High-entropy all-solid-state electrolyte and preparation method and application thereof

Abstract

The invention discloses a high-entropy all-solid-state electrolyte as well as a preparation method and application thereof, and belongs to the technical field of solid-state batteries. The chemical formula of the high-entropy all-solid-state electrolyte is Li M Zr < c > Cl < 6-x > Br < x >, and M is a doped metal element and comprises Yb, Ce, Er and In; 0 < = x < = 2.5, a + 3b + 4c = 6, 1 < = a < = 5, and 0.2 < = b < = 1. According to the invention, multiple elements such as Yb, Ce, Er, Zr and the like are selected for cation high-entropy substitution of In sites, and Cl / Br mixed anions are combined, so that a synergistic effect is generated. Chemical disorder and lattice distortion caused by high entropy reduce a Li < + > migration energy barrier, and phase transformation induced by mixed anions forms a more favorable Li < + > migration channel, so that the ionic conductivity is remarkably improved, the electrochemical oxidation stability is greatly improved, and the contradiction that the two are difficult to obtain in the traditional method is successfully solved. The lithium ion solid-state battery assembled by the high-entropy all-solid-state electrolyte is particularly suitable for a high-voltage positive electrode system, and can show high coulombic efficiency and good cycling stability.

Description

Technical Field

[0001] This invention belongs to the field of solid-state battery technology, and specifically relates to a high-entropy all-solid-state electrolyte, its preparation method, and its application. Background Technology

[0002] The high flammability of liquid electrolytes makes batteries extremely dangerous in the event of thermal runaway. Solid electrolytes, as a type of non-flammable super ionic conductor, possess extremely high thermal stability and mechanical strength. Among them, halide solid electrolytes have recently attracted much attention due to their excellent lithium-ion conductivity and good electrochemical compatibility with cathode materials. However, when the voltage exceeds 4.3 volts, chloride ions in halide solid electrolytes undergo severe oxidation, leading to a decline in performance and a significant increase in the interfacial resistance between the cathode and the halide solid electrolyte. Furthermore, the poor electrochemical stability of halide solid electrolytes easily triggers side reactions during solid-state battery cycling, resulting in structural damage, reduced cycle stability, and battery failure.

[0003] The high-entropy design of solid-state electrolytes can exhibit unique chemical / physical properties not found in traditional materials. Differences in atomic radii within high-entropy materials induce localized lattice distortions, thereby altering the energy barriers for element migration. This effect effectively modulates the kinetics of different elements within the structure, demonstrating the potential of high-entropy materials to mitigate corrosion and improve material stability. High-entropy stability effect (configurational entropy S) config >1.5R) can induce a thermodynamically stable state and promote a uniform distribution of elements. Therefore, high-entropy halide solid electrolytes hold promise for maintaining high Li content. + While improving electrical conductivity, it also enhances the electrochemical stability of halide solid electrolytes. However, the formation conditions for high-entropy structures are quite stringent, and the selection and ratio of elements incorporated into the electrolyte have a significant impact on the performance of the prepared high-entropy materials.

[0004] To address the high entropy of halide electrolytes, there are three main approaches based on the doping elements: cation high entropy doping (cation doping), anion high entropy doping (anion doping), and mixed cation-anion high entropy doping (mixed cation-anion doping). Among these, anion doping is the most widely used method to improve the high-voltage stability of halide solid electrolytes. However, due to the high electronegativity of common anions such as F, improving high-voltage stability often comes at the cost of sacrificing ionic conductivity, leading to a decrease in the electrochemical performance of halide solid electrolytes. Therefore, selecting appropriate elements to form a stable high-entropy structure and developing halide solid electrolytes that simultaneously satisfy high room-temperature ionic conductivity, high oxidation stability potential, good cycling stability, and low resource cost is of great significance. Summary of the Invention

[0005] To overcome the shortcomings of existing technologies, the main objective of this invention is to provide a high-entropy all-solid-state electrolyte, its preparation method, and its applications. This invention introduces localized chemical disorder and distortion at cation sites to disrupt site energies, causing energy overlap between adjacent sites and thus promoting ion mobility. Furthermore, by limiting the vibrational range of chloride ions through localized lattice distortion, the oxidation reaction is kinetically suppressed, ultimately achieving a high-entropy state design for a halide solid-state electrolyte that simultaneously achieves high-pressure stability and high ionic conductivity.

