Oxide solid-state electrolyte and preparation method therefor, all-solid-state battery and electric device

Abstract

The present invention belongs to the technical field of solid-state electrolytes, and provides an oxide solid-state electrolyte and a preparation method therefor, an all-solid-state battery and an electric device. The chemical formula of the electrolyte is Aa-bMbXcTi2-cZ dP3-dOe, wherein a=1-2, b=0-1, c=0-1, d=0-1.5, and e=(12-d)-12; A comprises any one of Li, Na and K; M comprises at least one of Na, K, Rb, Cs, Be, Mg, Ca, Sr and Ba; X comprises at least one of Al, Ga, In, La, Y, Sc, Fe and Cr; Z comprises at least one of B, S, Si, V, Tc, Re, As, Xe, W, Se, Nb and Mn; and A is different from M, and b, c and d are not 0 at the same time. By subjecting key lattice sites in the electrolyte to doping modification, the ionic conductivity is improved.

Description

An oxide solid electrolyte and its preparation method, an all-solid-state battery, and an electrical device thereof.

[0001] Cross-references to related applications

[0002] This disclosure claims priority to Chinese Patent Application No. 2025100106042, filed on January 3, 2025, entitled "An Oxide Solid Electrolyte and Its Preparation Method, and an All-Solid-State Battery", the entire contents of which are incorporated herein by reference. Technical Field

[0003] This disclosure relates to the field of solid-state electrolyte technology, and particularly to an oxide solid-state electrolyte and its preparation method, an all-solid-state battery, and an electrical device thereof. Background Technology

[0004] Compared to the electrolyte in traditional liquid lithium batteries, solid-state electrolytes not only transport lithium ions but also act as a separator to prevent short circuits. After decades of research and development, solid-state electrolytes (SSEs) are classified into three categories: inorganic solid-state electrolytes (ISEs), solid-state polymer electrolytes (SPEs), and composite polymer electrolytes (CPEs). Solid-state inorganic electrolytes include halide solid-state electrolytes, sulfide solid-state electrolytes, and oxide solid-state electrolytes.

[0005] Currently reported oxide solid-state batteries (SSEs) include garnet-type, lisicon-type, and nASICON-type materials. Among them, LATP, as a nASICON-type SSE, has been widely studied in solid-state lithium batteries due to its advantages such as non-flammability, high conductivity, wide electrochemical window, and ease of processing. However, the preparation of LATP faces major challenges, including unsatisfactory phase purity, low sintering activity, high production cost, and poor ionic conductivity. Summary of the Invention

[0006] To address the shortcomings of existing technologies, the purpose of this disclosure is to provide an oxide solid electrolyte and its preparation method, an all-solid-state battery, and an electrical device, so as to improve the ionic conductivity of the oxide solid electrolyte.

[0007] The embodiments of this disclosure are implemented as follows:

[0008] In a first aspect, embodiments of this disclosure provide an oxide solid electrolyte, the chemical formula of which is A. a-b M b X c Ti 2-c Z d P 3-d O eWhere a = 1 to 2, b = 0 to 1, c = 0 to 1, d = 0 to 1.5, e = (12-d) to 12; A includes any one of Li, Na and K; M includes one or more of Na, K, Rb, Cs, Be, Mg, Ca, Sr and Ba; X includes one or more of Al, Ga, In, La, Y, Sc, Fe and Cr; Z includes one or more of B, S, Si, V, Tc, Re, As, Xe, W, Se, Nb and Mn; where A and M are not the same, and b, c and d are not simultaneously 0.

[0009] This disclosure utilizes multiple functional ions to target A a-b M b X c Ti 2-c Z d P 3-d O e Doping modification of key lattice sites includes partially replacing Li, Na, or K ions with large-size cations (M ions), partially replacing Ti ions with low-valent cations (X ions), and partially replacing PO4 with other polyanions (formed by Z and O complexes). 3- Achieving synergistic effects through multi-ion co-doping can further improve ionic conductivity. Specifically, introducing ions with larger atomic radii (such as Na+) at the Li site... + K + (etc.), which can effectively improve the lattice constant, for Li + It provides a wider diffusion channel, thereby lowering the ion migration energy barrier and promoting Li + Rapid migration in electrolytes; use of low-valent cations (such as Al) 3+ Ga 3+ Replacing Ti ions with other polyanions (such as BO3+, etc.) increases the concentration of Li or Na vacancies in the crystal lattice, accelerates the migration rate of lithium ions, and further improves ionic conductivity; using other polyanions with valences of -3, -4, or -5 (such as BO3+, etc.) 3- SiO4 4- SO4 2- (etc.) partially replaces the traditional -3 valent PO4 3- This not only increases the concentration of Li or Na in the lattice, but also enhances the stability of the crystal structure and improves the ionic conductivity due to the introduction of high-valence anions. Therefore, the oxide solid-state electrolyte provided in this disclosure achieves a conductivity exceeding 1 mS / cm at room temperature through the synergistic effect of multi-ion doping. -1 It has ultra-high ionic conductivity.

[0010] In some embodiments of this disclosure, the chemical formula of the oxide solid electrolyte is Li. a-b M b Xc Ti 2-c Z d P 3-d O 12 Wherein, M includes one or more of the elements Na, K, Rb, Cs, Be, Mg, and Ca; X includes one or more of the elements Al, Ga, In, La, Y, Sc, Fe, and Cr; Z includes one or more of the elements S, Si, V, Nb, W, Se, and Mn; or, the chemical formula of the oxide solid electrolyte is Li a-b M b X c Ti 2-c Z d P 3-d O 12-d , where Z includes B.

[0011] In some embodiments of this disclosure, the chemical formula of the oxide solid electrolyte is Na. a-b M b X c Ti 2-c Z d P 3-d O 12 Wherein, M includes one or more of the elements K, Rb, Cs, Be, Mg, and Ca; X includes one or more of the elements Al, Ga, In, La, Y, Sc, Fe, and Cr; Z includes one or more of the elements S, Si, V, Nb, W, Se, and Mn; or, the chemical formula of the oxide solid electrolyte is Na. a-b M b X c Ti 2-c Z d P 3-d O 12-d , where Z includes B.

[0012] In some embodiments of this disclosure, the chemical formula of the oxide solid electrolyte is K. a-b M b X c Ti 2-c Z d P 3-d O 12 Wherein, M includes one or more of Rb, Cs, Be, Mg, and Ca; X includes one or more of Al, Ga, In, La, Y, Sc, Fe, and Cr; Z includes one or more of S, Si, V, Nb, W, Se, and Mn; or, the chemical formula of the oxide solid electrolyte is K. a-b M b X c Ti 2-c Zd P 3-d O 12-d , where Z includes B.

