High-entropy alloy composite solid electrolyte and preparation method thereof

Abstract

The invention relates to the technical field of solid electrolyte, and provides high-entropy alloy composite solid electrolyte and a preparation method thereof. The preparation method of the high-entropy alloy composite solid electrolyte comprises the following steps: S1, taking a carbon source, and carrying out first heat treatment to obtain graphite carbon nitride; grinding and mixing the graphite carbon nitride and cobalt powder, carrying out secondary heat treatment, soaking in an acid solution, washing, and drying to obtain a nitrogen-doped hollow porous carbon cage; s2, a metal compound is taken and dissolved in a solvent, the nitrogen-doped hollow porous carbon cage is added for mixing, drying and heat treatment, and a high-entropy alloy precursor is obtained; s3, acetonitrile, polyethylene oxide, lithium salt and the high-entropy alloy precursor are mixed, poured and dried, and the high-entropy alloy composite solid electrolyte is obtained. According to the technical scheme, the problems that the electrochemical performance of the high-entropy alloy composite solid electrolyte is insufficient and the mechanical performance of an electrolyte membrane is poor in the prior art are solved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of solid electrolyte, in particular, to a high-entropy alloy composite solid electrolyte and a preparation method thereof. BACKGROUND

[0002] In the prior art, the research mainly focuses on the basic application and performance of high-entropy alloy, and does not deeply explore the influence of high-entropy effect on polymer electrolyte film, such as: In the patent application with publication number CN113097563A, the prepared high-entropy alloy electrolyte mainly discloses its surface characteristics and basic method, without deeply exploring the micro-mechanism of the high-entropy alloy for improving the electrochemical performance of the composite solid electrolyte; In the patent application with publication number CN116895811A, the research mainly focuses on a certain electrochemical performance, which has low application generalization ability and does not highlight the improvement of electrolyte diaphragm interface compatibility; In the patent application with publication number CN117895182A, the prepared high-entropy alloy diaphragm describes a simple application under the micro-mechanism, without highlighting the improvement of mechanical performance under actual conditions and the toughness of hard brittleness; In the patent application with publication number CN119050461A, the prepared composite electrolyte has excellent cycle performance and good diaphragm thickness, but the impedance is high, which will generate a large amount of heat in the actual lithium battery application, and does not highlight the actual application scheme; In the patent application with publication number CN117254209A, the composite electrolyte film synthesis method is quite controllable according to the demand, but lacks the highlight of mechanical performance and electrochemical ability.

[0003] Therefore, the existing high-entropy alloy composite solid electrolyte still has the problems of insufficient electrochemical performance and poor mechanical performance of electrolyte film. SUMMARY

[0004] The present application provides a high-entropy alloy composite solid electrolyte and a preparation method thereof, which solves the problem of insufficient electrochemical performance and poor mechanical performance of electrolyte film in the related art.

[0005] The technical scheme of the present application is as follows: The present application provides a preparation method of a high-entropy alloy composite solid electrolyte, comprising the following steps: S1, a carbon source is subjected to first heat treatment to obtain graphite carbon nitride; the graphite carbon nitride is mixed with cobalt powder by grinding, subjected to second heat treatment, soaked in an acid solution, washed, dried, and a nitrogen-doped hollow porous carbon cage is obtained; S2. Dissolve the metal compound in a solvent, add the nitrogen-doped hollow porous carbon cage for mixing, dry, and heat treat to obtain a high-entropy alloy precursor. S3. Acetonitrile, polyethylene oxide, lithium salt and the high-entropy alloy precursor are mixed, cast and dried to obtain a high-entropy alloy composite solid electrolyte.

[0006] As a further technical solution, the soaking time in the acid solution is 8-16 hours, preferably 10-12 hours, and more preferably 12 hours.

[0007] As a further technical solution, when the metal compound is dissolved in the solvent, the dissolution and mixing time is 10-60 min, preferably 10-30 min, and more preferably 20 min.

[0008] As a further technical solution, the first heat treatment includes a first heat treatment stage and a second heat treatment stage in sequence; The first stage of heat treatment involves heating to 500-620°C at a heating rate of 4-6°C / min, holding at that temperature for 2-6 hours, and then cooling to room temperature. The second heat treatment involves heating to 500-550℃ at a heating rate of 4-6℃ / min and holding at that temperature for 2-3 hours.

