. Separately, 5.62 g of NH₄HCO₃ was dissolved in 27 mL of deionized water and added to the suspended filter cake over 40 minutes. The white suspension was separated by vacuum filtration and dried at 110 °C. The dried solid was calcined at 900 °C for 12 hours. The prepared material was cubic LLZO containing a small amount of La₂O₃. Niobium was provided in the form of a polyoxometalate, in this example, [Nb₆O₃]. 19 ] 8 .

[0138] Example 22 - CO02-82B –Li 6.4 La 2.9 Y 0.1 Zr 1.4 Nb 0.6 O 12 Preparation Solution A was prepared as follows: 12.9 g of 37% HCl and 6.88 g of ZrOCl2·8H2O were dissolved in 30 mL of deionized water. After dissolution, 7.10 g of La2O3 was added and stirred to dissolve. The solution was then diluted to 150 mL, and 0.46 g of YCl3·6H2O was added and stirred to dissolve.

[0139] Solution B was prepared by the following method: 9.09 g of K8Nb6O 19 .15H2O solution (19.4% K8Nb6O) 19Dilute the solution (0.15H2O, 0.87% KOH) to 50 mL. Add 8.69 g of Na2CO3 to the solution and stir to dissolve.

[0140] Solution A was added to solution B within 1 hour and 40 minutes. The resulting white precipitate was aged for 1 hour, and then separated and washed by vacuum filtration.

[0141] The filter cake was resuspended in 50 mL of deionized water, and 5.91 g of LiOH·H₂O was added and dissolved. Separately, 5.56 g of NH₄HCO₃ was dissolved in 27 mL of deionized water and added to the suspended filter cake over 40 minutes. The white suspension was separated by vacuum filtration and dried at 110 °C. The dried solid was calcined at 900 °C for 12 hours. The prepared material is cubic LLZO. Niobium is provided in the form of a polyoxometalate, in this example, [Nb₆O₃]. 19 ] 8- .

[0142] Example 23 - MC07-018 –Li 5.8 Al 0.4 La3Zr2O 12 [Al 13 O4(OH) 24 The preparation method of [NO3]7 is as follows: Dissolve 18.76 g of Al(NO3)3·9H2O in water to prepare 100 ml of solution. Heat the solution to 50°C, and then add 6.36 g of Na2CO3 over 70 minutes. Maintain the temperature at 50°C until the solution becomes clear and colorless, and then cool the solution to room temperature. A solution with a total mass of 105.5 g is obtained.

[0143] Solution A was prepared by the following method: 11.60 g of [Al] 13 O4(OH) 12 Dissolve 9.04 g of (NO3)7 solution and 9.04 g of ZrOCl2·8H2O in 20 ml of deionized water. After complete dissolution, add 12.2 g of 37% HCl and 6.72 g of La2O3 and stir to dissolve. After dissolution, dilute the solution with water to 100 ml.

[0144] Solution B was prepared by dissolving 9.70 g of Na₂CO₃ in 100 ml of water. The mixture was stirred until completely dissolved.

[0145] Solution A was added to solution B over 1 hour at room temperature. The resulting white precipitate was separated by centrifugation and then resuspended in a solution of 5.60 g LiOH·H₂O in 50 ml deionized water, stirred until resuspended. The suspension was prepared to a volume of 100 ml. Over 40 minutes, a solution of 5.28 g NH₄HCO₃ in 30 ml deionized water was added to the suspended filter cake. The suspension was then separated by filtration and dried at 110 °C. The dried solid was heated to 900 °C for 10 hours to obtain Li. 5.8 Al 0.4 La3Zr2O 12 XRD analysis confirmed that the crystal structure is cubic. It contains a small amount of LaAlO3 impurities. Aluminum is provided in the form of a polyoxometalate.

[0146] Example 24 - MC07-062C –Li 6.4 La3Zr 1.7 W 0.3 O 12 Solution A was prepared as follows: 4.3 g of 37% HCl and 8.35 g of ZrOCl2·8H2O were dissolved in 30 mL of deionized water. After dissolution, 2.40 g of La2O3 was added and stirred until dissolved. The solution was then diluted to 100 mL.