[0013] The oxide solid electrolytes disclosed herein include Li-source electrolytes, Na-source electrolytes, and K-source electrolytes, with chemical formulas of Li, Na, and K, respectively. a-b M b X c Ti 2-c Z d P 3-d O 12 Or Li a-b M b X c Ti 2-c Z d P 3-d O 12-d Na a-b M b X c Ti 2-c Z d P 3-d O 12 Or Na a-b M b X c Ti 2-c Z d P 3-d O 12-d and K a-b M b X c Ti 2-c Z d P 3-d O 12 or K a-b M b X c Ti 2-c Z d P 3-d O 12-d Among the electrolytes mentioned above, large-size cations (such as Na+) are used. + K + (etc.) partially replace Li, Na, or K ions, and use low-valent cations (such as Al) 3+ Ga 3+ (etc.) partially replace Ti ions and utilize other polyanions (such as BO3) 3- SiO4 4- SO4 2- (etc.) partially replace PO4 3- Achieving synergistic effects of multi-ion co-doping can further improve ionic conductivity.

[0014] In some embodiments of this disclosure, the oxide solid electrolyte includes Lia Al c Ti 2-c (PO4) 3-d (ZO4) d Na a Al c Ti 2-c (PO4) 3-d (ZO4) d and K a Al c Ti 2-c (PO4) 3-d (ZO4) d Any one of the following, where a = 1 to 2, c = 0 to 1, d = 0 to 1.5, and Z includes one or more of the elements S, Si, V and Nb.

[0015] In some embodiments of this disclosure, the oxide solid electrolyte includes Li a Al c Ti 2-c (PO4) 3-d (ZO3) d Na a Al c Ti 2-c (PO4) 3-d (ZO3) d and K a Al c Ti 2-c (PO4) 3-d (ZO3) d Any one of the following; where a = 1 to 2, c = 0.5 to 1, d = 0.15 to 1.5, and Z includes B.

[0016] In some embodiments of this disclosure, the oxide solid electrolyte includes Li 1.44 Al 0.5 Ti 1.5 (PO4) 2.94 (SO4) 0.06 Li 1.35 Al 0.5 Ti 1.5 (PO4) 2.85 (SO4) 0.15 Li 1.51 Al 0.5 Ti 1.5 (PO4) 2.99 (SiO4) 0.01 Li 1.53 Al 0.5 Ti 1.5 (PO4) 2.97 (SiO4) 0.03Li 1.55 Al 0.5 Ti 1.5 (PO4) 2.95 (SiO4) 0.05 Li 1.5 Al 0.5 Ti 1.5 (PO4)3, Li 1.5 Al 0.5 Ti 1.5 (PO4) 2.85 (BO3) 0.15 and Li 1.5 Al 0.5 Ti 1.5 (PO4) 2.95 (BO3) 0.05 Any one of them.

[0017] Secondly, embodiments of this disclosure provide a method for preparing an oxide solid electrolyte, comprising: mixing and reacting a titanium source compound with a catalyst to obtain a solution containing TiO2. 2+ The solution was then mixed with a complexing agent, A2CO3, M-source compound, X-source compound, NH4H2PO4, and Z-source compound, and added to a solution containing TiO2. 2+ In a solution, the mixture is stirred to form a sol; after drying the sol, it is then ball-milled, shaped, and sintered to obtain an oxide solid electrolyte.

[0018] Among them, the M source compound includes MCO3, the X source compound includes XNO3, and the Z source compound includes AZO4 and / or H3BO3. A includes any one of Li, Na, and K; M includes one or more of Na, K, Rb, Cs, Be, Mg, Ca, Sr, and Ba; X includes one or more of Al, Ga, In, La, Y, Sc, Fe, and Cr; and Z includes one or more of S, B, Si, V, Tc, Re, As, Xe, W, Se, Nb, and Mn.

[0019] This disclosure describes the reaction of a titanium source compound with a catalyst to obtain a product containing TiO2. 2+ The solution was then mixed with a complexing agent, A2CO3, M-source compound, X-source compound, NH4H2PO4, and Z-source compound, and added to a solution containing TiO2. 2+In a solution, stirring forms a sol, achieving uniform mixing of all components and creating a homogeneous sol. Further steps such as ball milling and sintering are used to adjust the microstructure of the electrolyte material, forming a nanostructure with a high specific surface area, thereby preparing an oxide solid electrolyte material with high ionic conductivity. In other words, this disclosure utilizes the sol-gel method to prepare electrolyte materials, achieving uniform mixing of all components and effectively controlling the microstructure of the material to form a nanostructure with a high specific surface area, thus further improving the ionic conductivity of the electrolyte.

[0020] In some embodiments of this disclosure, the titanium source compound includes C 12 H 28 O4Ti.

[0021] C 12 H 28 O4Ti, as a titanium source compound, exhibits good solubility in organic solvents, enabling it to form a homogeneous solution. It also possesses high reactivity, allowing for the rapid generation of high-purity and high-quality titanium oxides under relatively mild conditions, thereby improving the ionic conductivity of solid electrolytes.

[0022] In some embodiments of this disclosure, the catalyst includes HNO3.

[0023] HNO3, as a catalyst, can effectively increase the reaction rate, promote the conversion of titanium source compounds, and facilitate the formation of purer and more homogeneous TiO2. 2+ The solution can also enhance the stability and uniformity of the sol, promoting the formation of high-quality sols.

[0024] In some embodiments of this disclosure, the complexing agent includes citric acid.

[0025] Citric acid, as a polycarboxylic acid, possesses excellent complexing ability, effectively forming stable complexes with metal ions (such as titanium and aluminum). Through complexation with metal ions, citric acid can influence the crystal structure and phase composition of materials during sintering, thereby enhancing ionic conductivity.

[0026] In some embodiments of this disclosure, drying includes: a drying temperature of 100-150°C and a drying time of 12-24 hours.

[0027] Within the above temperature and time range, it can effectively remove moisture and other volatile solvents from the sol and ensure uniform drying of the material.

[0028] In some embodiments of this disclosure, ball milling includes a mass ratio of ball milling raw material to ball milling beads of 1:(5-10).

[0029] In some embodiments of this disclosure, the ball milling speed is 300-400 r / min and the ball milling time is 24-48 h.

