Lithium titanium aluminum phosphate material as well as preparation method and application thereof

Abstract

The invention relates to the field of electrolyte material preparation, in particular to a lithium titanium aluminum phosphate material and a preparation method and application thereof. The invention provides a preparation method of a titanium-aluminum-lithium phosphate material, which comprises the following steps: mixing and sintering raw materials to obtain the titanium-aluminum-lithium phosphate material, wherein the raw materials comprise aluminum titanate, a titanium source, a lithium source, a phosphorus source and an additive; and the additive is selected from at least one of Nb2O5, TeO2, SiO2, H3BO3, B2O3 and LiBF4. The preparation method provided by the invention can obviously improve the purity of the lithium titanium aluminum phosphate material, thereby improving the ionic conductivity of the material.

Description

Technical Field

[0001] This invention relates to the field of electrolyte material preparation, specifically to a lithium titanium aluminum phosphate material, its preparation method, and its application. Background Technology

[0002] With the widespread application of lithium-ion batteries in consumer electronics, electric vehicles, and other fields, the requirements for their safety, energy density, and cycle life are increasing. Traditional lithium-ion batteries use organic electrolytes as electrolytes, which have drawbacks such as high activity, volatility, and flammability, which to some extent limits their further development. Therefore, lithium metal batteries based on solid-state electrolytes have attracted much attention due to their higher safety and energy density. Among them, lithium aluminum titanium phosphate (LATP), as a promising solid-state electrolyte material, has become a research hotspot due to its high ionic conductivity, wide electrochemical window, and good chemical stability.

[0003] In related technologies, the prepared lithium titanium aluminum phosphate may exhibit several issues: either the formation of insulating AlPO4 impurities at grain boundaries and the volatilization of lithium salts to form non-lithium titanium aluminum phosphate impurities, which hinder ion conduction and reduce the ionic conductivity of the lithium titanium aluminum phosphate material; or the poor crystallinity of the lithium titanium aluminum phosphate material further hinders ion conduction, resulting in lithium titanium aluminum phosphate with high bulk impedance and low ionic conductivity. In summary, the lithium titanium aluminum phosphate materials prepared in related technologies exhibit high bulk impedance and low ionic conductivity. Summary of the Invention

[0004] Therefore, the technical problem to be solved by the present invention is to overcome the defects of large bulk impedance and low ionic conductivity of lithium titanium aluminum phosphate materials in related technologies, thereby providing a lithium titanium aluminum phosphate material, its preparation method and application.

[0005] This invention provides a method for preparing lithium titanium aluminum phosphate material, comprising the following steps:

[0006] The raw materials are mixed and sintered to obtain the lithium titanium aluminum phosphate material.

[0007] The raw materials include aluminum titanate, titanium source, lithium source, phosphorus source, and additives.

[0008] The preparation of the aluminum titanate includes the following steps: mixing aluminum salt, titanium salt, carbonate and water, adjusting the pH value with an alkaline solution to carry out a precipitation reaction, and then filtering, washing, drying and calcining to obtain the aluminum titanate;

[0009] The additive is selected from at least one of Nb2O5, TeO2, SiO2, H3BO3, B2O3, and LiBF4; the amount of additive in the raw material accounts for 0-5 wt% of the total mass.

[0010] Optionally, the preparation of the aluminum titanate includes the following steps: mixing an aluminum salt solution, a titanium salt solution, and a carbonate solution, adjusting the pH value with an alkaline solution to carry out a precipitation reaction, followed by filtration, washing, drying, and calcination to obtain the aluminum titanate;

[0011] Further optionally, the preparation of the aluminum titanate includes the following steps: mixing an aluminum salt solution and a titanium salt solution and adding them to a carbonate solution, adjusting the pH value with an alkaline solution to carry out a precipitation reaction, and then filtering, washing, drying and calcining to obtain the aluminum titanate;

[0012] Optionally, after the precipitation reaction is completed, at least one of the aluminum in the aluminum salt solution or the titanium in the titanium salt solution is completely consumed.

[0013] Preferably, the chemical formula of the lithium titanium aluminum phosphate material is Li y Al x Ti 2-x (PO4)3, where 0 < x < 2, 1 < y < 3.