[0147] Composition B was prepared by dissolving 5.19 g of KOH in 100 mL of water. Then, 1.17 g of (NH4) was added. 10 H2W 12 O 42 ].xH2O (89.1% of which is WO3) forms a grayish-white suspension.

[0148] Solution A was added to composition B over 1 hour at room temperature. A white precipitate was formed by centrifugation.

[0149] The filter cake was then resuspended in a solution of 18.29 g LiNO3 in 40 ml of deionized water and stirred until resuspended. Over 40 minutes, a solution of 18.29 g NH4HCO3 in 97 ml of deionized water was added to the suspended filter cake. The suspension was then separated by filtration and dried at 110 °C. The dried solid was heated to 900 °C for 10 hours to obtain Li. 6.4 La3Zr 1.7 W 0.3 O 12XRD analysis confirmed a cubic crystal structure containing small amounts of La₂O₃ and Li₂ZrO₃ impurities. Understandably, the La dosage was too low to achieve stoichiometry. It is speculated that this is because the resulting LiHCO₃ solution leaches Zr and W from the precipitate. The La₂O₃ dosage was essentially determined iteratively until a suitable value was reached. Tungsten was provided in the form of a polyoxometalate.

[0150] Example 25 - MC07-026 – Li 6.4 La3Zr 1.7 W 0.3 O 12 via [H2W 12 O 40 ] 6- Solution A was prepared as follows: 12.2 g of 37% HCl and 7.68 g of ZrOCl2·8H2O were dissolved in 20 ml of deionized water. After complete dissolution, 6.72 g of La2O3 was added and stirred until dissolved. The solution was then diluted with water to 100 ml.

[0151] Solution B was prepared by mixing 9.50 g of KOH and 1.04 g of (NH4) 10 H2W 12 O 42 ].xH2O (91.5% WO3) was dissolved in 100 ml of water to obtain a clear, colorless solution.

[0152] At room temperature, solution A was added to solution B over 1 hour. The resulting white precipitate was separated by centrifugation.

[0153] The filter cake was then resuspended in a solution of 6.67 g LiNO3 in 100 ml of deionized water and stirred until resuspended. The suspension was prepared to a volume of 150 ml. The suspension was then frozen and lyophilized. The dried solid was heated to 900 °C for 10 hours to obtain Li. 6.4 La3Zr 1.7 W 0.3 O 12 XRD analysis confirmed a cubic crystal structure. A small amount of La₂Zr₂O₇ impurity was present. Tungsten was provided in the form of a polyoxometalate. Example 26-MC07-007B-Li 6.4 La3Zr 1.7 W 0.3 O 12 Solution A was prepared as follows: 13.3 g of 37% HCl and 8.36 g of ZrOCl2·8H2O were dissolved in 20 mL of deionized water. After complete dissolution, 7.34 g of La2O3 was added and stirred until dissolved. The solution was then diluted with water to 100 mL.

[0154] Composition B was prepared by the following method: 9.97 g KOH and 1.17 g (NH4) were added. 10 H2W 12 O 42 ].xH2O (89.1% WO3) dissolved in 100 mL of water. (NH4) 10 H2W 12 O 42 The solubility of ].xH2O is low, forming a turbid suspension.

[0155] Solution A was added to composition B at room temperature over 1 hour. The resulting white precipitate was separated by centrifugation.

[0156] The filter cake was then resuspended in a solution of 7.26 g LiNO3 in 50 ml of deionized water and stirred until resuspended. The suspension was prepared to a volume of 100 ml. The suspension was then frozen and lyophilized. The dried solid was heated to 900 °C for 10 hours to obtain Li. 6.4 La3Zr 1.7 W 0.3 O 12 XRD analysis confirmed that the crystal structure is cubic. A small amount of La₂Zr₂O₇ impurity was present. Tungsten was provided as a polyoxometalate.