[0030] In some embodiments of this disclosure, the sintering process includes: first holding at 550-600°C for 1-3 hours, and then holding at 950-1050°C for 5-6 hours.

[0031] In some embodiments of this disclosure, the heating rate of the sintering process is 5-10°C / min.

[0032] Setting the mass ratio of raw material to milling beads to 1:(5-10), the milling speed to 300-400 r / min, and the milling time to 24-48 h can effectively improve fineness and uniformity, effectively control particle morphology and size distribution, promote the interaction between materials, reduce impurities and agglomeration, and improve physicochemical properties.

[0033] Thirdly, this disclosure provides an all-solid-state battery, including the oxide solid-state electrolyte in any of the above embodiments or the oxide solid-state electrolyte prepared by the preparation method in any of the above embodiments.

[0034] Fourthly, embodiments of this disclosure provide an electrical device including the all-solid-state battery described in any of the above embodiments.

[0035] Beneficial effects: This disclosure introduces ions with larger atomic radii (such as Na, K, etc.) at the Li site, which can effectively improve the lattice constant and enhance the lattice performance of Li. + It provides a wider diffusion channel, thereby lowering the ion migration energy barrier and promoting Li + Rapid migration in electrolytes; partial substitution of Ti ions with low-valent cations (such as Al, Ga, etc.) increases the concentration of Li or Na vacancies in the lattice, accelerates the migration rate of lithium ions, and further improves ionic conductivity. Attached Figure Description

[0036] To more clearly illustrate the technical solutions of the embodiments of this disclosure, the accompanying drawings used in the embodiments will be briefly described below. It should be understood that the following drawings only show some embodiments of this disclosure and should not be regarded as a limitation of the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0037] Figure 1 shows Li 1.5 Al 0.5 Ti 1.5 (PO4)3 doped SO4 2- XRD patterns before and after;

[0038] Figure 2 shows the powder sample Li obtained in Example 2 of this disclosure. 1.35 Al 0.5 Ti 1.5 (PO4) 2.85 (SO4) 0.15 SEM images and EDS elemental analysis;

[0039] Figure 3 shows Li 1.5 Al 0.5 Ti 1.5 (PO4)3-doped SiO4 4- XRD patterns before and after;

[0040] Figure 4 shows LiTi2(PO4)3 doped with Al 3+ XRD patterns before and after;

[0041] Figure 5 shows Li 1.5 Al 0.5 Ti 1.5 (PO4)3 doped SO4 2- Electrochemical impedance spectroscopy at room temperature before and after;

[0042] Figure 6 shows Li 1.5 Al 0.5 Ti 1.5 (PO4)3-doped SiO4 4- Electrochemical impedance spectroscopy at room temperature before and after;

[0043] Figure 7 shows LiTi2(PO4)3 doped with Al 3+ Electrochemical impedance spectroscopy at room temperature before and after. Detailed Implementation

[0044] To make the objectives, technical solutions, and advantages of the embodiments of this disclosure clearer, the technical solutions in the embodiments of this disclosure will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0045] The following provides a detailed description of an oxide solid electrolyte, its preparation method, an all-solid-state battery, and an electrical device according to embodiments of this disclosure.

[0046] This disclosure provides an oxide solid electrolyte with the chemical formula A. a-b M b X c Ti 2-c Z d P 3-d O eWhere a = 1 to 2, b = 0 to 1, c = 0 to 1, d = 0 to 1.5, e = (12-d) to 12; A includes any one of Li, Na and K; M includes one or more of Na, K, Rb, Cs, Be, Mg, Ca, Sr and Ba; X includes one or more of Al, Ga, In, La, Y, Sc, Fe and Cr; Z includes one or more of B, S, Si, V, Tc, Re, As, Xe, W, Se, Nb and Mn; where A and M are not the same, and b, c and d are not simultaneously 0.

[0047] Specifically, the values ​​of a can be 1.0, 1.2, 1.5, 1.8, 2.0, etc.; the values ​​of b can be 0.0, 0.3, 0.5, 0.8, 1.0, etc.; the values ​​of c can be 0.0, 0.3, 0.5, 0.8, 1.0, etc.; and the values ​​of d can be 0.0, 0.10, 0.15, 0.3, 0.5, 0.8, 1.0, 1.3, 1.5, etc.

[0048] This disclosure achieves the following: 1. Introducing ions with larger atomic radii (such as Na, K, etc.) into the Li site can effectively increase the lattice constant, thus improving the Li... + It provides a wider diffusion channel, thereby lowering the ion migration energy barrier and promoting Li + 1. Rapid migration in electrolytes; 2. Partial substitution of Ti ions with low-valent cations (such as Al, Ga, etc.) to increase the concentration of Li or Na vacancies in the crystal lattice, thereby accelerating the lithium ion migration rate and further improving ionic conductivity; 3. Employing other polyanions with -3, -4, or -5 valence (such as BO3) 3- SiO4 4- SO4 2- (etc.) partially replaces the traditional -3 valent PO4 3- This not only increases the concentration of Li or Na in the crystal lattice, but also enhances the stability of the crystal structure and improves the ionic conductivity due to the introduction of high-valence anions; in other words, through the synergistic effect of multi-ion doping, it achieves a conductivity exceeding 1 mS / cm at room temperature. -1 It has ultra-high ionic conductivity.

[0049] When A represents Li, Na, and K respectively, the chemical formula of the oxide solid electrolyte is Li a-b M b X c Ti 2-c Z d P 3-d O 12 Na a-b M b X c Ti 2-c Zd P 3-d O 12 and K a-b M b X c Ti 2-c Z d P 3-d O 12 Wherein, M includes one or more of the elements Na, K, Rb, Cs, Be, Mg, and Ca; X includes one or more of the elements Al, Ga, In, La, Y, Sc, Fe, and Cr; Z includes one or more of the elements S, Si, V, Nb, W, Se, and Mn; or, when A is Li, Na, and K respectively, the chemical formula of the oxide solid electrolyte is Li a-b M b X c Ti 2-c Z d P 3-d O 12-d Na a-b M b X c Ti 2-c Z d P 3-d O 12-d and K a-b M b X c Ti 2-c Z d P 3-d O 12-d Z includes B.

[0050] As an example, the oxide solid electrolyte includes Li a Al c Ti 2-c (PO4) 3-d (ZO4) d Na a Al c Ti 2-c (PO4) 3-d (ZO4) d and K a Al c Ti 2-c (PO4) 3-d (ZO4) d Any one of the following; wherein a = 1 to 2, c = 0 to 1, d = 0 to 1.5, and Z includes one or more of the elements S, Si, V, and Nb; or, the oxide solid electrolyte includes Li a Al c Ti 2-c (PO4) 3-d(ZO3) d Na a Al c Ti 2-c (PO4) 3-d (ZO3) d and K a Al c Ti 2-c (PO4) 3-d (ZO3) d Any one of the following, where a = 1 to 2, c = 0 to 1, d = 0 to 1.5, and Z includes B.

