A halide oxide solid electrolyte material, and a preparation method and application thereof

Abstract

This invention relates to the field of solid-state battery technology, and in particular to a halide oxide solid electrolyte material, its preparation method, and its application. The halide oxide solid electrolyte provided by this invention is an oxygen-containing halide with both crystalline and amorphous states, and its molecular formula is Li. 3+ x VO x Cl 6‑x Where 0 < x ≤ 2. Multi-step control can precisely regulate the ratio of crystalline to amorphous states in halide oxide solid electrolyte materials, yielding the optimal crystal structure.

Description

Technical Field

[0001] This invention relates to the field of solid-state battery technology, and in particular to a halide oxide solid electrolyte material, its preparation method, and its application. Background Technology

[0002] All-solid-state lithium batteries have become one of the most competitive candidates for next-generation battery systems due to their high energy density, long cycle life, and high safety. The key to developing high-performance all-solid-state lithium batteries lies in preparing solid electrolyte materials with high room-temperature lithium-ion conductivity, a wide electrochemical stability window, and good compatibility with the electrode / electrolyte interface.

[0003] Currently, research on inorganic solid-state electrolyte materials mainly focuses on oxide-type, sulfide-type, and halide-type solid-state electrolytes. Oxide-type solid-state electrolytes exhibit good electrochemical stability, but their rigid lattice leads to poor electrode / electrolyte interface contact, accompanied by low lithium-ion conductivity and high grain boundary impedance, making them unsuitable for high-power-density all-solid-state lithium batteries. Sulfide-type solid-state electrolytes possess room-temperature lithium-ion conductivity comparable to or even exceeding that of liquid electrolytes, but their limited electrochemical stability and structural and interfacial instabilities are bottlenecks restricting their further development. Halide-type solid-state electrolytes can combine the oxidation resistance of oxides with the high ionic conductivity and mechanical ductility of sulfides, and their preparation process is simple, requiring no harsh environment or extremely high sintering temperature, making them very promising for high-performance all-solid-state lithium battery applications.

[0004] Currently, common halides still suffer from insufficient ionic conductivity. To improve ionic conductivity, oxygen doping is typically used to induce amorphization of materials to prepare halide oxides, such as the recently reported Li... 1.2 TaO 1.2 Cl 3.8 Halogen oxide solid electrolytes (J. Phys. Chem. Lett. 2025, 16, 8283−8289) have a room-temperature ionic conductivity as high as 9 mS cm⁻¹. -1 However, this method is only effective for certain specific halides, as reported in the literature (ChemSusChem 2025,00,e202500495). For highly crystalline halides, oxygen doping can actually reduce their room temperature ionic conductivity. Summary of the Invention

[0005] Therefore, the technical problem to be solved by this invention is to overcome the insufficient ionic conductivity in existing technologies, and to precisely control the ratio of crystalline and amorphous states in halide oxide solid electrolyte materials through multi-step control, thereby obtaining an optimal crystal structure. To achieve the above objective, the technical solution adopted by this invention is as follows:

[0006] This invention provides a method for preparing a halide oxide solid electrolyte material, comprising the following steps:

[0007] S11: Under a protective atmosphere, LiCl organic dispersion, Li2O organic dispersion and VCl3 organic dispersion are added to ethyl acetate and reacted at 50-100℃ for 2-8 h to obtain the reaction dispersion; during the reaction, the volume of ethyl acetate is kept constant.

[0008] S12: The reaction dispersion was spray-dried at 180-260℃, then compressed and Joule-thermally synthesized to obtain ceramic sheets;

[0009] S13: The ceramic sheet is ground, pressed, and annealed in a protective atmosphere to obtain the halide oxide solid electrolyte material; the molecular formula of the halide oxide solid electrolyte material is Li. 3+x VO x Cl 6-x , where 0 < x ≤ 2.

[0010] The halide oxide solid electrolyte material is an oxygen-containing halide in which crystalline and amorphous states coexist.