[0014] Preferably, in the preparation of the aluminum titanate, Al 3 Ti 4+ and CO3 2- The molar ratio of added components was (1.8-2.2):1:(4.8-5.2);

[0015] More preferably, in the precipitation reaction, Al 3+ Ti 4+ and CO3 2- The molar ratio is 2:1:5.

[0016] Preferably, the precipitation reaction is carried out in an environment with a pH of 5-8;

[0017] More preferably, the precipitation reaction is carried out in an environment with a pH of 6-6.5;

[0018] Preferably, the calcination temperature is 1000-1500℃ and the time is 2-12h.

[0019] Preferably, the aluminum salt in the aluminum salt solution is selected from Al2(SO4)3;

[0020] Preferably, the titanium salt in the titanium salt solution is selected from at least one of Ti2(SO4)3 and TiOSO4;

[0021] Preferably, the carbonate in the carbonate solution is selected from at least one of NH4HCO3, NaHCO3, and Na2CO3;

[0022] Preferably, the alkali in the alkaline solution is selected from NH3·H2O;

[0023] Preferably, the concentration of the aluminum salt solution is 1–30 mg / mL;

[0024] Preferably, the concentration of the titanium salt solution is 1–30 mg / mL;

[0025] Preferably, the concentration of the carbonate solution is 1–200 mg / mL;

[0026] Preferably, the concentration of the alkaline solution is 1 to 15 mol / mL.

[0027] Preferably, the titanium source is selected from at least one of TiO2, Ti2(SO4)3, TiO, TiOSO4, Ti2O3, H4TiO4, and Ti(NO3)4;

[0028] Preferably, the lithium source is selected from at least one of Li2CO3, LiOH·H2O, and LiNO3;

[0029] Preferably, the phosphorus source is selected from at least one of NH4H2PO4, H3PO4, and (NH4)2HPO4;

[0030] Preferably, the amount of additives in the raw materials is greater than 0 wt% and less than or equal to 5 wt% of the total mass.

[0031] Preferably, the sintering temperature is 400-1000℃ and the time is 3-36h.

[0032] The present invention also provides a lithium titanium aluminum phosphate material, which is prepared by the preparation method described above.

[0033] The present invention also provides a solid electrolyte, wherein the solid electrolyte comprises lithium titanium aluminum phosphate material prepared by the preparation method described above or the lithium titanium aluminum phosphate material described above;

[0034] Optionally, polymers may also be included;

[0035] Optionally, the polymer is selected from at least one of polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride, polymethyl methacrylate, polypropylene oxide, polyvinylidene chloride, and polyethylene;

[0036] Optionally, the polymer has a weight-average molecular weight of 10-5 million.

[0037] The present invention also provides a solid-state battery, wherein the solid-state battery includes the solid electrolyte described above.

[0038] The technical solution of this invention has the following advantages:

[0039] The present invention provides a method for preparing lithium titanium aluminum phosphate material, comprising the following steps: mixing and sintering raw materials to obtain the lithium titanium aluminum phosphate material; wherein, the raw materials include aluminum titanate, titanium source, lithium source, phosphorus source, and additives; the preparation of aluminum titanate comprises the following steps: mixing aluminum salt, titanium salt, carbonate, and water, adjusting the pH value with an alkaline solution to carry out a precipitation reaction, followed by filtration, washing, drying, and calcination to obtain the aluminum titanate; the additives are selected from at least one of Nb2O5, TeO2, SiO2, H3BO3, B2O3, and LiBF4; the amount of additives in the raw materials accounts for 0-5 wt% of the total mass.

[0040] This invention obtains aluminum titanate by mixing aluminum salt, titanium salt, carbonate, and water, adjusting the pH value with an alkaline solution, and then carrying out a precipitation reaction. This preparation method helps to reduce the introduction of impurities, resulting in a more uniform reaction. The obtained aluminum titanate has the advantages of high purity, fine particle size, and uniform element distribution. After mixing the above aluminum titanate, titanium source, lithium source, and phosphorus source and sintering, lithium titanium aluminum phosphate is obtained, which can significantly improve the purity of lithium titanium aluminum phosphate material and thus improve the ionic conductivity of the material.