[0009] As a further technical solution, the second heat treatment is carried out in a nitrogen atmosphere, heated to 800-820°C at a heating rate of 1-4°C / min, held at that temperature for 2-3 hours, and then cooled to room temperature.

[0010] As a further technical solution, the mass ratio of the graphite carbon nitride to the cobalt powder is 1:0.8~1.2; Preferably, the mass ratio of the graphitic carbon nitride to the cobalt powder is 1:1; The acid solution includes a hydrochloric acid solution, and the molar mass ratio of the hydrochloric acid solution to the carbon source is 1 mol: 40~50 g.

[0011] As a further technical solution, the molar mass ratio of the metal compound and the nitrogen-doped hollow porous carbon cage is 1 mmol: 0.02~0.05 g.

[0012] As a further technical solution, in step S2, the heat treatment is carried out at a heating rate of 3~8℃ / min to 580~620℃, held at that temperature for 2~3 hours, and then cooled to room temperature.

[0013] As a further technical solution, the mass ratio of acetonitrile to polyethylene oxide is 30~40:4; The mass of the high-entropy alloy precursor is 5% to 15% of the mass of the polyethylene oxide, preferably 10%.

[0014] As a further technical solution, the molar ratio of the ethylene oxide repeating units of the polyethylene oxide to the lithium ions in the lithium salt is 16-20:1, for example, it can be 16:1, 18:1, 20:1.

[0015] In the present application, the molar ratio of the ethylene oxide repeating units of the polyethylene oxide to the lithium ions in the lithium salt (EO:Li) is controlled to be 16-20:1, because in the case of less than EO:Li=16:1, the amorphous region of the separator is destroyed and leads to ion aggregation, and in the case of more than EO:Li=20:1, it leads to a significant decrease in conductivity and poor flexibility of the separator.

[0016] As a further technical solution, the lithium salt includes lithium bis-trifluoromethanesulfonimide.

[0017] As a further technical solution, the metal compound includes an acetylacetone metal compound, and the acetylacetone metal compound includes Fe(AcAc)3, Co(AcAc)3, Ni(AcAc)2, Mn(AcAc)3, Zn(AcAc)2.

[0018] The innovative design provides unique advantages for solid-state electrolytes, creates a multi-component synergistic environment by introducing multiple metal elements such as iron, cobalt, nickel, significantly improves the stability of the material and forms a high-entropy effect, and adjusts the proportion of each metal element to optimize the ion conductivity and life of the electrolyte and forms an organic-inorganic composite electrolyte with high-entropy alloy, which has both energy storage particle conduction and flexibility.

[0019] The present application also provides a high-entropy alloy composite solid-state electrolyte prepared by the preparation method.

[0020] The working principle and beneficial effects of the present application are as follows: In the present application, by optimizing the internal structure of the solid-state electrolyte, the multi-component effect and diffusion delay effect are synergistically used to improve ion diffusion and flexible stress and strain, the acetonitrile solvent containing high-entropy alloy is added, the content of high-entropy material is controlled, and the viscosity of the polyethylene oxide slurry is adjusted, so that the precise control of the viscoelasticity of the high-entropy alloy filler solution and the design of the new solid-state electrolyte are realized.

[0021] The multi-element synergistic effect of the metal compound of the high-entropy alloy enables it to maintain high mechanical properties under repeated stress. The existing patent only studies the electrochemical performance of the electrolyte, and does not involve the research on the improvement of ion conduction and mechanical properties by high-entropy alloy. The design of the composite electrolyte enables it to adapt to the volume change of the electrode material during charging and discharging, and reduces the interfacial stress. BRIEF DESCRIPTION OF DRAWINGS

[0022] The present invention will now be described in further detail with reference to the accompanying drawings and specific embodiments.