[0006] To achieve the above objectives, the present invention provides a high-entropy all-solid-state electrolyte, wherein the chemical formula of the high-entropy all-solid-state electrolyte is Li. a M b Zr c Cl 6-x Br x Where M is a doped metal element, including Yb, Ce, Er, and In; 0≤x≤2.5, a+3b+4c=6, 1≤a≤5, and 0.2≤b≤1.

[0007] Furthermore, the high-entropy all-solid-state electrolyte Li a M b Zr c Cl 6-x Br x In the equation, 1.0≤x≤1.8, 2.5≤a≤3.5, and 0.6≤b≤1.

[0008] In another aspect, the present invention provides a method for preparing the aforementioned high-entropy all-solid-state electrolyte, comprising the following steps: weighing halides LiCl, LiBr, YbCl3, CeCl3, ErCl3, InCl3 and ZrCl4 according to the chemical formula ratio of the high-entropy all-solid-state electrolyte, and then mixing, grinding and pulverizing the weighed raw materials to obtain the pulverized precursor; The pulverized precursor is ball-milled, and then the ball-milled precursor is sintered under an inert atmosphere and cooled to obtain the high-entropy all-solid electrolyte.

[0009] Furthermore, the sintering temperature is 240~300℃, and the holding time is 4~24h.

[0010] Furthermore, the heating rate of the sintering is 0.5~3℃ / min.

[0011] Furthermore, the mixing and grinding time is 15-30 minutes.

[0012] Furthermore, during the pulverization process, the pulverization speed is 20,000~30,000 rpm / min, the total running time is 3~5 min, and the pulverizer is allowed to stand for 1~2 min after every 30 seconds of operation.

[0013] Furthermore, during the ball milling process, the ball milling speed is 200-600 rpm / min.

[0014] Furthermore, the ball milling adopts a circulating ball milling method, with 24 to 48 cycles, each cycle consisting of 15 minutes of ball milling followed by 5 minutes of resting.

[0015] In another aspect, the present invention provides the application of the aforementioned high-entropy all-solid-state electrolyte in lithium-ion solid-state batteries.

[0016] Compared with the prior art, the present invention has the following beneficial effects: (1) This invention achieves a synergistic effect by selecting multiple elements such as Yb, Ce, Er, and Zr to perform high-entropy substitution of In sites with cations, combined with Cl / Br mixed anions. The chemical disorder and lattice distortion caused by high-entropy substitution reduce the chemical density of Li. + The migration energy barrier, while the mixed anion-induced phase transition forms a more favorable Li + The migration channel significantly improves both ionic conductivity and electrochemical oxidation stability, successfully resolving the contradiction that traditional methods often fail to achieve both simultaneously.

[0017] (2) By designing specific cationic elements and ratios, the present invention utilizes the cationic elements introduced into the electrolyte to cause local lattice distortion, which kinetically limits the vibration range of chloride ions, effectively suppresses oxidation reaction under high voltage, and thus achieves high voltage stability.

[0018] (3) Optimized preparation process: The present invention adopts a two-step mechanical activation method of "high-speed crushing + ball milling" to ensure the uniform mixing of multiple elements at the atomic level, which lays the foundation for the formation of a uniform and stable high-entropy structure. Controlling the slow heating rate of sintering helps to obtain electrolyte sheets with fine grains and dense structure, thereby improving their overall performance.