[0041] Furthermore, the preparation method of lithium titanium aluminum phosphate material provided by the present invention includes additives in the raw materials. Adding additives not only lowers the reaction temperature, reduces the decomposition of lithium salts at high temperatures and the generation of insulating impurities in AlPO4, but also effectively promotes element diffusion, reduces the porosity of lithium titanium aluminum phosphate particles, and increases their relative density, thus enabling lithium titanium aluminum phosphate to possess high ionic conductivity and low bulk impedance. Attached Figure Description

[0042] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0043] Figure 1 This is a scanning electron microscope image of aluminum titanate in Example 1 of the present invention;

[0044] Figure 2 This is a scanning electron microscope image of the lithium aluminum titanium phosphate material obtained in Example 1 of the present invention;

[0045] Figure 3 This is the XRD pattern of lithium titanium aluminum phosphate obtained in Example 1 of the present invention. Detailed Implementation

[0046] The following embodiments are provided to better understand the present invention and are not limited to the preferred embodiments described. They do not constitute a limitation on the content and scope of protection of the present invention. Any product that is the same as or similar to the present invention, derived by any person under the guidance of the present invention or by combining the features of the present invention with other prior art, falls within the protection scope of the present invention.

[0047] For experiments not specifically described in the examples, the procedures or conditions should be followed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.

[0048] Example 1

[0049] This embodiment provides a lithium aluminum titanium phosphate material, the preparation method of which includes the following steps:

[0050] (1) Mix 1 L of Al2(SO4)3 aqueous solution and 1 L of TiOSO4 aqueous solution thoroughly, then add to 0.4 L of NH4HCO3 solution to carry out precipitation reaction. During the reaction, adjust the pH value to 6 with NH3·H2O solution. After filtration, washing, drying, and calcination at 1300℃ for 5 h, aluminum titanate is obtained. Figure 1 (Scanning electron microscope image of the prepared aluminum titanate); wherein, the concentration of Al2(SO4)3 aqueous solution is 15 mg / mL; the concentration of TiOSO4 aqueous solution is 7 mg / mL; the concentration of NH4HCO3 aqueous solution is 43.3 mg / mL; and the concentration of NH3·H2O solution is 2 mol / mL;

[0051] (2) The 5.00g aluminum titanate, 10.98g TiO2, 37.96g NH4H2PO4, 6.10g Li2CO3 and 1.80g Nb2O5 obtained in step (1) were mixed and sintered at 900℃ for 12h. After natural cooling and crushing, the lithium aluminum titanium phosphate material was obtained. Figure 2 The image shows a scanning electron microscope (SEM) image of the prepared lithium aluminum titanium phosphate material. Figure 3 The image shows the XRD pattern of the prepared lithium titanium aluminum phosphate material. It can be seen from the image that the prepared lithium titanium aluminum phosphate material has complete peak shapes and high crystallinity. Its chemical formula is Li. 1.5 Al 0.5 Ti 1.5 (PO4)3.

[0052] Example 2

[0053] This embodiment provides a lithium aluminum titanium phosphate material, the preparation method of which includes the following steps:

[0054] (1) Mix 1 L of Al2(SO4)3 aqueous solution and 1 L of TiOSO4 aqueous solution evenly, add to 0.4 L of NH4HCO3 solution to carry out precipitation reaction. During the reaction, adjust the pH value to 6 by NH3·H2O. After filtration, washing, drying and calcination at 1300℃ for 5 h, aluminum titanate is obtained. The concentration of Al2(SO4)3 aqueous solution is 15 mg / mL; the concentration of TiOSO4 aqueous solution is 7 mg / mL; the concentration of NH4HCO3 aqueous solution is 43.3 mg / mL; and the concentration of NH3·H2O solution is 3.5 mol / mL.

[0055] (2) The 5.00g aluminum titanate, 22.69g TiO2, 63.26g NH4H2PO4, 8.80g Li2CO3 and 2.99g Nb2O5 obtained in step (1) were mixed and sintered at 900℃ for 12h. After natural cooling and crushing, the lithium aluminum titanium phosphate material was obtained, with the chemical formula Li. 1.3 Al 0.3 Ti 1.7 (PO4)3.