[0157] Example 27 - LT02-147 –Li 6.4 La3Zr 1.4 Nb 0.6 O 12 Solution A was prepared by dissolving 266.1 g of 37% HCl and 137.4 g of ZrOCl2·8H2O in 775 ml of deionized water. After complete dissolution, 146.6 g of La2O3 was added and stirred to dissolve.

[0158] Composition B was prepared by the following method: 137.1 g of K8Nb6O 19 Solution (31.6% K8Nb6O) 19 15H₂O (5.44% KOH) was diluted with deionized water to 860 ml, and then 168.5 g of Na₂CO₃ was added. A white precipitate was formed.

[0159] At room temperature, solution A is added to composition B over 1 hour. The mixture is aged for 1 hour. The resulting white precipitate is separated by filtration and washed until the conductivity of the filtrate is less than 800 µS.

[0160] The filter cake was then resuspended in a solution of 114.5 g LiOH·H2O in 850 ml of deionized water and stirred until resuspended. The total volume was prepared to 1750 ml. CO2 gas was bubbled into the suspension for 75 minutes until the pH dropped to 11.50. The suspension was aged for approximately 45 minutes; if the pH exceeded 11.5, more CO2 was added. The suspension was then separated by filtration and dried at 110 °C. The dried solid sample was heated to 900 °C for 10 hours to obtain Li. 6.4 La3Zr 1.4 Nb 0.6 O 12 XRD analysis confirmed a cubic crystal structure. No significant impurities were found. This method may be particularly effective because the solution from which lithium-containing precipitates are removed is a lithium carbonate solution, which can be reused without further purification. Therefore, this reduces lithium loss. Niobium is provided in the form of a polyoxometalate.

[0161] Example 28 - CO02-68 –Li 6.4 La3Zr 1.4 Ta 0.6 O 12 Solution A was prepared as follows: 9.0 g of 37% HCl and 4.63 g of ZrOCl2·8H2O were dissolved in 30 mL of deionized water. After dissolution, 4.95 g of La2O3 was added and stirred until dissolved. The solution was then diluted to 112 mL.

[0162] Solution B was prepared by dissolving 5.90 g of Na₂CO₃ in 50 mL of deionized water. Then, 1.92 g of K₈Ta₆O₃ was added. 19 Add 0.16H2O and stir to dissolve.

[0163] Solution A was added to solution B within 1 hour and 40 minutes. The resulting white precipitate was aged for 1 hour, and then separated and washed by vacuum filtration.

[0164] The filter cake was resuspended in 50 mL of deionized water, and 4.46 g of LiOH·H₂O was added and dissolved. Separately, 4.20 g of NH₄HCO₃ was dissolved in 20 mL of deionized water and added to the suspended filter cake over 40 minutes. The white suspension was separated by vacuum filtration and dried at 110 °C. The dried solid was calcined at 900 °C for 12 hours. The prepared material was pure cubic LLZO containing a small amount of La₂O₃. Due to weighing errors in this example, Ta was insufficiently added during the reaction, which may be the cause of impurities. Tantalum was provided in the form of a polyoxometalate.

[0165] Example 29 - MC07-068A –Li 6.65 La 2.875 Rb 0.125 Zr 1.4 Nb 0.6 O 12 9.22 g K8Nb6O 19 .15H₂O was dissolved in 100 ml of deionized water to form a clear, colorless solution. 8.29 g of La(NO₃)₃·6H₂O was dissolved in 50 ml of deionized water to form a clear, colorless solution. Lanthanum nitrate solution was added to potassium hexaniobate solution over 40 minutes, forming a thick, white precipitate. The precipitate was washed and separated by centrifugation, then resuspended in 15 ml of deionized water. 2.43 g of Rb₂CO₃ was added, and the suspension was stirred until homogeneous. The suspension was freeze-dried and then calcined at 1000 °C for 10 hours to form RbLaNb₂O₇. XRD analysis showed that the purity of this material was 80%, with the remainder being Rb₂CO₃.

[0166] Solution A was prepared as follows: 9 ml of 36% HCl and 6.33 g of ZrOCl2·8H2O were dissolved in 30 ml of deionized water. After dissolution, 5.88 g of La2O3 was added and stirred until dissolved. The solution was then diluted to 100 ml.