[0019] (4) The lithium-ion solid-state battery assembled using the high-entropy all-solid-state electrolyte of the present invention is particularly suitable for high-voltage cathode systems, and can exhibit high coulombic efficiency and good cycle stability, and has important commercial application prospects. Attached Figure Description

[0020] Figure 1 The X-ray diffraction pattern of the high-entropy all-solid-state electrolyte material of Embodiment 1 of the present invention is shown; Figure 2 The electrochemical impedance spectroscopy spectra of the high-entropy all-solid-state electrolyte material of Example 1 and the Li3InCl6 electrolyte material of Comparative Example 1 are shown. Figure 3The cyclic voltammetry spectra of the high-entropy all-solid-state electrolyte material of Example 1 and the Li3InCl6 electrolyte material of Comparative Example 1 are shown. Detailed Implementation

[0021] It should be noted that, unless otherwise specified, the embodiments and features described in this application can be combined with each other. Furthermore, regarding the numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Each smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included within this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range. The invention will now be described in detail with reference to embodiments.

[0022] To achieve the above objectives, a first aspect of the present invention provides a high-entropy all-solid-state electrolyte, the high-entropy all-solid-state electrolyte having the chemical formula Li. a M b Zr c Cl 6-x Br x Where M is a doped metal element, including Yb, Ce, Er, and In; 0≤x≤2.5, a+3b+4c=6, 1≤a≤5, and 0.2≤b≤1.

[0023] This invention employs high-entropy substitution of In sites with cations using multiple elements such as Yb, Ce, Er, and Zr, combined with a Cl / Br mixed anion. The phase transition caused by the mixed Cl / Br anion obtained through bromination leads to disproportionate octahedral expansion and distortion, forming a structure favorable for Li... + The migration transport path. Specifically, in the (001) plane, the Li-M electrostatic repulsion may promote the migration of Li... + Diffusion to the M-free (002) layer enables fast in-plane Li + Movement, and promotes exchange between 2d and 4h sites.

[0024] In a preferred embodiment of the present invention, the high-entropy all-solid-state electrolyte Li a M b Zr c Cl 6-x Br x In the equation, 1.0≤x≤1.8, 2.5≤a≤3.5, and 0.6≤b≤1.

[0025] The value of x has a crucial impact on electrolyte performance. Specifically, the framework constructed by mixed anions induces structural disorder, giving the electrolyte better flexibility and compaction capabilities. This results in tighter interfacial contact during use, effectively suppressing the problem of limited ion transport caused by poor contact. Furthermore, Br, with its stronger polarization ability... - It can be used for migrating ions (such as Li) + This results in more effective charge shielding, weakens the interaction between the Br and the framework, significantly reduces the migration energy barrier, and thus achieves higher ionic conductivity. Therefore, too low a Br doping level is insufficient to achieve the above effects, while too high a doping level may lead to decreased crystal structure stability or even collapse, causing early performance degradation of the electrolyte.

[0026] In some preferred embodiments of the present invention, the chemical formula of the high-entropy all-solid-state electrolyte may be selected, for example, from Li. 2.95 Yb 0.05 Ce 0.05 Er 0.05 In 0.8 Zr 0.05 Cl 4.55 Br 1.45 Li 2.95 Yb 0.05 Ce 0.05 Er 0.05 In 0.8 Zr 0.05 Cl6, Li 2.95 Yb 0.05 Ce 0.05 Er 0.05 In 0.8 Zr 0.05 Cl 3.5 Br 2.5 Li 2.95 Yb 0.05 Ce 0.05 Er 0.05 In 0.65 Zr 0.1625 Cl 4.6 Br 1.4 Li 2.95 Yb 0.05 Ce 0.05 Er 0.05 In 0.45 Zr 0.315 Cl 5.0 Br 1.0 Li 1.0 Yb 0.1 Ce 0.05 Er 0.05 In 0.8 Zr 0.5 Cl 3.5 Br2.5 、Li 1.0 Yb 0.05 If 0.05 Er 0.05 And 0.45 Zr 0.8 Cl 4.75 No 1.25 、Li 5.0 Yb 0.05 If 0.05 Er 0.05 And 0.05 Zr 0.1 Cl 4.55 No 1.45 、Li 3.5 Yb 0.05 If 0.05 Er 0.05 And 0.05 Zr 0.475 Cl 4.6 No 1.4 、Li 3.5 Yb 0.05 If 0.05 Er 0.05 And 0.05 Zr 0.475 Cl6、Li 3.5 Yb 0.05 If 0.05 Er 0.05 And 0.45 Zr 0.175 Cl 4.75 No 1.25 、Li 3.5 Yb 0.05 If 0.05 Er 0.05 And 0.45 Zr 0.175 Cl 3.5 No 2.5 、Li 2.5 Yb 0.05 If 0.05 Er 0.05 And 0.45 Zr 0.425 Cl 5.0 No 1.0 、Li 2.5 Yb 0.05 If 0.05 Er 0.05 And 0.85 Zr 0.125 Cl 3.5 No 2.5 、Li 2.5 Yb 0.05 If 0.05 Er0.05 In 0.65 Zr 0.275 Cl 4.6 Br 1.4 、Li3Yb 0.05 Ce 0.05 Er 0.05 In 0.65 Zr 0.15 Cl 4.6 Br 1.4 、Li3Yb 0.05 Ce 0.05 Er 0.05 In 0.85 Cl 4.75 Br 1.25 、Li3Yb 0.05 Ce 0.05 Er 0.05 In 0.45 Zr 0.3 Cl 4.2 Br 1.8 、Li3Yb 0.05 Ce 0.05 Er 0.05 In 0.45 Zr 0.3 Cl6.