[0051] Specifically, as an example, the oxide solid electrolyte includes Li 1.44 Al 0.5 Ti 1.5 (PO4) 2.94 (SO4) 0.06 Li 1.35 Al 0.5 Ti 1.5 (PO4) 2.85 (SO4) 0.15 Li 1.51 Al 0.5 Ti 1.5 (PO4) 2.99 (SiO4) 0.01 Li 1.53 Al 0.5 Ti 1.5 (PO4) 2.97 (SiO4) 0.03 Li 1.55 Al 0.5 Ti 1.5 (PO4) 2.95 (SiO4) 0.05 Li 1.5 Al 0.5 Ti 1.5 (PO4)3, Li 1.5 Al 0.5 Ti 1.5 (PO4) 2.85 (BO3) 0.15 and Li 1.5 Al 0.5 Ti 1.5 (PO4) 2.95 (BO3) 0.05 Any one of them.

[0052] The preparation method of the above-mentioned oxide solid electrolyte is described below.

[0053] A method for preparing an oxide solid electrolyte includes: mixing and reacting a titanium source compound with a catalyst to obtain a solution containing TiO2. 2+ The solution was then mixed with a complexing agent, A2CO3, M-source compound, X-source compound, NH4H2PO4, and Z-source compound, and added to a solution containing TiO2. 2+ In a solution, a sol is formed by stirring; after drying the sol, it is successively ball-milled, shaped, and sintered to obtain an oxide solid electrolyte; wherein, the M source compound includes MCO3, the X source compound includes XNO3, and the Z source compound includes AZO4 and / or H3BO3, wherein A includes any one of Li, Na, and K; M includes one or more of Na, K, Rb, Cs, Be, Mg, Ca, Sr, and Ba; X includes one or more of Al, Ga, In, La, Y, Sc, Fe, and Cr; and Z includes one or more of S, Si, V, Tc, Re, As, Xe, W, Se, Nb, and Mn.

[0054] In this preparation method, a titanium source compound is reacted with a catalyst to generate a product containing TiO2. 2+ A solution is prepared by adding a complexing agent and other compounds, and the mixture is stirred to form a homogeneous sol. This sol is then subjected to ball milling and sintering to obtain an oxide solid electrolyte material with high ionic conductivity. Therefore, this disclosure utilizes the sol-gel method to prepare electrolyte materials, achieving both uniform mixing of components and effective control over the material's microstructure, resulting in a nanostructure with a high specific surface area. This enhances the migration rate of lithium ions and further improves ionic conductivity.

[0055] Among them, titanium source compounds include, but are not limited to, C 12 H 28 O4Ti; catalysts including but not limited to HNO3; complexing agents including but not limited to citric acid.

[0056] As an example, Li a-b M b X c Ti 2-c Z d P 3-d O 12 The preparation method includes the following steps:

[0057] C 12 H 28 When O4Ti is added to deionized water and stirred, Ti(OH)4 precipitate is immediately formed. After washing and filtering with water, a small amount of deionized water is added to the Ti(OH)4 precipitate, and an appropriate amount of concentrated HNO3 is added to generate TiO2. 2+After the precipitate has completely dissolved, citric acid stabilizing solution is immediately added. Then, Na₂CO₃, MCO₃, and XNO₃ are added and stirred until completely dissolved. Next, NH₄H₂PO₄ and Na₂O₄ are added and stirred for half an hour to form a sol. The sol is then dried at 100-150℃ for 12-24 hours. The dried material is then placed in a ball mill jar and wet-milled at a bead ratio of 1:(5-10) with an appropriate amount of alcohol. The parameters are set to 300-400 r / min and 24-48 h. The ball-milled sample is then dried, ground, and pressed into tablets. The tablets are placed in an alumina crucible and sintered in a muffle furnace. The temperature is increased to 550-600℃ at a rate of 5-10℃ / min and held for 1-3 hours. The temperature is then increased to 950-1050℃ and held for 5-6 hours before natural cooling to obtain the target product.

[0058] As an example, Na a-b M b X c Ti 2-c Z d P 3-d O 12 The preparation method includes the following steps:

[0059] C 12 H 28 When O4Ti is added to deionized water and stirred, Ti(OH)4 precipitate is immediately formed. After washing and filtering with water, a small amount of deionized water is added to the Ti(OH)4 precipitate, and an appropriate amount of concentrated HNO3 is added to generate TiO2. 2+ After the precipitate has completely dissolved, citric acid stabilizing solution is immediately added. Then, Na₂CO₃, MCO₃, and XNO₃ are added and stirred until completely dissolved. Next, NH₄H₂PO₄ and Na₂O₄ are added and stirred for half an hour to form a sol. The sol is then dried at 100-150℃ for 12-24 hours. The dried material is then placed in a ball mill jar and wet-milled at a bead ratio of 1:(5-10) with an appropriate amount of alcohol. The parameters are set to 300-400 r / min and 24-48 h. The ball-milled sample is then dried, ground, and pressed into tablets. The tablets are placed in an alumina crucible and sintered in a muffle furnace. The temperature is increased to 550-600℃ at a rate of 5-10℃ / min and held for 1-3 hours. The temperature is then increased to 950-1050℃ and held for 5-6 hours before natural cooling to obtain the target product.

[0060] As an example, K a-b M b X c Ti 2-c Z d P 3-d O 12 The preparation method includes the following steps:

[0061] C 12 H 28 When O4Ti is added to deionized water and stirred, Ti(OH)4 precipitate is immediately formed. After washing and filtering with water, a small amount of deionized water is added to the Ti(OH)4 precipitate, and an appropriate amount of concentrated HNO3 is added to generate TiO2. 2+ After the precipitate has completely dissolved, citric acid stabilizing solution is immediately added. Then, K₂CO₃, MCO₃, and XNO₃ are added and stirred until completely dissolved. Next, NH₄H₂PO₄ and KZO₄ are added and stirred for half an hour to form a sol. The sol is then dried at 100-150℃ for 12-24 hours. The dried material is then placed in a ball mill jar and wet-milled at a bead ratio of 1:(5-10) with an appropriate amount of alcohol, using parameters set to 300-400 r / min and 24-48 h. The ball-milled sample is then dried, ground, and pressed into tablets. The tablets are placed in an alumina crucible and sintered in a muffle furnace. The temperature is increased to 550-600℃ at a rate of 5-10℃ / min and held for 1-3 hours. The temperature is then further increased to 950-1050℃ and held for 5-6 hours before natural cooling to obtain the target product.