[0011] Preferably, the solvents in the LiCl organic dispersion, Li2O organic dispersion, and VCl3 organic dispersion are all toluene or xylene. Xylene and ethyl acetate are poorly miscible and easily form water-in-oil emulsion droplets.

[0012] Preferably, the protective atmosphere is argon.

[0013] Preferably, the concentration of LiCl in the LiCl organic dispersion is 2-5 mol / L, the concentration of Li2O in the Li2O organic dispersion is 1-3 mol / L, and the concentration of VCl3 in the VCl3 organic dispersion is 1-5 mol / L.

[0014] Preferably, the molar ratio of LiCl, Li2O and VCl3 is 2:1:1.

[0015] Preferably, the volume ratio of the LiCl organic dispersion, Li2O organic dispersion, VCl3 organic dispersion, and ethyl acetate is 1:1:1:4-6. The temperature of the ethyl acetate is controlled at 50-100℃ and is continuously replenished as the ethyl acetate evaporates; after the liquid is added dropwise to the ethyl acetate, a liquid-phase reaction is carried out in the apparatus for up to 2-8 hours.

[0016] Preferably, in step S11, the organic dispersions are added to ethyl acetate using a microfluidic method. During microfluidic operation, the flow rate of the LiCl organic dispersion is 1-20 μL / min, the concentration of the Li₂O organic dispersion is 10-15 μL / min, and the concentration of the VCl₃ organic dispersion is 5-10 μL / min. These three dispersions are introduced into a container filled with ethyl acetate through a unique microfluidic system. The flow rates of the different dispersions vary, and the size of the droplets from the three raw material organic dispersions is adjusted by changing the size of the conduit, thus forming numerous small reaction vessels within the ethyl acetate.

[0017] Preferably, in step S12, the Joule heating current is 8-12 A and the time is 30-150 s.

[0018] Preferably, in step S12, the feed rate for spray drying is 100-500 mL / h. Too low a feed rate results in the atomized droplets remaining in the high-temperature zone for too long, causing premature thermal decomposition or localized sintering of the precursor during drying, forming hard agglomerates. Such powders have a reduced specific surface area, poor compressibility, and may exhibit non-uniform composition.

[0019] Preferably, in steps S12 and S13, the tablet is compressed using hydraulic pressure with a strength of 400-900 MPa.

[0020] Preferably, in step S13, the grinding is carried out by ball milling, with a ball milling speed of 600-800 rpm, a time of 4-8 hours, and a ball-to-material ratio of 30-50:1.

[0021] Furthermore, the ball milling process utilizes a ZrO2 jar containing ZrO2 balls.

[0022] Preferably, in step S13, the annealing temperature is 200-800℃ and the time is 3-15 h. An annealing time that is too short cannot adequately eliminate the stress defects generated in the powder during ball milling, nor can it achieve sufficient grain boundary relaxation and localized structural ordering (localized crystallization). The product retains a high level of amorphous composition or micro-stress, resulting in excessively high grain boundary resistance.

[0023] The present invention also provides a halide oxide solid electrolyte material prepared by the above preparation method.

[0024] Preferably, the molecular formula of the halide oxide solid electrolyte material is Li. 3+x VO x Cl 6-x , where x = 0.05 - 1.9.

[0025] Furthermore, the molecular formula of the halide oxide solid electrolyte material, where x=1, is Li4VOCl5.

[0026] The present invention also provides an all-solid-state lithium battery, wherein the electrolyte of the all-solid-state lithium battery is the halide oxide solid electrolyte material.

[0027] Compared with the prior art, the above-described technical solution of the present invention has the following advantages:

[0028] This invention employs microfluidic technology, which can improve the mixing efficiency of raw materials by adjusting the flow rate ratio and channel size, thus creating a favorable environment for subsequent nucleation and growth and greatly improving the problem of uneven mixing in dry ball milling.