[0027] In a second aspect of the present invention, a method for preparing a high-entropy all-solid-state electrolyte is provided, comprising the following steps: According to the chemical formula ratio of the high-entropy all-solid electrolyte, the halides LiCl, LiBr, YbCl3, CeCl3, ErCl3, InCl3 and ZrCl4 were weighed, and then the weighed raw materials were mixed, ground and pulverized to obtain the pulverized precursor. The pulverized precursor is ball-milled, and then the ball-milled precursor is sintered under an inert atmosphere and cooled to obtain the high-entropy all-solid electrolyte.

[0028] In a preferred embodiment of the present invention, the sintering temperature is 240~300℃ and the holding time is 4~24h.

[0029] In a preferred embodiment of the present invention, the sintering heating rate is 0.5~3℃ / min. By controlling the sintering heating rate within the above range, the present invention helps to obtain smaller grains, resulting in a better microstructure and higher density. Simultaneously, it can better eliminate pores in the material, reduce internal defects, and thus improve the material's density and mechanical properties.

[0030] In a preferred embodiment of the present invention, the mixing and grinding time is 15-30 minutes.

[0031] In a preferred embodiment of the present invention, during the pulverization process, the pulverization speed is 20,000~30,000 rpm / min, the total running time is 3~5 min, and a resting period of 1~2 min is taken after every 30 seconds of running. The present invention, through high-speed pulverization, not only physically refines the reactants but also makes the elements more uniformly mixed, creating favorable conditions for the uniform combination of multiple elements in subsequent high-speed ball milling, ultimately forming a uniform product with a single composition.

[0032] In a preferred embodiment of the present invention, the ball milling speed is 200-600 rpm during the ball milling process. The ball milling of the present invention can be carried out in a ball mill equipped with zirconia balls (5 mm in diameter) at a ball-to-material ratio of 20-50:1.

[0033] In a preferred embodiment of the present invention, the ball milling is a circulating ball milling, with 24 to 48 cycles, each cycle consisting of 15 minutes of ball milling followed by 5 minutes of resting.

[0034] A third aspect of the present invention also provides the application of the aforementioned high-entropy all-solid-state electrolyte in lithium-ion solid-state batteries.

[0035] For the reasons stated above, applying the high-entropy all-solid-state electrolyte of this invention to lithium-ion solid-state batteries can demonstrate high coulombic efficiency and good cycle stability.

[0036] The present application will be further described in detail below with reference to specific embodiments, which should not be construed as limiting the scope of protection claimed in the present application.

[0037] Example 1 A high-entropy all-solid-state electrolyte with the chemical formula Li 2.95 Yb 0.05 Ce 0.05 Er 0.05 In 0.8 Zr 0.05 Cl 4.55 Br 1.45 .