[0062] For example, MCO3 includes, but is not limited to, Na2CO3, K2CO3, Rb2CO3, Cs2CO3, BeCO3, MgCO3, CaCO3, SrCO3, and BaCO3. XNO3 includes, but is not limited to, Al(NO3)3, Ga(NO3)3, In(NO3)3, La(NO3)3, Y(NO3)3, Sc(NO3)3, and Fe(NO3)3. LiZO4 includes, but is not limited to, Li2SO4, Li4SiO4, Li3VO4, LiTcO4, Li2ReO4, Li3AsO4, LiXeO4, Li2WO4, Li2SeO4, and LiMn2O4.

[0063] In the examples above, the drying temperature can be 100℃, 110℃, 120℃, 130℃, 140℃, 150℃, etc., and the drying time can be 12h, 15h, 18h, 20h, 24h, etc.; the ball ball mass ratio during ball milling can be 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, etc., the rotation speed can be 300r / min, 330r / min, 350r / min, 380r / min, 400r / min, etc., and the ball milling time can be 24h, 25h, 26h, 27h, 28h, etc. The heating rate during the sintering process can be 5℃ / min, 6℃ / min, 7℃ / min, 8℃ / min, 9℃ / min, 10℃ / min, etc., the temperature for the first sintering can be 550℃, 580℃, 600℃, etc., and the holding time for the first sintering can be 1h, 2h, 3h, etc.; the temperature for the second sintering can be 950℃, 980℃, 1000℃, 1030℃, 1050℃, etc., and the holding time for the second sintering can be 5.0h, 5.5h, 6.0h, etc.

[0064] The features and performance of this disclosure will be further described in detail below with reference to embodiments.

[0065] Example 1

[0066] This embodiment provides an oxide solid electrolyte with the chemical formula Li. 1.44 Al 0.5 Ti 1.5 (PO4) 2.94 (SO4) 0.06 Its preparation method includes the following steps:

[0067] 2.8g of C 12 H 28 O4Ti was added to 18 mL of deionized water, and upon stirring, Ti(OH)4 precipitate was immediately formed. After washing and filtering, 8 mL of deionized water was added to the Ti(OH)4 precipitate, followed by 1.75 mL of concentrated HNO3 (65%) to generate TiO2. 2+After the precipitate has completely dissolved, 4.3 g of citric acid stabilizing solution is immediately added. Then, 0.37 g of Li₂CO₃ and 1.23 g of Al(NO₃)₃·9H₂O are added and stirred until completely dissolved. Then, 2.22 g of NH₄H₂PO₄ and 0.043 g of Li₂SO₄ are added and stirred for half an hour to form a sol. The sol is then dried at 150 °C for 12 h. The dried material is then placed in a ball mill jar and wet-milled with a ball ratio of 1:10 and an appropriate amount of alcohol. The ball milling speed is 400 r / min and the milling time is 24 h. The ball-milled sample is then dried, ground, and pressed into tablets. The tablets are placed in an alumina crucible and sintered in a muffle furnace. The temperature is increased to 600 °C at a heating rate of 10 °C / min and held for 1 h. Then, the temperature is increased to 950 °C and held for 5 h before naturally cooling to obtain the target product.

[0068] Example 2

[0069] This embodiment provides an oxide solid electrolyte with the chemical formula Li. 1.35 Al 0.5 Ti 1.5 (PO4) 2.85 (SO4) 0.15 Its preparation method includes the following steps:

[0070] 2.8g of C 12 H 28 O4Ti was added to 18 mL of deionized water, and upon stirring, Ti(OH)4 precipitate was immediately formed. After washing and filtering, 8 mL of deionized water was added to the Ti(OH)4 precipitate, followed by 1.75 mL of concentrated HNO3 to generate TiO2. 2+ After the precipitate has completely dissolved, 4.3 g of citric acid stabilizing solution is immediately added. Then, 0.324 g of Li₂CO₃ and 1.23 g of Al(NO₃)₃·9H₂O are added and stirred until completely dissolved. Then, 2.15 g of NH₄H₂PO₄ and 0.108 g of Li₂SO₄ are added and stirred for half an hour to form a sol. The sol is then dried at 150 °C for 12 h. The dried material is then placed in a ball mill jar and wet-milled with a ball ratio of 1:10 and an appropriate amount of alcohol. The ball milling speed is 400 r / min and the milling time is 24 h. The ball-milled sample is then dried, ground, and pressed into tablets. The tablets are placed in an alumina crucible and sintered in a muffle furnace. The temperature is increased to 600 °C at a heating rate of 10 °C / min and held for 1 h. Then, the temperature is increased to 950 °C and held for 5 h before naturally cooling to obtain the target product.

[0071] Example 3

[0072] This embodiment provides an oxide solid electrolyte with the chemical formula Li. 1.51 Al 0.5 Ti1.5 (PO4) 2.99 (SiO4) 0.01 Its preparation method includes the following steps:

[0073] 2.8g of C 12 H 28 O4Ti was added to 18 mL of deionized water, and upon stirring, Ti(OH)4 precipitate was immediately formed. After washing and filtering, 8 mL of deionized water was added to the Ti(OH)4 precipitate, followed by 1.75 mL of concentrated HNO3 to generate TiO2. 2+ After the precipitate has completely dissolved, 4.3 g of citric acid stabilizing solution is immediately added. Then, 0.392 g of Li₂CO₃ and 1.23 g of Al(NO₃)₃·9H₂O are added, and after complete dissolution by stirring, 2.258 g of NH₄H₂PO₄ and 0.0079 g of Li₄SiO₄ are added, and the mixture is stirred for half an hour to form a sol. The sol is then dried at 150 °C for 12 h. The dried material is then placed in a ball mill jar and wet-milled at a bead ratio of 1:10 with an appropriate amount of alcohol added. The parameters are set to 400 rpm and 24 h. The ball-milled sample is then dried, ground, and pressed into tablets. The tablets are placed in an alumina crucible and sintered in a muffle furnace. The temperature is increased to 600 °C at a rate of 10 °C / min and held for 1 h. The temperature is then increased to 950 °C and held for 5 h before natural cooling to obtain the target product.