[0029] Meanwhile, this invention uses spray drying to obtain uniform particles, and then rapidly sintersulates them using Joule heating, achieving efficient and controllable generation of amorphous phase materials through instantaneous heating and ultra-rapid cooling.

[0030] The present invention also uses a muffle furnace for secondary sintering. By controlling the sintering time and temperature, the amorphous part of the material is transformed into crystal, and the degree of crystallization of the material can be controlled to obtain the final locally crystallized solid electrolyte. Attached Figure Description

[0031] To make the content of this invention easier to understand, the invention will be further described in detail below with reference to specific embodiments and accompanying drawings.

[0032] Figure 1 This is an ionic conductivity diagram of various embodiments of the present invention, where the horizontal axis is the real part Z' of the impedance at different frequencies, and the vertical axis is the negative number of the real part Z” of the impedance at different frequencies;

[0033] Figure 2 These are the ionic conductivity diagrams of various comparative examples of the present invention. The horizontal axis represents the real part Z' of the impedance at different frequencies, and the vertical axis represents the negative number of the real part Z” of the impedance at different frequencies.

[0034] Figure 3 This is the X-ray diffraction (XRD) pattern of Embodiment 1 of the present invention;

[0035] Figure 4 This is the X-ray diffraction pattern of Embodiment 2 of the present invention;

[0036] Figure 5 This is the X-ray diffraction pattern of Embodiment 3 of the present invention;

[0037] Figure 6 This is the X-ray diffraction pattern of Embodiment 4 of the present invention. Detailed Implementation

[0038] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, so that those skilled in the art can better understand and implement the present invention. However, the embodiments described are not intended to limit the present invention.

[0039] Example 1:

[0040] Step 1: Precise preparation of precursor dispersion

[0041] The operation was performed in an argon-filled glove box (H₂O < 0.1 ppm, O₂ < 0.1 ppm). Using an analytical balance, accurately weigh the following: 8.48 g (0.2 mol) LiCl powder, 2.99 g (0.1 mol) Li₂O powder, and 15.73 g (0.1 mol) VCl₃ powder. Place the weighed LiCl, Li₂O, and VCl₃ into three separate dry glass bottles. Add 100 mL of dry, deoxygenated xylene solvent to each bottle: 100 mL to the LiCl bottle, 100 mL to the Li₂O bottle, and 100 mL to the VCl₃ bottle. Seal the three bottles, remove them from the glove box, and place them on a magnetic stirrer. Stir at 50°C for 12 hours until complete decomposition and a homogeneous dispersion are formed. The concentration of LiCl in the LiCl dispersion is 2 mol / L, the concentration of Li₂O in the Li₂O dispersion is 1 mol / L, and the concentration of VCl₃ in the VCl₃ dispersion is 1 mol / L.

[0042] Step 2: Setup and Operation of the Microfluidic Reaction System

[0043] Setting up a microfluidic reaction apparatus: Three precision syringe pumps are used, each connected to a sealed syringe containing one of the three dispersions described above. The syringe outlets are connected to a three-way mixer via PTFE capillary tubes (0.5 mm inner diameter), and the mixer outlet capillary tube extends to the bottom of the reaction vessel.

[0044] A 1 L four-necked flask was used as the reaction vessel. 500 mL of dry ethyl acetate was added beforehand, and the mixture was heated to a constant temperature of 80°C. A reflux condenser and a constant-pressure dropping funnel were connected to replenish the evaporated solvent. The flow rates of the syringe pumps were set as follows: LiCl-xylene dispersion 10 μL / min, Li₂O-xylene dispersion 10 μL / min, and VCl₃-xylene dispersion 10 μL / min. The three liquid streams instantly formed water-in-oil emulsion droplets within the mixer and were directly added to the heated ethyl acetate. The reaction was continued for 4 hours. During this time, ethyl acetate was slowly added through the dropping funnel to maintain a stable liquid level. After the reaction, a suspension containing a large amount of precursor precipitate was obtained.