[0038] The preparation method of this high-entropy all-solid-state electrolyte includes the following steps: Step 1: Weigh out the various chlorides according to the chemical ratio, totaling about 10g. The halides are LiCl, LiBr, YbCl3, CeCl3, ErCl3, InCl3 and ZrCl4, in a ratio of 1.5:1.45:0.05:0.05:0.05:0.8:0.05.

[0039] Step 2: Place the weighed raw materials into a mortar and grind them for 20 minutes to obtain the ground precursor.

[0040] Step 3: Pour the ground precursor into a grinder and grind it at a speed of 25,000 rpm for a total running time of 4 minutes, with a resting time of 1 minute after every 30 seconds of grinding.

[0041] Step 4: Pour the pulverized precursor into a zirconia jar containing 30g of zirconia balls (5mm in diameter) and ball mill. The ball milling speed is 550 rpm / min, and the milling is performed for 48 cycles. Each cycle consists of 15 minutes of ball milling followed by 5 minutes of resting.

[0042] Step 5: After ball milling, the precursor is placed in a crucible and then placed in a muffle furnace. After sintering and cooling in an argon atmosphere, the target all-solid electrolyte is obtained. The sintering temperature is 260℃, the heating rate is 0.5℃ / min, and the holding time is 8h.

[0043] Example 2 A high-entropy all-solid-state electrolyte with the chemical formula Li 2.95 Yb 0.05 Ce 0.05 Er 0.05 In 0.8 Zr 0.05 Cl6. Its preparation method is the same as in Example 1, except that the raw materials are different.

[0044] Example 3 A high-entropy all-solid-state electrolyte with the chemical formula Li 2.95 Yb 0.05 Ce 0.05 Er 0.05 In 0.8 Zr 0.05 Cl 3.5 Br 2.5 The preparation method is the same as in Example 1, except that the raw materials are different.

[0045] Example 4 A high-entropy all-solid electrolyte is prepared in a way that differs from that in Example 1, except that the pulverization time in step 3 is adjusted to 1 minute, while the other steps remain unchanged.

[0046] Example 5 A high-entropy all-solid-state electrolyte is prepared in a manner that differs from that in Example 1, except that the heating rate in step 5 is adjusted to 3°C / min, while the other steps remain unchanged.

[0047] Example 6 A high-entropy all-solid-state electrolyte with the chemical formula Li2.95 Yb 0.05 Ce 0.05 Er 0.05 In 0.45 Zr 0.315 Cl 5.0 Br 1.0 The preparation method is the same as in Example 1, except that the raw materials are different.

[0048] Example 7 A high-entropy all-solid-state electrolyte with the chemical formula Li 2.95 Yb 0.05 Ce 0.05 Er 0.05 In 0.65 Zr 0.1625 Cl 4.6 Br 1.4 The preparation method is the same as in Example 1, except that the raw materials are different.

[0049] Example 8 A high-entropy all-solid-state electrolyte with the chemical formula Li 1.0 Yb 0.1 Ce 0.05 Er 0.05 In 0.8 Zr 0.5 Cl 3.5 Br 2.5 The preparation method is the same as in Example 1, except that the raw materials are different.

[0050] Example 9 A high-entropy all-solid-state electrolyte with the chemical formula Li 1.0 Yb 0.1 Ce 0.05 Er 0.05 In 0.8 Zr 0.5 Cl6. Its preparation method is the same as in Example 1, except that the raw materials are different.

[0051] Example 10 A high-entropy all-solid-state electrolyte with the chemical formula Li 5.0 Yb 0.05 Ce 0.05 Er 0.05 In 0.05 Zr 0.1 Cl 4.55 Br 1.45 The preparation method is the same as in Example 1, except that the raw materials are different.

[0052] Example 11 A high-entropy all-solid-state electrolyte with the chemical formula Li 3.5 Yb 0.05 Ce 0.05 Er 0.05 In 0.05 Zr 0.475 Cl 4.6 Br 1.4 The preparation method is the same as in Example 1, except that the raw materials are different.

[0053] Example 12 A high-entropy all-solid-state electrolyte with the chemical formula Li3Yb 0.05 Ce 0.05 Er 0.05 In 0.65 Zr 0.15 Cl 4.6 Br 1.4 The preparation method is the same as in Example 1, except that the raw materials are different.