[0023] Figure 1 This is a comparison image of the high-entropy alloy solution before and after mixing and drying in Example 1 of the present invention; Figure 2 This is a comparison image of the high-entropy alloy composite product of Example 1 of the present invention before and after sintering at 600℃; Figure 3 This is a diagram illustrating the process from slurry to coating of the high-entropy alloy composite solid electrolyte membrane prepared in Example 1 of the present invention. Figure 4 This is a scanning electron microscope image of the high-entropy alloy composite solid electrolyte prepared in Example 1 of the present invention; Figure 5 A Schematic diagram of the Arrhenius structure of a pure PEO-based membrane and a high-entropy alloy composite solid electrolyte membrane prepared in Example 1 of this invention. Figure 6 The above are EIS spectra of the high-entropy alloy composite solid electrolyte membranes prepared in Examples 1 and 6-7 of this invention. Figure 7 The tensile properties of the pure PEO-based membrane and the high-entropy alloy composite solid electrolyte membrane prepared in Example 1 of this invention are shown in the diagram. Detailed Implementation

[0024] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0025] In the following examples and comparative examples, the lithium salt is lithium bis(trifluoromethanesulfonate)imide; EO:Li refers to the molar ratio of the repeating ethylene oxide unit of the polyethylene oxide to the lithium ions in the lithium salt.

[0026] Example 1 The preparation method of high-entropy alloy composite solid electrolyte includes the following steps: S1. Preparation of nitrogen-doped hollow porous carbon cages (NC) 45g of urea was placed in a ceramic container and placed in a muffle furnace. The heating rate was preferably 5℃ / min, and the temperature was raised to 550℃. The holding time was 4h. After cooling to room temperature, the temperature was raised to 530℃ at the same heating rate and held for 2.5h to complete the secondary heat treatment and obtain graphite carbon nitride. S2, graphite carbon nitride and cobalt powder were ground at a mass ratio of 1:1, mixed uniformly, and then placed in a ceramic canister and put into a tube furnace, heated to 800°C at a heating rate of 2°C / min under nitrogen protection, and kept for 2h, and then taken out after cooling to room temperature; S3, the obtained black powder was soaked in 1mol hydrochloric acid for 12h, and washed with deionized water until neutral, to obtain a nitrogen-doped hollow porous carbon cage, named NC-800°C; S4, mixing FeCoNiMnZn with the solution of nitrogen-doped hollow porous carbon cage (NC) Five metal compounds (Fe(AcAc)3, Co(AcAc)3, Ni(AcAc)2, Mn(AcAc)3, Zn(AcAc)2) were dissolved in DMF at a weight of 1mmol, stirred at low speed for 20min, 0.035g nitrogen-doped hollow porous carbon cage (NC) was added and stirred again for 20min, to obtain a high-entropy alloy precursor solution; S5, preparation of high-entropy alloy precursor The above prepared solution was placed in a beaker and put into a vacuum oven (temperature 40°C) for 6h, until it was dried (high-entropy alloy solution before and after drying, as shown in Figure 1 The precursor was put into a tube furnace, and the temperature was raised to 600°C at a heating rate of 5°C / min and kept for 2h, and finally naturally cooled to room temperature, to obtain a composite product of FeCoNiMnZn high-entropy alloy and nitrogen-doped hollow carbon cage (composite product of high-entropy alloy and nitrogen-doped hollow carbon cage before and after sintering at 600°C, as shown in Figure 2 ); S6, preparation of composite solid electrolyte The stirring paddle and stirrer were connected, a capacity of 45mL acetonitrile was placed in a three-hole flask, 4g polyethylene oxide (PEO) was added to the flask, and a mass fraction of 10wt% FeCoNiMnZn high-entropy alloy and nitrogen-doped hollow carbon cage composite product was taken, lithium salt (EO:Li=18:1) was added, and stirred for 12h, the polymer solution was poured on a polytetrafluoroethylene plate, dried, and cut to obtain a high-entropy alloy composite solid electrolyte (high-entropy alloy composite solid electrolyte film from slurry to coating process display, as shown in Figure 3 ; the scanning electron microscope image of the high-entropy alloy composite solid electrolyte is shown in Figure 4 ).