[0074] Example 4

[0075] This embodiment provides an oxide solid electrolyte with the chemical formula Li. 1.53 Al 0.5 Ti 1.5 (PO4) 2.97 (SiO4) 0.03 Its preparation method includes the following steps:

[0076] 2.8g of C 12 H 28 O4Ti was added to 18 mL of deionized water, and upon stirring, Ti(OH)4 precipitate was immediately formed. After washing and filtering, 8 mL of deionized water was added to the Ti(OH)4 precipitate, followed by 1.75 mL of concentrated HNO3 to generate TiO2. 2+After the precipitate has completely dissolved, 4.3 g of citric acid stabilizing solution is immediately added. Then, 0.376 g of Li₂CO₃ and 1.23 g of Al(NO₃)₃·9H₂O are added, and after complete dissolution by stirring, 2.243 g of NH₄H₂PO₄ and 0.0236 g of Li₄SiO₄ are added, and the mixture is stirred for half an hour to form a sol. The sol is then dried at 150 °C for 12 h. The dried material is then placed in a ball mill jar and wet-milled at a bead ratio of 1:10 with an appropriate amount of alcohol added. The parameters are set to 400 rpm and 24 h. The ball-milled sample is then dried, ground, and pressed into tablets. The tablets are placed in an alumina crucible and sintered in a muffle furnace. The temperature is increased to 600 °C at a rate of 10 °C / min and held for 1 h. The temperature is then increased to 950 °C and held for 5 h before natural cooling to obtain the target product.

[0077] Example 5

[0078] This embodiment provides an oxide solid electrolyte with the chemical formula Li. 1.55 Al 0.5 Ti 1.5 (PO4) 2.95 (SiO4) 0.05 Its preparation method includes the following steps:

[0079] 2.8g of C 12 H 28 O4Ti was added to 18 mL of deionized water, and upon stirring, Ti(OH)4 precipitate was immediately formed. After washing and filtering, 8 mL of deionized water was added to the Ti(OH)4 precipitate, followed by 1.75 mL of concentrated HNO3 to generate TiO2. 2+ After the precipitate has completely dissolved, 4.3 g of citric acid stabilizing solution is immediately added. Then, 0.36 g of Li₂CO₃ and 1.23 g of Al(NO₃)₃·9H₂O are added, and after complete dissolution by stirring, 2.228 g of NH₄H₂PO₄ and 0.039 g of Li₄SiO₄ are added, and the mixture is stirred for half an hour to form a sol. The sol is then dried at 150 °C for 12 h. The dried material is then placed in a ball mill jar and wet-milled at a bead ratio of 1:10 with an appropriate amount of alcohol added. The parameters are set to 400 rpm and 24 h. The ball-milled sample is then dried, ground, and pressed into tablets. The tablets are placed in an alumina crucible and sintered in a muffle furnace. The temperature is increased to 600 °C at a rate of 10 °C / min and held for 1 h. The temperature is then increased to 950 °C and held for 5 h before natural cooling to obtain the target product.

[0080] Example 6

[0081] This embodiment provides an oxide solid electrolyte with the chemical formula Li. 1.5 Al 0.5 Ti 1.5(PO4)3, its preparation method includes the following steps:

[0082] 2.8g of C 12 H 28 O4Ti was added to 18 mL of deionized water, and upon stirring, Ti(OH)4 precipitate was immediately formed. After washing and filtering, 8 mL of deionized water was added to the Ti(OH)4 precipitate, followed by 1.75 mL of concentrated HNO3 to generate TiO2. 2+ After the precipitate has completely dissolved, 4.3 g of citric acid stabilizing solution is immediately added. Then, 0.4 g of Li₂CO₃ and 1.23 g of Al(NO₃)₃·9H₂O are added and stirred until completely dissolved. Then, 2.267 g of NH₄H₂PO₄ is added and stirred for half an hour to form a sol. The sol is then dried at 150 °C for 12 h. The dried material is then placed in a ball mill jar and wet-milled with a ball ratio of 1:10 and an appropriate amount of alcohol. The ball milling speed is 400 r / min and the milling time is 24 h. The milled sample is then dried, ground, and pressed into tablets. The tablets are placed in an alumina crucible and sintered in a muffle furnace. The temperature is increased to 600 °C at a heating rate of 10 °C / min and held for 1 h. Then, the temperature is increased to 950 °C and held for 5 h before naturally cooling to obtain the target product.

[0083] Comparative Example

[0084] This comparative example provides an oxide solid electrolyte with the chemical formula LiTi2(PO4)3, and its preparation method includes the following steps:

[0085] 3.73g of C 12 H 28 O4Ti was added to 18 mL of deionized water, and upon stirring, Ti(OH)4 precipitate was immediately formed. After washing and filtering with water, 11 mL of deionized water was added to the Ti(OH)4 precipitate, followed by 2.33 mL of concentrated HNO3 to generate TiO2. 2+ After the precipitate has completely dissolved, 5.7 g of citric acid stabilizing solution is immediately added. Then, 0.27 g of Li₂CO₃ is added, and after stirring until completely dissolved, 2.267 g of NH₄H₂PO₄ is added. After stirring for half an hour, a sol is formed. The sol is then dried at 150 °C for 12 h. The dried material is then placed in a ball mill jar and wet-milled with an appropriate amount of alcohol at a bead ratio of 1:10. The ball milling speed is 400 r / min, and the milling time is 24 h. The milled sample is then dried, ground, and pressed into tablets. The tablets are placed in an alumina crucible and sintered in a muffle furnace. The temperature is increased to 600 °C at a heating rate of 10 °C / min and held for 1 h. Then, the temperature is increased to 950 °C and held for 5 h before naturally cooling to obtain the target product.

[0086] The preparation methods of the above embodiments and comparative examples are basically the same, the difference being that the prepared oxide solid electrolytes are different. For some parameters, please refer to Table 1.

[0087] Table 1 shows the oxide solid electrolytes prepared in the examples and comparative examples.

[0088] Experimental Example 1

[0089] I. In this experimental example, the molecular structures of the oxide solid electrolytes prepared in Examples 1-2 and 6 were determined. Figure 1 shows the molecular structure of Li. 1.5 Al 0.5 Ti 1.5 (PO4)3 doped SO4 2- XRD patterns before and after, Figure 2 shows Li 1.5 Al 0.5 Ti 1.5 (PO4)3-doped SiO4 4- Please refer to Figure 1 and Figure 2 for the XRD patterns before and after.