[0054] Example 13 A high-entropy all-solid-state electrolyte with the chemical formula Li 2.5 Yb 0.05 Ce 0.05 Er 0.05 In 0.45 Zr 0.425 Cl 4.2 Br 1.8 The preparation method is the same as in Example 1, except that the raw materials are different.

[0055] Example 14 A high-entropy all-solid-state electrolyte with the chemical formula Li 2.5 Yb 0.05 Ce 0.05 Er 0.05 In 0.45 Zr 0.425 Cl 5.0 Br 1.0 The preparation method is the same as in Example 1, except that the raw materials are different.

[0056] Comparative Example 1 A chloride-based all-solid-state electrolyte with the chemical formula Li3InCl6.

[0057] Comparative Example 2 A high-entropy all-solid-state electrolyte with the chemical formula Li 2.95 Yb 0.05 Ce 0.05 Er 0.05 In0.8 Zr 0.05 Cl3Br3. Its preparation method is the same as in Example 1, differing only in the raw materials.

[0058] Performance testing: Ionic conductivity: Ionic conductivity was tested using the electrochemical impedance spectroscopy (EIS). First, 200 mg of the electrolyte synthesized in the above examples and comparative examples was weighed and directly cold-pressed into sheets. Then, a symmetrical battery structure was assembled using a stainless steel blocking electrode and the electrolyte sheet. The assembled battery was subjected to electrochemical impedance spectroscopy (EIS) testing using an electrochemical workstation. The frequency range of the EIS test was set to 1 MHz to 1 Hz, and the voltage amplitude was 10 mV. Based on the characteristics of the EIS curve, the total impedance value was extracted. Combined with the thickness and area of ​​the electrolyte sheet, the ionic conductivity was calculated using the following formula: σ = L / (R × S), where: σ represents the ionic conductivity (unit: S / cm); L is the thickness of the solid electrolyte sheet (unit: cm); R is the bulk resistance of the electrolyte measured by the electrochemical impedance spectroscopy (EIS) (unit: Ω); and S is the effective contact area between the electrode and the electrolyte (unit: cm²). 2 The test results are shown in Table 1.

[0059] Oxidation potential: The ionic conductivity was measured using cyclic voltammetry. First, the synthesized electrolyte (SE) was assembled into a battery with a Li-In | LPSCl | SE | SE+VGCF structure. The assembled battery was then subjected to cyclic voltammetry (CV) testing using an electrochemical workstation, with a voltage range of 2.7 to 5.0 V and a scan rate of 0.1 mV / s. The CV curves were observed, and the oxidation peak was identified. The potential corresponding to the oxidation peak is the oxidation potential of the electrolyte. The test results are shown in Table 1.

[0060] Table 1

[0061] pass Figure 1 Powder X-ray diffraction (XRD) showed that Li 2.95 Yb 0.05 Ce 0.05 Er 0.05 In 0.8 Zr 0.05 Cl 4.55 Br 1.45 All diffraction peaks of the sample (Example 1) point to Li3InCl6, indicating that Li 2.95 Yb 0.05 Ce 0.05 Er 0.05 In 0.8 Zr 0.05 Cl 4.55 Br1.45 The long-range order of the Li3InCl6 structure was maintained.

[0062] Figure 2 Electrochemical impedance spectroscopy was used to calculate the concentrations of Li3InCl6 and Li. 2.95 Yb 0.05 Ce 0.05 Er 0.05 In 0.8 Zr 0.05 Cl 4.5 5Br 1.45 The ionic conductivity of (Example 1) was 0.78 mS / cm and 1.35 mS / cm, respectively, indicating that the high-entropy electrolyte with increased disorder caused by the incorporation of multiple dopants significantly improved the ionic conductivity.