[0045] Step 4: Spray drying to prepare uniform precursor powder

[0046] The suspension obtained in step two is directly transferred to the feed tank of the spray dryer. The spray drying parameters are set as follows: inlet temperature 220℃, outlet temperature approximately 100℃, feed rate 300 mL / h, and atomizer speed adjusted according to the equipment to ensure sufficient atomization. The powder at the bottom of the drying tower is collected to obtain a dry, loose precursor powder.

[0047] Step 5: Joule heating rapid synthesis

[0048] Approximately 2 g of the spray-dried powder was placed into a mold with a diameter of 13 mm. Using a hydraulic press, the powder was pressed into a dense ceramic blank disc at 600 MPa for 3 minutes. The disc was then subjected to Joule heat treatment with a current adjusted to 10 A for 90 seconds. After the reaction was complete, a hard ceramic disc was obtained.

[0049] Step Six: High-energy ball milling for refining

[0050] The Joule-synthesized ceramic flakes were initially crushed in a mortar. 5 g of the crushed powder was weighed and placed in a 125 mL zirconia ball mill jar along with 200 g of zirconia (ZrO2) grinding balls (a mixture of 3 mm and 5 mm diameter balls) at a ball-to-powder ratio of 40:1. The jar was sealed and purged three times under an argon atmosphere. The jar was then placed in a planetary ball mill and run at 600 rpm for 4 hours (30-minute runs followed by 10-minute breaks to prevent overheating). After milling, the powder was removed from the glove box, yielding an ultrafine, dark gray powder.

[0051] Step 7: Low-temperature annealing to obtain locally crystalline electrolytes

[0052] Two g of the ball-milled powder was pressed again into discs with a diameter of 13 mm using a hydraulic press at 600 MPa. The discs were placed in an alumina boat and then placed in a tube furnace. High-purity argon gas (50 sccm flow rate) was introduced into the furnace tubes, and after purging for 30 minutes, the temperature was increased to 350°C at a rate of 5°C / min and held at this temperature for 5 hours. After the holding period, the furnace was cooled to room temperature to obtain the final product, Li4VOCl5 electrolyte ceramic discs, which can be ground into powder for characterization.

[0053] Example 2:

[0054] Steps one through four are the same as in Example 1.

[0055] Step 5: Joule heating for rapid synthesis, with the same pressing parameters as in Example 1 (600 MPa). Joule heating parameters: current 12 A, time set to 60 seconds.

[0056] Step 6: High-energy ball milling for finer refining, the same as in Example 1.

[0057] Step 7: Low-temperature annealing to obtain locally crystalline electrolytes, with tableting parameters the same as in Example 1 (600 MPa). Annealing procedure: Under an argon atmosphere, heat to 350°C and hold for 8 hours.

[0058] Example 3:

[0059] The differences from Example 1 are as follows:

[0060] Step 1: Accurately weigh 12.72 g (0.3 mol) LiCl powder, 4.485 g (0.15 mol) Li₂O powder, and 23.595 g (0.15 mol) VCl₃ powder. Disperse and dilute to volume with xylene respectively: LiCl 100 mL (3 mol / L), Li₂O 100 mL (1.5 mol / L), and VCl₃ 100 mL (1.5 mol / L).

[0061] Step 2: Inject the three dispersions into a precision syringe pump, and then into a T-type mixer through a PTFE capillary tube (0.4 mm inner diameter). Set the flow rates as follows: LiCl dispersion 15 μL / min, Li2O dispersion 15 μL / min, VCl3 dispersion 15 μL / min.

[0062] Step 3: The microdroplet mixture is fed into a 1 L reactor containing ethyl acetate, which is maintained at 95°C. The total reaction time is controlled at 2.5 hours. Ethyl acetate is continuously added during this period to maintain the liquid level.

[0063] Step 4: Spray dry the reaction suspension. Parameters set: inlet temperature 250℃, feed rate 450mL / h. Collect the precursor powder.

[0064] Step 5 (Joule heating): Press the precursor powder into tablets at 700 MPa, adjust the current to 11 A, and heat treat for 80 seconds.