[0056] Example 3

[0057] This embodiment provides a lithium aluminum titanium phosphate material, the preparation method of which includes the following steps:

[0058] (1) Mix 1 L of Al2(SO4)3 aqueous solution and 1 L of Ti2(SO4)3 aqueous solution evenly, add to 0.6 L of NaHCO3 solution to carry out precipitation reaction. During the reaction, adjust the pH value to 6.5 with NH3·H2O. After filtration, washing, drying and calcination at 1400℃ for 3 h, aluminum titanate is obtained. The concentration of Al2(SO4)3 aqueous solution is 20 mg / mL; the concentration of Ti2(SO4)3 aqueous solution is 11.22 mg / mL; the concentration of NaHCO3 aqueous solution is 40.9 mg / mL; and the concentration of NH3·H2O solution is 6 mol / mL.

[0059] (2) The 5.00g aluminum titanate, 9.88g Ti2O3, 32.34g H3PO4, 6.92g LiOH·H2O and 1.08g TeO2 obtained in step (1) were mixed and sintered at 800℃ for 24h. After natural cooling and crushing, the lithium aluminum titanium phosphate material was obtained, with the chemical formula Li. 1.5 Al 0.5 Ti 1.5 (PO4)3.

[0060] Example 4

[0061] This embodiment provides a lithium titanium aluminum phosphate material, which is prepared in a similar manner to that of Embodiment 1, except that Nb2O5 in step (2) of Embodiment 1 is replaced with an equal weight of SiO2.

[0062] Example 5

[0063] This embodiment provides a lithium titanium aluminum phosphate material, which is prepared in a similar manner to that of Example 1, except that Nb2O5 in step (2) of Example 1 is replaced with an equal weight of H3BO3.

[0064] Example 6

[0065] This embodiment provides a lithium titanium aluminum phosphate material, which is prepared in a similar manner to that of Example 1, except that Nb2O5 in step (2) of Example 1 is replaced with an equal weight of B2O3.

[0066] Example 7

[0067] This embodiment provides a lithium aluminum titanium phosphate material, which is prepared in a similar manner to that of Example 1, except that Nb2O5 in step (2) of Example 1 is replaced with an equal weight of LiBF4.

[0068] Comparative Example 1

[0069] This comparative example provides a lithium titanium aluminum phosphate material, which is prepared in a similar manner to Example 1, except that no additive (Nb2O5) is added.

[0070] Comparative Example 2

[0071] This comparative example provides a lithium aluminum titanium phosphate material, the preparation method of which includes the following steps:

[0072] (1) Weigh 15g Al2(SO4)3 and 7g TiOSO4, mix them, and calcine them at 1300℃ for 5h to obtain aluminum titanate;

[0073] (2) The 5.00g aluminum titanate, 10.98g TiO2, 37.96g NH4H2PO4, 6.10g Li2CO3 and 1.80g Nb2O5 obtained in step (1) were mixed and sintered at 900℃ for 12h. After natural cooling and crushing, the lithium aluminum titanium phosphate material was obtained, with the chemical formula Li. 1.5 Al 0.5 Ti 1.5 (PO4)3.

[0074] Comparative Example 3

[0075] This comparative example provides a lithium aluminum titanium phosphate material, the preparation method of which includes the following steps:

[0076] 9.41g Al2(SO4)3, 13.17g TiO2, 37.96g NH4H2PO4, 6.10g Li2CO3 and 2.0g Nb2O5 were mixed and sintered at 900℃ for 12h. After natural cooling and crushing, the lithium titanium aluminum phosphate material was obtained, with the chemical formula Li. 1.5 Al 0.5 Ti 1.5 (PO4)3.

[0077] Test Example 1

[0078] The bulk impedance and ionic conductivity of the lithium titanium aluminum phosphate materials prepared in each embodiment and comparative example were tested. The test results are shown in Table 1. The test methods are as follows:

[0079] Lithium aluminum titanium phosphate powder was placed on a tablet press and subjected to a pressure of 20 MPa to obtain a disc with a diameter of 14 mm and a thickness of 1.5 mm. A uniform layer of silver paste was then coated on both sides. A symmetrical cell was assembled by sandwiching the disc between two stainless steel plates. The bulk impedance of the lithium aluminum titanium phosphate was measured on an electrochemical workstation at a frequency of 10⁻¹⁰. 6 The frequency is Hz, and the amplitude is 10mV. The ionic conductivity is calculated according to the formula: σ=L / (R*S), where σ is the ionic conductivity (S / cm), L is the thickness of the disc, S is the area of ​​the disc, and R is the volume impedance of the disc under test (Ω).