[0027] Example 2 The preparation method of the high-entropy alloy composite solid electrolyte comprises the following steps: S1, preparation of nitrogen-doped hollow porous carbon cage (NC) Put 40g urea in the porcelain and place it in the muffle furnace, the heating rate is preferably 4℃ / min, heat to 500℃, the holding time is preferably 6h, after cooling to room temperature, heat to 500℃ at the same heating rate and hold for 3h, complete the second heat treatment, and obtain graphite carbon nitride; S2, graphite carbon nitride and cobalt powder are ground at a mass ratio of 1:0.8, mixed uniformly, placed in a ceramic square canister, and placed in a tube furnace, heated to 810℃ at a heating rate of 1℃ / min under nitrogen protection, and held for 2.5h, and then taken out after cooling to room temperature; S3, the obtained black powder is soaked in 1mol hydrochloric acid for 8h, and washed with deionized water until neutral, to obtain nitrogen-doped hollow porous carbon cage, named NC-810℃; S4, mixing FeCoNiMnZn with nitrogen-doped hollow porous carbon cage (NC) solution Five metal compounds (Fe(AcAc)3, Co(AcAc)3, Ni(AcAc)2, Mn(AcAc)3, Zn(AcAc)2) are dissolved in DMF at a weight of 1mmol, stirred at low speed for 10min, 0.02g nitrogen-doped hollow porous carbon cage (NC) is added, and stirred again for 20min, to obtain high-entropy alloy precursor solution; S5, preparation of high-entropy alloy precursor The above prepared solution is placed in a beaker and placed in a vacuum oven (temperature 40℃) for 6h, until it is dried, the precursor is placed in a tube furnace, heated to 600℃ at a heating rate of 4℃ / min, and held for 3h, and finally naturally cooled to room temperature, to obtain the composite product of FeCoNiMnZn high-entropy alloy and nitrogen-doped hollow carbon cage; S6, preparation of composite solid electrolyte Connect the stirring paddle and the stirrer, and place 40mL of acetonitrile in a three-hole flask, add 4g of polyethylene oxide (PEO) to the flask, and take 10wt% of the composite product of FeCoNiMnZn high-entropy alloy and nitrogen-doped hollow carbon cage, add lithium salt (EO:Li=18:1), stir for 12h, pour the polymer solution onto a polytetrafluoroethylene plate, dry, and cut to obtain a high-entropy alloy composite solid electrolyte.

[0028] Example 3 The preparation method of the high-entropy alloy composite solid electrolyte comprises the following steps: S1, preparation of nitrogen-doped hollow porous carbon cage (NC): Put 50g urea in porcelain and place it in a muffle furnace, the heating rate is preferably 6℃ / min, heat to 620℃, the holding time is preferably 2h, after cooling to room temperature, heat to 550℃ at the same heating rate, hold for 2h, complete the second heat treatment, and obtain graphite carbon nitride; S2, graphite carbon nitride and cobalt powder are ground in a mass ratio of 1:1.2, mixed uniformly, placed in a ceramic capsule, and placed in a tube furnace, heated to 820℃ at a heating rate of 4℃ / min under nitrogen protection, and held for 2h, and then taken out after cooling to room temperature; S3, the obtained black powder is soaked in 1mol hydrochloric acid for 16h, and washed with deionized water until neutral, to obtain nitrogen-doped hollow porous carbon cage, named NC-820℃; S4, mixing FeCoNiMnZn with the solution of nitrogen-doped hollow porous carbon cage (NC) Five metal compounds (Fe(AcAc)3, Co(AcAc)3, Ni(AcAc)2, Mn(AcAc)3, Zn(AcAc)2) are dissolved in DMF at a weight of 1mmol, stirred at low speed for 20min, 0.05g nitrogen-doped hollow porous carbon cage (NC) is added, and stirred again for 20min, to obtain a high-entropy alloy solution; S5, preparation of high-entropy alloy precursor The above prepared solution is placed in a beaker and placed in a vacuum oven (temperature 40℃) for 6h, until it is dried, the precursor is placed in a tube furnace, heated to 600℃ at a heating rate of 6℃ / min, held for 1h, and finally naturally cooled to room temperature, to obtain a composite product of FeCoNiMnZn high-entropy alloy and nitrogen-doped hollow carbon cage; S6, preparation of composite solid electrolyte Connect the stirring paddle and the stirrer, place 50mL of acetonitrile in a three-hole flask, add 4g of polyethylene oxide (PEO) to the flask, and take 10wt% of the composite product of FeCoNiMnZn high-entropy alloy and nitrogen-doped hollow carbon cage, add lithium salt (EO:Li=18:1), stir for 12h, pour the polymer solution onto a polytetrafluoroethylene plate, dry, and cut to obtain a high-entropy alloy composite solid electrolyte.