[0090] As shown in Figure 1, by comparing the XRD diffraction peak positions of the doped sample and the original sample, we can see that the doped SO4 2- This causes the diffraction peaks to shift towards a direction with a larger 2θ, and the shift increases with the doping ratio. This is because SO4 2- The ionic radius is smaller than that of PO4. 3- The ionic radius of SO4 2- Replace PO4 3- When the position is changed, the cell parameter will decrease, which will increase 2θ, and the corresponding diffraction peak will shift towards the direction where 2θ is larger.

[0091] The EDS elemental analysis in Figure 2 shows that S element is uniformly distributed inside the sample, proving that SO42- 2- Successfully doped with Li 1.5 Al 0.5 Ti 1.5 (PO4)3.

[0092] Figure 3 shows Li 1.5 Al 0.5 Ti 1.5 (PO4)3-doped SiO4 4- Please refer to Figure 3 for the XRD patterns before and after. By comparing the XRD diffraction peak positions of the doped sample and the original sample, it can be seen that the doped SiO4... 4- This causes the diffraction peaks to shift towards a direction with a smaller 2θ, and the shift increases with the doping ratio. This is because SiO4 4- The ionic radius is larger than that of PO4. 3- The ionic radius of SiO44- Replace PO4 3- When the position is changed, the cell parameter increases, which in turn makes 2θ smaller, and the corresponding diffraction peak will shift towards the direction where 2θ is smaller.

[0093] Figure 4 shows LiTi2(PO4)3 doped with Al 3+ Please refer to Figure 4 for the XRD patterns before and after. By comparing the XRD diffraction peak positions of the doped sample and the original sample, it can be seen that the doped Al... 3+ This causes the diffraction peaks to shift towards a direction with a larger 2θ, and the shift increases with the doping ratio. This is because Al 3+ The ionic radius is smaller than that of Ti. 4+ The ionic radius when Al 3+ Replace Ti 4+ When the position is changed, the cell parameter will decrease, which will increase 2θ, and the corresponding diffraction peak will shift towards the direction where 2θ is larger.

[0094] Experimental Example 2

[0095] I. In this experimental example, the oxide solid electrolytes prepared in Examples 1-6 and the comparative examples were subjected to ionic conductivity and electrochemical impedance tests.

[0096] The determination of ionic conductivity involved performing electrochemical impedance spectroscopy (EIS) on the solid electrolyte at 20°C intervals within a temperature range of 25-120°C. After each temperature change, the test mold was kept at that temperature for 1 hour to ensure electrolyte temperature stability. Once the impedance of the solid electrolyte was measured, its ionic conductivity at different temperatures was calculated using formula 1-1.

[0097] Where σ is the ionic conductivity (S cm⁻¹) -1 ), d and S are the thickness (cm) and area (cm²) of the solid electrolyte sheet, respectively. 2 Z is the measured total electrolyte impedance (Ω). After obtaining the lithium-ion conductivity of the solid electrolyte at different temperatures, the activation energy for lithium-ion conduction can be calculated using Arrhenius formula 1-2:

[0098] Where E a Let A0 be the activation energy for lithium-ion conduction, k be the Boltzmann constant, and T be the temperature (K).

[0099] Electrochemical impedance spectroscopy (EIS) is a common technique for measuring the impedance of solid electrolytes. It involves applying small-amplitude alternating current potentials of different frequencies across the solid electrolyte and measuring the change in the phase angle of the impedance as a function of the sinusoidal wave frequency, thus obtaining impedance spectra at different frequencies. The impedance measurement results are displayed using a Nyquist plot, where the x-axis represents the real part of the impedance and the y-axis represents the absolute value of the imaginary part. The impedance Z(w) is given by equation 1-3: Z(w) = Z Re -jZ Im (1-3)

[0100] Z Re Z is the real part of the impedance. Im Let $\frac{\pi}{\pi}$ be the imaginary part of the impedance, and $\pi$ be the phase factor. In this experiment, the impedance spectrum of the solid electrolyte was measured using an EC-lab electrochemical workstation manufactured by Bio-logic, France. The frequency was set to 7 MHz–1 Hz, and the voltage amplitude was 10 mV.

[0101] Please refer to Table 2 for the measurement results of the above items.

[0102] Table 2. Ionic conductivity and impedance test results of the oxide solid electrolytes prepared in the examples and comparative examples.

[0103] As can be seen from Table 2, this disclosure utilizes multiple functional ions to target A. a-b M b X c Ti 2-c Z d P 3-d O 12 Doping of key lattice sites can significantly improve ionic conductivity and reduce impedance.

[0104] Figure 5 shows Li 1.5 Al 0.5 Ti 1.5 (PO4)3 doped SO4 2- Please refer to Figure 5 for the room temperature electrochemical impedance spectroscopy before and after. By comparing the electrochemical impedance of the doped sample and the original sample, it can be seen that with SO4... 2- As the doping ratio increases, the electrochemical impedance continuously decreases, indicating that SO42-... 2- Doping can improve ionic conductivity.

[0105] Figure 6 shows Li 1.5 Al 0.5 Ti 1.5 (PO4)3-doped SiO4 4-Please refer to Figure 6 for the room temperature electrochemical impedance spectroscopy before and after. By comparing the electrochemical impedance of the doped sample and the original sample, it can be seen that with the SiO4... 4- As the doping ratio increases, the electrochemical impedance continuously decreases, indicating that SiO4... 4- Doping can improve ionic conductivity.

[0106] Figure 7 shows LiTi2(PO4)3 doped with Al 3+ Please refer to Figure 7 for the room temperature electrochemical impedance spectroscopy before and after. By comparing the electrochemical impedance of the doped sample and the original sample, it can be seen that with Al... 3+ As the doping ratio increases, the electrochemical impedance continuously decreases, indicating that Al 3+ Doping can improve ionic conductivity.

[0107] The embodiments described above are some, but not all, of the embodiments of this disclosure. The detailed description of the embodiments of this disclosure is not intended to limit the scope of the claimed disclosure, but merely to illustrate selected embodiments of the disclosure. All other embodiments obtained by those skilled in the art based on the embodiments of this disclosure without inventive effort are within the scope of protection of this disclosure. Industrial applicability

[0108] This disclosure significantly improves the ionic conductivity of oxide solid electrolytes at room temperature through the synergistic effect of multi-ion doping, which is beneficial to further improve the electrochemical performance of all-solid-state batteries. The preparation process of oxide solid electrolytes is simple, easy to control, and has good prospects for industrial application.