[0167] Composition B was prepared by the following method: 5.44 g of K8Nb6O 19 .15H2O solution (21.3% K8Nb6O) 19 15H₂O (3.87% KOH) was diluted to 100 mL with deionized water. 1.13 g of RbLaNb₂O₇ (80% purity, the remainder being Rb₂CO₃) was added, and the mixture was stirred to form a homogeneous suspension. Then, 7.28 g of Na₂CO₃ was added and stirred to dissolve, resulting in the formation of a white precipitate.

[0168] Add solution A to mixture B within 1 hour. Separate the resulting white precipitate by centrifugation and washing.

[0169] The filter cake was resuspended in 40 mL of deionized water, and 6.18 g of LiOH·H₂O was added and dissolved. Separately, 5.82 g of NH₄HCO₃ was dissolved in 28 mL of deionized water and added to the suspended filter cake over 40 minutes. The white suspension was separated by vacuum filtration and dried at 110 °C. The dried solid was then calcined at 900 °C for 10 hours. XRD analysis confirmed a cubic crystal structure. Niobium was provided as a polyoxometalate.

[0170] The effect of pH on the non-lithiation precursor material was investigated. Solution A was prepared as follows: 7.01 g ZrOCl2·8H2O was dissolved in 30 mL of deionized water. 12.7 g 37% HCl was added to the solution, and then 7.01 g La2O3 was dissolved in the solution with stirring. The solution was then diluted to 150 mL with deionized water.

[0171] Solution B was prepared by the following method: 7.91 g of K8Nb6O 19 Solution (21.3% K8Nb6O) 19 15H₂O (3.87% KOH) was diluted to 50 ml with deionized water. 8.12 g of Na₂CO₃ was dissolved in the solution with stirring.

[0172] At room temperature, add solution A to solution B over 1 hour. Then adjust the pH of the reaction to the desired value of 3.5-4.5 using 37% HCl. Once a stable pH is reached, separate the precipitate, wash it by centrifugation, and then resuspend it in 50 mL of deionized water.

[0173] 6.20 g of LiOH·H₂O was dissolved in the slurry, and the total volume of the slurry was prepared to 100 mL with deionized water. Separately, 5.84 g of NH₄HCO₃ was dissolved in 27 mL of deionized water with stirring. The NH₄HCO₃ solution was added to the slurry over 40 minutes with stirring. The precipitate was separated by filtration and then dried in an oven at 110 °C. The dried solid was calcined at 900 °C for 12 hours.

[0174] At pH values ​​of 4.0, 4.2, 4.4, and 4.5, cubic lithium lanthanum zirconium niobium oxide (LLZNO) without impurities was formed. At pH values ​​of 3.6, 3.7, 3.8, and 3.9, cubic lithium lanthanum zirconium niobium oxide (LLZNO) containing a small amount of impurities was formed. At pH value of 3.5, cubic LLZNO did not form.

[0175] The above embodiments describe numerous embodiments of the method according to the first aspect of this application and numerous embodiments of doped LLZO according to the second aspect of this application. The above embodiments also describe numerous embodiments of the compositions according to the third and fourth aspects of this application.

[0176] Although this application has been described and illustrated with reference to specific embodiments, those skilled in the art will understand that many different variations of this application are possible, which are not specifically described herein. Only some possible variations are illustrated here.

[0177] The numerous embodiments described above demonstrate that lithium-ionized solid electrolyte materials (such as lithium lanthanum zirconium oxide) can be doped with a wide variety of dopants. Those skilled in the art will recognize that other dopants can also be used.

[0178] The numerous embodiments described above demonstrate that a variety of different types of polyoxometalates can be used as a source of one or more dopants. Those skilled in the art will recognize that other polyoxometalates can also be used. Furthermore, not all dopants need to be provided in the form of a polyoxometalate.