[0029] Example 4 The difference between this example and Example 1 is only that EO:Li=16:1.

[0030] Example 5 The difference between this example and Example 1 is only that EO:Li=20:1.

[0031] Example 6 The difference between the present embodiment and embodiment 1 is only that the mass fraction of the composite product of the FeCoNiMnZn high-entropy alloy and the nitrogen-doped hollow carbon cage is 5wt%.

[0032] Embodiment 7 The difference between the present embodiment and embodiment 1 is only that the mass fraction of the composite product of the FeCoNiMnZn high-entropy alloy and the nitrogen-doped hollow carbon cage is 15wt%.

[0033] Experimental example The Arrhenius diagram of the pure PEO-based film and the high-entropy alloy composite solid-state electrolyte (PHEA) added with the composite product (HEA) of the high-entropy alloy and the nitrogen-doped hollow carbon cage prepared in embodiment 1 is shown in Figure 5 The EIS diagrams of embodiments 1, 6-7 are shown in Figure 6 . Figure 5 The Arrhenius diagram and the EIS diagram of the high-entropy alloy composite solid-state electrolyte prepared in embodiment 1 are shown in Figure 6 The ion transport characteristics of the CSEs are analyzed by the Nyquist diagram. A CHI660E type electrochemical workstation of Shanghai Chenhua is used to construct a SS / CSEs / SS configuration, and the frequency response analysis is performed based on the EChemS standard at 10mV alternating current amplitude from 106 to 0.01Hz. The impedance spectrum at different temperatures (25-80℃) is fitted by the Arrhenius equation to make the Arrhenius diagram.

[0034] According to the Arrhenius diagram of Figure 5 , the ion conductivity of the pure PEO diaphragm is lower than that of the PEO diaphragm added with the composite product of the high-entropy alloy and the nitrogen-doped hollow carbon cage in the test: the conductivity of the pure PEO diaphragm is the lowest, the activation energy (E a ) is high (the slope is steep), the conductivity of the PEO diaphragm after adding the high-entropy alloy product is significantly improved and the activation energy (Ea) is reduced (the slope is flat), therefore, the addition of the high-entropy alloy product can inhibit the crystallization region of the polymer and provide more migration channels (Li + ), and the high-entropy alloy composite solid-state electrolyte prepared in embodiment 1 of the present application shows more excellent electrochemical performance.

[0035] According to the Arrhenius diagram of Figure 6The EIS spectrum of the product of the composite of the high-entropy alloy and the nitrogen-doped hollow carbon cage with the mass fraction of 10% added in embodiment 1 (PHEA-10), the product of the composite of the high-entropy alloy and the nitrogen-doped hollow carbon cage with the mass fraction of 5% added in embodiment 6 (PHEA-5), and the product of the composite of the high-entropy alloy and the nitrogen-doped hollow carbon cage with the mass fraction of 15% added in embodiment 7 (PHEA-15) is shown in the figure, and it can be known from the figure that the impedance of the product of the composite of the high-entropy alloy and the nitrogen-doped hollow carbon cage with the mass fraction of 10% added in embodiment 1 (PHEA-10) is the lowest, which is 13.33 Ω (the thickness of the diaphragm before measurement is 85 μm); and the EIS curve of the product of the composite of the high-entropy alloy with different added amounts shows that the EIS is the lowest (the intercept) when the added amount of the product is 10%, which proves that the impedance is the smallest, the current is the largest under the same condition, and the electrochemical performance decreases when the added amount of the product is increased, which indicates that the nanoparticles are aggregated to form a dead zone and block the path of Li+ when the content of HEA exceeds the threshold value.

[0036] Figure 7 The tensile property diagram of the pure PEO film and the high-entropy alloy composite solid electrolyte film is shown in the figure, and it can be known from the figure that the tensile property of the product of the composite of the high-entropy alloy and the nitrogen-doped hollow carbon cage with the mass fraction of 10% added in embodiment 1 (PEO-HEA-10) is the best compared with the pure PEO film and the PEO film of the product of the composite of the high-entropy alloy and the nitrogen-doped hollow carbon cage with the mass fraction of 5% added (PEO-HEA-5). Figure 7 0.5 1.0 The tensile property of the product of the composite of the high-entropy alloy and the nitrogen-doped hollow carbon cage with the mass fraction of 10% added in embodiment 1 (PEO-HEA-10) is the best, which indicates that the HEA nanoparticles may destroy the regular arrangement of the PEO chain, reduce the crystalline region, and thus improve the chain segment movement ability of the amorphous region and delay the fracture.