Claims

1. An oxide solid electrolyte, characterized in that, The chemical formula of the oxide solid electrolyte is A. a-b M b X c Ti 2-c Z d P 3-d O e Where a = 1 to 2, b = 0 to 1, c = 0 to 1, d = 0 to 1.5, e = (12-d) to 12; A includes any one of Li, Na, and K; M includes one or more of Na, K, Rb, Cs, Be, Mg, Ca, Sr, and Ba; X includes one or more of Al, Ga, In, La, Y, Sc, Fe, and Cr; Z includes one or more of B, S, Si, V, Tc, Re, As, Xe, W, Se, Nb, and Mn. Among them, A and M are different, and b, c and d are not all 0 at the same time.

2. The oxide solid electrolyte according to claim 1, characterized in that, The chemical formula of the oxide solid electrolyte is Li a-b M b X c Ti 2-c Z d P 3-d O 12 Wherein, M includes one or more of the elements Na, K, Rb, Cs, Be, Mg, and Ca; X includes one or more of the elements Al, Ga, In, La, Y, Sc, Fe, and Cr; Z includes one or more of the elements S, Si, V, Nb, W, Se, and Mn; or, the chemical formula of the oxide solid electrolyte is Li a-b M b X c Ti 2-c Z d P 3-d O 12-d , where Z includes B.

3. The oxide solid electrolyte according to claim 1, characterized in that, The chemical formula of the oxide solid electrolyte is Na. a-b M b X c Ti 2-c Z d P 3-d O 12 Wherein, M includes one or more of the elements K, Rb, Cs, Be, Mg, and Ca; X includes one or more of the elements Al, Ga, In, La, Y, Sc, Fe, and Cr; Z includes one or more of the elements S, Si, V, Nb, W, Se, and Mn; or, the chemical formula of the oxide solid electrolyte is Na. a-b M b X c Ti 2-c Z d P 3-d O 12-d , where Z includes B.

4. The oxide solid electrolyte according to claim 1, characterized in that, The chemical formula of the oxide solid electrolyte is K. a-b M b X c Ti 2-c Z d P 3-d O 12 Wherein, M includes one or more of Rb, Cs, Be, Mg, and Ca; X includes one or more of Al, Ga, In, La, Y, Sc, Fe, and Cr; Z includes one or more of S, Si, V, Nb, W, Se, and Mn; or, the chemical formula of the oxide solid electrolyte is K. a-b M b X c Ti 2-c Z d P 3-d O 12-d , where Z includes B.

5. The oxide solid electrolyte according to claim 1, characterized in that, The oxide solid electrolyte includes Li a Al c Ti 2-c (PO4) 3-d (ZO4) d Na a Al c Ti 2-c (PO4) 3-d (ZO4) d and K a Al c Ti 2-c (PO4) 3-d (ZO4) d Any one of them; Where a = 1 to 2, c = 0 to 1, d = 0 to 1.5, and Z includes one or more of the elements S, Si, V and Nb.

6. The oxide solid electrolyte according to claim 1, characterized in that, The oxide solid electrolyte includes Li a Al c Ti 2-c (PO4) 3-d (ZO3) d Na a Al c Ti 2-c (PO4) 3-d (ZO3) d and K a Al c Ti 2-c (PO4) 3-d (ZO3) d Any one of the following, where a = 1 to 2, c = 0 to 1, d = 0 to 1.5, and Z includes B.

7. The oxide solid electrolyte according to claim 1, characterized in that, The oxide solid electrolyte includes Li 1.44 Al 0.5 Ti 1.5 (PO4) 2.94 (SO4) 0.06 Li 1.35 Al 0.5 Ti 1.5 (PO4) 2.85 (SO4) 0.15 Li 1.51 Al 0.5 Ti 1.5 (PO4) 2.99 (SiO4) 0.01 Li 1.53 Al 0.5 Ti 1.5 (PO4) 2.97 (SiO4) 0.03 Li 1.55 Al 0.5 Ti 1.5 (PO4) 2.95 (SiO4) 0.05 Li 1.5 Al 0.5 Ti 1.5 (PO4)3, Li 1.5 Al 0.5 Ti 1.5 (PO4) 2.85 (BO3) 0.15 and Li 1.5 Al 0.5 Ti 1.5 (PO4) 2.95 (BO3) 0.05 Any one of them.

8. A method for preparing an oxide solid electrolyte as described in any one of claims 1-7, characterized in that, include: The titanium source compound was mixed with a catalyst and reacted to obtain a product containing TiO2. 2+ The solution was then mixed with a complexing agent, A2CO3, M-source compound, X-source compound, NH4H2PO4, and Z-source compound, and added to the solution containing TiO2. 2+ In a solution, the mixture is stirred to form a sol; after drying the sol, it is then subjected to ball milling, molding, and sintering to obtain the oxide solid electrolyte. Wherein, the M source compound includes MCO3, the X source compound includes XNO3, and the Z source compound includes AZO4 and / or H3BO3; wherein, A includes any one of Li, Na, and K; M includes one or more of Na, K, Rb, Cs, Be, Mg, Ca, Sr, and Ba; X includes one or more of Al, Ga, In, La, Y, Sc, Fe, and Cr; and Z includes one or more of S, B, Si, V, Tc, Re, As, Xe, W, Se, Nb, and Mn.

9. The preparation method according to claim 8, characterized in that, The titanium source compound includes C 12 H 28 O4Ti.

10. The preparation method according to claim 8 or 9, characterized in that, The catalyst includes HNO3.

11. The preparation method according to any one of claims 8-10, characterized in that, The complexing agent includes citric acid.

12. The preparation method according to any one of claims 8-11, characterized in that, The drying process includes: a drying temperature of 100-150℃ and a drying time of 12-24 hours.

13. The preparation method according to any one of claims 8-12, characterized in that, The ball milling process includes a mass ratio of raw material to grinding beads of 1:(5-10).

14. The preparation method according to any one of claims 8-13, characterized in that, The ball milling speed is 300-400 r / min, and the ball milling time is 24-48 h.

15. The preparation method according to any one of claims 8-14, characterized in that, The sintering process includes: first holding at 550-600℃ for 1-3 hours, and then holding at 950-1050℃ for 5-6 hours.

16. The preparation method according to claim 15, characterized in that, The heating rate during the sintering process is 5-10℃ / min.

17. An all-solid-state battery, characterized in that, The oxide solid electrolyte includes any one of claims 1-7 or an oxide solid electrolyte prepared by any one of claims 8-16.

18. An electrical appliance, characterized in that, Including the all-solid-state battery as described in claim 17.

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