[0065] Step 6 (ball milling): ball-to-material ratio 45:1, rotation speed 600 rpm, time 4 hours.

[0066] Step 7 (annealing): Press the tablets at a pressure of 700 MPa and anneal at 350°C for 5 hours in argon atmosphere.

[0067] Example 4:

[0068] The differences from Example 1 are as follows:

[0069] Step 1: Accurately weigh LiCl (4.24 g, 0.1 mol), Li₂O (1.495 g, 0.05 mol), and VCl₃ (7.865 g, 0.05 mol). The molar ratio is LiCl:Li₂O:VCl₃ = 2:1:1. Disperse each component separately with xylene and bring the volume to a final volume: LiCl 100 mL (concentration 1 mol / L), Li₂O 100 mL (concentration 0.5 mol / L), and VCl₃ 100 mL (concentration 0.5 mol / L).

[0070] Step 2: Set the flow rate: 5 μL / min for LiCl dispersion, 5 μL / min for Li2O dispersion, and 5 μL / min for VCl3 dispersion. Use a capillary tube with an inner diameter of 0.3 mm to form smaller droplets.

[0071] Step 3: Maintain the temperature of ethyl acetate in the reaction vessel at 60°C. Control the total reaction time to 7 hours. Slowly and evenly add ethyl acetate.

[0072] Step 4: Spray dry the reaction suspension. Parameters set: inlet temperature 190℃, feed rate 150mL / h. Collect the light green precursor powder.

[0073] Step 5 (Joule heating): Press the precursor powder into tablets at 500 MPa, adjust the current to 9 A, and heat treat for 120 seconds.

[0074] Step 6 (ball milling): ball-to-material ratio 35:1, rotation speed 600 rpm, time 4 hours.

[0075] Step 7 (annealing): anneal at 350°C for 12 hours under argon pressure of 500 MPa.

[0076] Comparative Example 1: Changes in Solvent System (Impact of Key Chemical Environments)

[0077] This invention is basically the same as that of Embodiment 1, with the following differences:

[0078] The only variable that changed was that in steps one and two, the solvent was completely replaced with tetrahydrofuran (THF) instead of xylene.

[0079] Detailed explanation and step adjustments:

[0080] All raw materials (LiCl, Li2O, VCl3) were dispersed using THF, and the concentrations were kept the same as in Example 1.

[0081] The receiving solvent in both the microfluidic system and the reaction vessel remains ethyl acetate. THF and ethyl acetate are highly miscible, which will prevent the stable formation of "water-in-oil" emulsion droplets, causing them to mix instantly into a homogeneous phase.

[0082] Expected Defects and Comparison Objective: Without the "microreactor" isolation effect of the microfluidic droplets, the reaction degenerates into a macroscopic homogeneous precipitation. The expected product precursor has a large particle size and extremely wide distribution, and may form dense aggregates. This will severely affect the subsequent heat treatment kinetics and the microscopic homogeneity of the final electrolyte. This comparison aims to verify the necessity of microfluidic droplet-confined reaction for obtaining nanoscale homogeneous precursors.

[0083] Comparative Example 2: Microfluidic reaction temperature too low

[0084] The only variable that changed was that in step two, the temperature of the ethyl acetate receiving solution was controlled at 40°C.

[0085] Detailed explanation and procedure adjustment: Keep all other parameters (concentration, flow rate, time, etc.) completely consistent with Example 1.

[0086] Expected Defects and Comparison Objective: Excessively low reaction temperatures significantly reduce the kinetic energy of reactant molecules and the reaction rate. This may lead to incomplete precursor precipitation or the formation of large amounts of amorphous, low-activity intermediates. After spray drying, this powder exhibits poor reactivity in subsequent Joule thermal synthesis, making complete conversion to the target crystalline phase difficult. This comparison aims to elucidate the crucial role of sufficient thermodynamic driving force in the formation of a well-reacting precursor.