[0063] Figure 3 The cyclic voltammetry spectra are shown in the curves for Li3InCl6 and Li. 2.95 Yb 0.05 Ce 0.05 Er 0.05 In 0.8 Zr 0.05 Cl 4.5 5Br 1.45 The oxidation potentials of (Example 1) are approximately 3.82 V and 4.2 V, respectively. More importantly, based on Li... 2.95 Yb 0.05 Ce 0.05 Er 0.05 In 0.8 Zr 0.05 Cl 4.55 Br 1.45 The battery current value decreased significantly, indicating that Cl The oxidation kinetics are hindered. In general, high-entropy electrolytes with increased disorder due to the incorporation of multiple dopants significantly improve electrolyte stability.

[0064] The embodiments described above are merely illustrative of implementation methods of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the present invention. The present invention can also be implemented in other specific ways or forms without departing from its spirit or essential characteristics. Therefore, the described embodiments should be considered illustrative rather than limiting in any respect. The scope of the present invention should be defined by the appended claims, and any variations equivalent to the intent and scope of the claims should also be included within the scope of the present invention.

Claims

1. A high-entropy all-solid-state electrolyte, characterized by, The high-entropy all-solid-state electrolyte has a chemical formula of Li a M b Zr c Cl 6-x Br x , wherein M is a doping metal element, including Yb, Ce, Er and In; 0<=x<=2.5, a+3b+4c=6, 1<=a<=5, 0.2<=b<=1, 0.1<=c<=0.

5.

2. The high-entropy all-solid-state electrolyte of claim 1, wherein, The high-entropy all-solid-state electrolyte Li a M b Zr c Cl 6-x Br x In the formula, 1.0≤x≤1.8, 2.5≤a≤3.5, 0.6≤b≤1.

3. A method of producing a high-entropy all-solid-state electrolyte as claimed in claim 1 or 2, characterized by, The method comprises the following steps: According to the chemical formula proportion of the high-entropy all-solid-state electrolyte, halides LiCl, LiBr, YbCl3, CeCl3, ErCl3, InCl3 and ZrCl4 are weighed, and then the weighed raw materials are mixed, ground and crushed to obtain a crushed precursor; The crushed precursor is ball milled, and then the ball milled precursor is sintered under an inert atmosphere, and then cooled to obtain the high-entropy all-solid-state electrolyte.

4. The method of claim 3, wherein the high-entropy all-solid-state electrolyte is prepared by the steps of: The sintering temperature is 240-300°C, and the holding time is 4-24h.

5. The method of claim 3, wherein the high-entropy all-solid-state electrolyte is prepared by the steps of: preparing a solution of a lithium salt and a solvent; adding a high-entropy metal salt to the solution; and adding a high-entropy metal oxide to the solution. The sintering temperature is 240-300°C, and the holding time is 4-24h.

6. The method of claim 3, wherein the high-entropy all-solid-state electrolyte is prepared by the steps of: preparing a solution of a lithium salt and a solvent; adding a high-entropy metal salt to the solution; and adding a high-entropy metal oxide to the solution. The sintering temperature is 240-300°C, and the holding time is 4-24h.

7. The method of claim 3, wherein the high-entropy all-solid-state electrolyte is prepared by the steps of: preparing a solution of a lithium salt and a solvent; adding a lithium metal powder to the solution; and drying the solution to obtain the high-entropy all-solid-state electrolyte. The sintering temperature is 240-300°C, and the holding time is 4-24h.

8. The method of claim 3, wherein the high-entropy all-solid-state electrolyte is prepared by the steps of: preparing a solution of a lithium salt and a solvent; adding a high-entropy metal salt to the solution; and adding a high-entropy metal oxide to the solution. In the crushing process, the crushing rotation speed is 20000-30000rmp / min, the total running time is 3-5min, and the standing time is 1-2min every 30s.

9. The method of claim 3, wherein the high-entropy all-solid-state electrolyte is prepared by a process comprising: mixing a lithium salt, a lithium ion-conductive solid electrolyte, and a binder to form a mixture; and coating the mixture on a substrate to form a film. In the ball milling process, the ball milling rotation speed is 200-600rmp / min. The ball milling adopts cyclic ball milling, and the cycle number is 24-48 cycles, each cycle is ball milling for 15min, and standing for 5min.

10. The high-entropy all-solid-state electrolyte according to claim 1 or 2 is applied in a lithium ion solid-state battery.

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