[0037] In embodiments 1, 4 and 5, the molar ratio (EO:Li) of the ethylene oxide repeating unit of the polyethylene oxide and the lithium ion in the lithium salt is controlled to be 18:1, the amorphous region of the diaphragm is damaged and the ion aggregation is caused when the EO:Li is 16:1 or less, and the number of the migratable carriers is reduced, the conductivity is significantly decreased and the flexibility of the diaphragm is poor when the EO:Li is 20:1 or more.

[0038] The above only describes the preferred embodiments of the present application and is not used to limit the present application, and any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.​​

Claims

1. A method for preparing a high-entropy alloy composite solid-state electrolyte, characterized in that, The preparation method comprises the following steps: S1, taking a carbon source for first heat treatment to obtain graphite carbon nitride; grinding and mixing the graphite carbon nitride with cobalt powder, second heat treatment, soaking in an acid solution, washing, drying, and obtaining nitrogen-doped hollow porous carbon cages; S2, dissolving a metal compound in a solvent, adding the nitrogen-doped hollow porous carbon cages for mixing, drying, and heat treatment to obtain a high-entropy alloy precursor; S3, mixing acetonitrile, polyethylene oxide, a lithium salt, and the high-entropy alloy precursor, casting, and drying to obtain a high-entropy alloy composite solid-state electrolyte.

2. The preparation method of the high-entropy alloy composite solid-state electrolyte according to claim 1, characterized in that, The first heat treatment comprises a first-stage heat treatment and a second-stage heat treatment. The first-stage heat treatment is heated to 500-620°C at a heating rate of 4-6°C / min, and kept for 2-6h, and then cooled to room temperature. The second-stage heat treatment is heated to 500-550°C at a heating rate of 4-6°C / min, and kept for 2-3h.

3. The method for preparing a high-entropy alloy composite solid electrolyte according to claim 1, characterized in that, The second heat treatment is carried out under a nitrogen atmosphere, heated to 800-820°C at a heating rate of 1-4°C / min, kept for 2-3h, and then cooled to room temperature.

4. The method for preparing a high-entropy alloy composite solid electrolyte according to claim 1, characterized in that, The mass ratio of the graphite carbon nitride to the cobalt powder is 1:0.8-1.

2. Preferably, the mass ratio of the graphite carbon nitride to the cobalt powder is 1:

1. The acid solution comprises a hydrochloric acid solution, and the molar mass ratio of the hydrochloric acid solution to the carbon source is 1mol:40-50g.

5. The method for preparing a high-entropy alloy composite solid electrolyte according to claim 1, characterized in that, The molar mass ratio of the metal compound to the nitrogen-doped hollow porous carbon cages is 1mmol:0.02-0.05g.

6. The method for preparing a high-entropy alloy composite solid electrolyte according to claim 1, characterized in that, In step S2, the heat treatment is heated to 580-620°C at a heating rate of 3-8°C / min, kept for 2-3h, and then cooled to room temperature.

7. The method for preparing a high-entropy alloy composite solid electrolyte according to claim 1, characterized in that, The mass ratio of the acetonitrile to the polyethylene oxide is 30-40:

4. The mass of the high-entropy alloy precursor is 5%-15% of the mass of the polyethylene oxide.

8. The method for preparing a high-entropy alloy composite solid electrolyte according to claim 7, characterized in that, The molar ratio of the ethylene oxide repeating units of the polyethylene oxide to the lithium ions in the lithium salt is 16-20:

1.

9. The method for preparing a high-entropy alloy composite solid electrolyte according to claim 8, characterized in that, The metal compound comprises an acetylacetone metal compound, and the acetylacetone metal compound comprises Fe(AcAc)3, Co(AcAc)3, Ni(AcAc)2, Mn(AcAc)3, and Zn(AcAc)2.

10. A high-entropy alloy composite solid-state electrolyte, characterized by, The preparation method is prepared by any one of claims 1-9.

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