[0087] Comparative Example 3: Spray drying feed rate is too slow

[0088] This invention is basically the same as Example 3 (high concentration-rapid path), with the following differences:

[0089] The only variable that changed was the spray drying feed rate, which was set to 50 mL / h in step four.

[0090] Detailed instructions and steps: Keep the spray drying inlet temperature constant at 250℃.

[0091] Expected Defects and Comparison Objective: An excessively low feed rate results in prolonged residence time of atomized droplets in the high-temperature zone. This causes premature thermal decomposition or localized sintering of the precursor during drying, leading to hard agglomerates. Such powders exhibit reduced specific surface area, decreased compressibility, and potentially non-uniform composition. This comparative example aims to demonstrate the impact of spray drying kinetics (drying rate) on powder physical properties and subsequent process adaptability.

[0092] Comparative Example 4: Insufficient Joule thermoelectric current

[0093] This invention is basically the same as Embodiment 2, with the following differences:

[0094] The only variable changed: In step five, the current was set to 6 A, and to ensure fairness in the comparison, the synthesis time was extended to 200 seconds.

[0095] Detailed explanation and step adjustment: The same pressed precursor discs as in Example 2 were used for comparison.

[0096] Expected drawbacks and comparative purpose: A low Joule heating current is unlikely to induce a strong Joule heating effect in a short time. Even with extended heating time, the overall thermal effect may be insufficient or the heating rate too slow, leading to incomplete solid-state reaction and hindering the target Li... 3+x VO x Cl 6-x The low phase content and poor grain development result in significantly lower densification and crystallinity compared to short-time rapid synthesis at optimized power. This comparison aims to verify the superiority of the "high power-short time" mode in Joule thermal synthesis for achieving rapid and complete phase transformation.

[0097] Comparative Example 5: Insufficient annealing time

[0098] This invention is basically the same as that of Embodiment 1, with the following differences:

[0099] The only variable that changed: In step seven, the annealing time was shortened to 1 hour.

[0100] Detailed explanation and procedure adjustment: The annealing temperature, atmosphere and all other preliminary steps are consistent with those in Example 1.

[0101] Expected Defects and Comparison Objective: Insufficiently short annealing times cannot adequately eliminate stress defects generated during ball milling, nor can they achieve sufficient grain boundary relaxation and localized structural ordering (localized crystallization). The product retains high levels of amorphous components or micro-stress, leading to excessively high grain boundary resistance. This comparison aims to emphasize the importance of sufficient heat treatment time for obtaining a "locally crystalline" electrolyte structure with low grain boundary resistance and high ion mobility.

[0102] To verify the intrinsic ionic conductivity performance of the halide oxide and its suitability in all-solid-state batteries, the solid electrolytes prepared in Examples 1-4 and Comparative Examples 1-5 were subjected to electrochemical impedance spectroscopy (EIS) tests, and all-solid-state batteries were fabricated and their electrochemical performance was tested.

[0103] EIS Test: 100 mg of solid electrolyte was weighed and poured into a mold cylinder. Stainless steel columns were added on both sides as positive / negative current collectors and components for pressing the sample. After adding the stainless steel mold, the entire mold was placed on a press and pressed to 3.5 t for 3 minutes. After pressing, an EIS test was performed, and the test results are as follows. Figure 1 , Figure 2 As shown in Table 1.

[0104] All-solid-state battery electrochemical performance testing: The negative electrode uses a lithium indium sheet of appropriate size, and the positive electrode uses the above-mentioned solid electrolyte powder and NCM811 powder (lithium nickel cobalt manganese oxide LiNi). 0.8 Co 0.1 Mn 0.1 O2 (a ternary layered oxide cathode material, CAS number 179802-95-0) is a mixture of O2 and O2 in a 3:7 ratio.