[0080] Table 1. Bulk impedance and ionic conductivity of lithium titanium aluminum phosphate materials in each embodiment and comparative example.

[0081] Volume impedance (Ω) Electrical conductivity (S / cm) Example 1 103.6 <![CDATA[9.4×10 -4 ]]> Example 2 88.5 <![CDATA[1.1×10 -3 ]]> Example 3 105.9 <![CDATA[9.2×10 -4 ]]> Example 4 113.3 <![CDATA[8.6×10 -4 ]]> Example 5 109.5 <![CDATA[8.9×10 -4 ]]> Example 6 102.6 <![CDATA[9.5×10 -4 ]]> Example 7 100.4 <![CDATA[9.7×10 -4 ]]> Comparative Example 1 124.9 <![CDATA[7.8×10 -4 ]]> Comparative Example 2 131.7 <![CDATA[7.4×10 -4 ]]> Comparative Example 3 167.9 <![CDATA[5.8×10 -4 ]]>

[0082] As can be seen from Table 1, the lithium titanium aluminum phosphate materials prepared in Examples 1-7 have significantly lower bulk impedance and higher conductivity compared to the lithium titanium aluminum phosphate materials prepared in Comparative Examples 1-3.

[0083] Test Example 2

[0084] The electrochemical performance of the secondary batteries prepared from lithium titanium aluminum phosphate in the various examples and comparative examples was tested. The preparation methods of the secondary batteries are as follows:

[0085] The 8-series nickel-cobalt-manganese ternary TLP813 material (molecular formula LiNi) 0.8 Co 0.07 Mn 0.13 O2), conductive carbon black, and PVDF binder are uniformly mixed at a mass ratio of 97:1:2 and dispersed in NMP and stirred for 10 hours to form a slurry. The slurry is then coated onto aluminum foil and dried in an oven at 70°C for 12 hours to form a positive electrode sheet.

[0086] Solid electrolytes and polyethylene (PE) with a weight-average molecular weight of 500,000 were mixed at a mass ratio of 30:70 and then melt-extruded at 180°C to prepare uniform cast sheets. Subsequently, the cast sheets were stretched at 130°C to prepare stretched films. Finally, the films were wound up and slit to prepare diaphragms.

[0087] Graphite anode material, conductive carbon black, styrene-butadiene rubber (SBR), and sodium carboxymethyl cellulose (CMC-Na) were uniformly mixed at a mass ratio of 96:1:2:1 and dispersed in distilled water and stirred for 10 hours to form a slurry. The slurry was then coated onto copper foil and dried in an oven at 70°C for 12 hours to form the anode sheet.

[0088] After stacking the positive electrode, separator, and negative electrode in sequence, the electrolyte is injected to assemble a square battery with a capacity of 20Ah. The electrolyte solvent is ethylene carbonate, and the solute is lithium hexafluorophosphate (solute concentration of 1mol / L).

[0089] The testing method is as follows:

[0090] Low-temperature discharge performance and constant-current charging ratio test: The above-mentioned square batteries were subjected to constant-current, constant-voltage charging and constant-current discharging tests at room temperature. Specifically, they were first charged to 4.2V at a constant current density of 0.1C, then charged to 0.05C at a constant voltage density, and then discharged to 2.7V at a constant current density of 0.1C. The constant-current charging capacity C1, constant-voltage charging capacity C2, and constant-current discharging capacity D1 were obtained respectively. Subsequently, constant-current, constant-voltage charging and constant-current discharging tests were conducted at -10℃. Specifically, they were charged to 4.2V at a constant current density of 0.1C, then charged to 0.05C at a constant voltage density, and then discharged to 2.7V at a constant current density of 0.1C. The constant-current charging capacity C3, constant-voltage charging capacity C4, and constant-current discharging capacity D2 were obtained respectively. D2 / D1×100% is the low-temperature discharge performance, and C3 / (C3+C4)×100% is the constant-current charging ratio at -10℃. The results are shown in Table 2.