[0179] Integers or elements mentioned in the foregoing description, if having known, obvious, or foreseeable equivalents, are incorporated herein as if listed separately. The true scope of this application should be determined with reference to the claims, which should be construed as covering any such equivalents. The reader should also understand that integers or features described herein as preferred, advantageous, convenient, etc., are optional and do not limit the scope of the independent claims. Furthermore, it should be understood that such optional integers or features, while potentially beneficial in some embodiments of this application, may not be desirable in others and therefore may not be present.

Claims

1. A reaction composition for forming doped lithium lanthanum zirconium oxide, comprising: One or more lithium, lanthanum and / or zirconium materials used to form the doped lithium lanthanum zirconium oxide, and at least one dopant provided as a polyoxometalate.

2. The reaction composition according to claim 1, comprising an anion source, wherein lithium can form an insoluble salt with the anion.

3. The reaction composition according to claim 2, wherein it comprises a carbonate ion source.

4. The reaction composition according to claim 2 or 3, wherein the carbonate ion source comprises hydroxide ions, carbonate ions, bicarbonate ions, or carbon dioxide.

5. The reaction composition according to any one of the preceding claims, comprising one or more lanthanum and / or zirconium materials for forming the doped lithium lanthanum zirconium oxide, and at least one dopant provided as a polyoxometalate for forming the doped lithium lanthanum zirconium oxide, but excluding lithium materials.

6. The reaction composition according to any one of the preceding claims, comprising a precipitate containing one or more lanthanum and / or zirconium materials for forming the doped lithium lanthanum zirconium oxide, and at least one dopant, optionally provided as a polyoxometalate.

7. The reaction composition according to any one of claims 1-4 and 6, comprising one or more lanthanum and / or zirconium materials for forming the doped lithium lanthanum zirconium oxide, and at least one dopant provided in the form of a polyoxometalate and one or more lithium materials for forming the doped lithium lanthanum zirconium oxide.

8. The reaction composition according to any one of the preceding claims, wherein the polyoxometalate comprises a transition metal, a Group 13 substance, a Group 15 substance, or a Group 16 substance.

9. The reaction composition according to any one of the preceding claims, comprising one or more dopants, said dopants comprising one or more alkali metals, alkaline earth metals, lanthanides, and rare earth substances.

10. The reaction composition according to any one of the preceding claims, wherein the pH value is at least 3.

5.

11. A method for preparing a reactive composition according to any one of the preceding claims, the method comprising mixing at least two compositions, wherein at least one composition comprises a polyoxometalate, at least one composition comprises a zirconium substance, and at least one composition comprises a lanthanide substance.

12. A multipart reactive composition for forming doped lithium lanthanum zirconium oxide, comprising: The first part comprises one or more lithium, lanthanum and / or zirconium materials for forming the doped lithium lanthanum zirconium oxide, optionally a base, and optionally a dopant provided as a polyoxometalate. as well as The second part, if no base is provided in the first part, contains a base, and if no polyoxometalate is provided in the first part, contains a dopant provided in the form of a polyoxometalate; or The third part, if lithium is not provided in the first or second part, contains lithium, optionally a lithium-ion solution.

13. A method for preparing doped lithium lanthanum zirconium oxide, the method comprising: Forming doped lithium lanthanum zirconium oxide from polyoxometalates, wherein the method includes forming a lithium-containing precipitate and heating the lithium-containing precipitate to form the doped lithium lanthanum zirconium oxide.

14. The method of claim 13, wherein the polyoxometalate comprises a transition metal, a Group 13 substance, a Group 15 substance, or a Group 16 substance.

15. The method according to claim 13 or 14, wherein the polyoxometalate comprises one or more of Mo, Nb, Te, Al, Ga, Sb, W and Ta.

16. The method according to any one of claims 13-15, comprising mixing at least two compositions, wherein at least one composition comprises a polyoxometalate.

17. The method according to any one of claims 13-16, comprising forming a solid (optionally a precipitate) comprising lanthanides, zirconium, and dopants derived from polyoxometalates.

18. The method of claim 17, further comprising contacting the precipitate with a solution containing lithium ions to form a lithium-containing precipitate.