[0105] First, 60 mg of electrolyte powder was weighed and poured into a mold, and pressed into a sheet under a pressure of 2 t for 3 min. Then, the mold was opened, and 40 mg of lithium phosphorus sulfur chloride (Li6PS5Cl, CAS number 179707-73-3) was weighed and poured into the mold from the same side, and pressed into a sheet under a pressure of 2.5 t for 3 min. Next, the mold was opened, and the mass of the mixture of solid electrolyte powder and NCM811 powder was weighed and recorded, not exceeding 5 mg. This mixture was poured into the center of the mold from the positive electrode side, and then pressed under a pressure of 3.5 t for 3 min. The mold was opened, and a lithium indium sheet was placed on the negative electrode side, and pressed under a pressure of 1.5 t for 3 min. Then, a stainless steel mold was added, and the entire mold was placed on a press for pressing at a pressure of 1.5 t. The mold fixing screws were tightened during pressing. After tightening, the assembly was completed, and a long-cycle test was then performed. The test results are shown in Table 2.

[0106] The test results above show that the battery assembled using the halide oxide solid electrolyte of the present invention as the positive electrode side solid electrolyte has high initial efficiency, long cycle life and high capacity retention, that is, it has excellent battery cycle characteristics.

[0107] Table 1 Ionic conductivity of each embodiment and comparative example

[0108]

[0109] Table 2. Cyclic Results of Each Embodiment and Comparative Example

[0110]

[0111] The crystallinity test method in Table 3 is as follows: After mixing the example sample with LiF at a mass ratio of 1:1, X-ray diffraction test is performed. Figures 3 to 6 The crystallinity percentage of the test results was determined using the Rietveld method, as shown in the following formula:

[0112]

[0113] Where α is the crystallinity, W c W is the weight of the crystal. std W is the weight of LiF. c / Wstd Obtained by the Rietveld method, where W is the total weight.

[0114] Table 3 Crystallinity of samples from each example

[0115]

[0116] 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 of producing a halide-oxide solid state electrolyte material, characterized by, Includes the following steps: S11: Under a protective atmosphere, LiCl organic dispersion, Li2O organic dispersion and VCl3 organic dispersion are added to ethyl acetate and reacted at 50-100℃ for 2-8 h to obtain the reaction dispersion; during the reaction, the amount of ethyl acetate is kept constant. S12: The reaction dispersion is spray-dried at 180-260℃, then compressed and Joule-thermally synthesized to obtain ceramic sheets; S13: The ceramic sheet is ground, pressed, and annealed in a protective atmosphere to obtain the halide oxide solid electrolyte material; the molecular formula of the halide oxide solid electrolyte material is Li. 3+x VO x Cl 6-x Where 0 < x ≤ 2; the solvents in the LiCl organic dispersion, Li2O organic dispersion and VCl3 organic dispersion are all toluene or xylene; in step S12, the Joule thermal synthesis current is 8-12 A, the time is 30-150 s, and the feed rate of spray drying is 100-500 mL / h; in step S13, the annealing temperature is 200-800℃, and the time is 3-15 h.

2. The method of claim 1, wherein: The concentration of LiCl in the LiCl organic dispersion is 2-5 mol / L, the concentration of Li2O in the Li2O organic dispersion is 1-3 mol / L, and the concentration of VCl3 in the VCl3 organic dispersion is 1-5 mol / L.

3. The method of claim 1, wherein: The volume ratio of the LiCl organic dispersion, Li2O organic dispersion, VCl3 organic dispersion and ethyl acetate is 1:1-2:1-2:4-6.

4. The method of claim 1, wherein: In step S11, the organic dispersion is added to ethyl acetate using a microfluidic method. During microfluidic operation, the flow rate of the LiCl organic dispersion is 1-20 μL / min, the concentration of the Li2O organic dispersion is 10-15 μL / min, and the concentration of the VCl3 organic dispersion is 5-10 μL / min.

5. A halide oxide solid electrolyte material prepared by the preparation method according to any one of claims 1-4.

6. An all-solid-state lithium battery, characterized by: The electrolyte of the all-solid-state lithium battery is the halide oxide solid electrolyte material as described in claim 5.

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