[0091] Table 2

[0092] Low temperature discharge performance -10℃ 0.1C charging constant current ratio Example 1 84％ 85.0％ Example 2 87％ 87.9％ Example 3 82％ 83.6％ Example 4 78％ 80.1％ Example 5 80％ 80.9％ Example 6 84％ 85.5％ Example 7 86％ 87.1％ Comparative Example 1 74％ 76.2％ Comparative Example 2 73％ 75.0％ Comparative Example 3 71％ 73.9％

[0093] As can be seen from Table 2, the battery cells prepared using lithium titanium aluminum phosphate obtained in Examples 1-7 have better low-temperature discharge performance and higher charging constant current ratio compared with the battery cells prepared using materials obtained in Comparative Examples 1-3.

[0094] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A method for producing a lithium titanium aluminum phosphate material, characterized by, The method comprises the following steps: Mixing and sintering raw materials to obtain the lithium titanium aluminum phosphate material; The raw materials comprise aluminum titanate, a titanium source, a lithium source, a phosphorus source, and an additive; The aluminum titanate is prepared by mixing an aluminum salt, a titanium salt, a carbonate, and water, adjusting the pH value with an alkali solution to perform a precipitation reaction, and then performing filtration, washing, drying, and calcination. The additive is selected from at least one of Nb2O5, TeO2, SiO2, H3BO3, B2O3, and LiBF4.

2. The production method according to claim 1, characterized by, The chemical formula of the lithium titanium aluminum phosphate material is Li y Al x Ti 2-x (PO4)3, wherein 0 3. The preparation method according to claim 1, characterized in that, The molar ratio of the addition of Al 3+ , Ti 4+ and CO3 2- in the preparation of said aluminum titanate is (1.8-2.2):1:(4.8-5.2); Preferably, the molar ratio of Al 3+ , Ti 4+ and CO3 2- in the precipitation reaction is 2:1:

5.

4. The method of claim 1, wherein, The precipitation reaction is performed in an environment with a pH value of 5-8. More preferably, the precipitation reaction is performed in an environment with a pH value of 6-6.

5. Preferably, the calcination temperature is 1000-1500°C, and the time is 2-12h.

5. The preparation method according to claim 1, characterized in that, The aluminum salt in the aluminum salt solution is selected from Al2(SO4)3. Preferably, the titanium salt in the titanium salt solution is selected from at least one of Ti2(SO4)3 and TiOSO4. Preferably, the carbonate in the carbonate solution is selected from at least one of NH4HCO3, NaHCO3, and Na2CO3. Preferably, the alkali in the alkali solution is NH3·H2O. Preferably, the concentration of the aluminum salt solution is 1-30mg / mL. Preferably, the concentration of the titanium salt solution is 1-30mg / mL. Preferably, the concentration of the carbonate solution is 1-200mg / mL. Preferably, the concentration of the alkali solution is 1-15mol / mL.

6. The method of claim 1, wherein, The titanium source is selected from at least one of TiO2, Ti2(SO4)3, TiO, TiOSO4, Ti2O3, H4TiO4, and Ti(NO3)4. Preferably, the lithium source is selected from at least one of Li2CO3, LiOH·H2O, and LiNO3. Preferably, the phosphorus source is selected from at least one of NH4H2PO4, H3PO4, and (NH4)2HPO4. Preferably, the amount of the additive in the raw materials accounts for greater than 0wt% and less than or equal to 5wt% of the total mass.

7. The preparation method according to claim 1, characterized in that, The sintering temperature is 400-1000°C, and the time is 3-36h.

8. A titanium aluminum lithium phosphate material, characterized in that, The lithium titanium aluminum phosphate material is prepared by the preparation method in any one of claims 1-7.

9. A solid state electrolyte, characterized by, The solid-state electrolyte comprises the lithium titanium aluminum phosphate material prepared by the preparation method in any one of claims 1-7 or the lithium titanium aluminum phosphate material in claim 8, and optionally further comprises a polymer.

10. A solid state battery, characterized by The solid-state electrolyte in claim 9. The solid-state electrolyte in claim 9.

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