CN113097563A - High-entropy inorganic electrolyte material, composite electrolyte material and preparation method thereof - Google Patents
High-entropy inorganic electrolyte material, composite electrolyte material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-entropy inorganic electrolyte material, a composite electrolyte material and a preparation method thereof, and also discloses a battery containing the high-entropy inorganic electrolyte material, wherein the chemical formula of the high-entropy inorganic electrolyte material is A x D x1‑E, wherein 0 <x< 1, A is selected from at least one metal element in IA and/or IIA, D is selected from at least five metal elements in IIIB, IVB, VB, VIB, VIIB, VIII, IB or IIB groups, E is selected from at least one element in VIA or VIIA; wherein the ions of the metal element A can be used as ion conduction intermediates in the battery for providing ion conduction A, D contains more than five metal atoms, and due to different atom sizes of different metal elements, lattice distortion is generated in the crystal structure of the material, so that the electricity of the material is influencedThe substructure, which produces a "high entropy effect" resulting in changes to ionic conductivity, has great commercial utility in the field of batteries, particularly in the field of solid-state batteries.
Description
Technical Field
The invention relates to the field of lithium batteries, in particular to a high-entropy inorganic electrolyte material, a composite electrolyte material and a preparation method thereof.
Background
The all-solid-state lithium ion battery has the characteristics of high safety, long cycle life, high energy density and the like, and has a very good application prospect in the field of high-safety chemical power sources. The solid electrolyte material is the core of the all-solid-state lithium battery, and many lithium ion solid electrolyte systems which have been studied so far mainly include oxide type solid electrolytes, sulfide type solid electrolytes, polymer type solid electrolytes, and inorganic-organic composite electrolytes. The sulfide solid electrolyte is mainly divided into binary and ternary solid electrolytes, GeS2、SiS2、P2S5The problems of low conductivity, poor electrochemical stability or poor chemical stability and the like generally exist in the base and other binary sulfide electrolytes, so that the situation is improved by adding another sulfide network modifier, namely a ternary sulfide solid electrolyte, such as Li with high conductivity10GeP2S12Since Ge, Sn, etc. are expensive, their commercial application is limited.
There are three main types of oxide electrolytes available, the NASICON configuration (e.g., Na)3Zr2Si2PO12) Perovskite configuration (e.g. Li) x3La x2/3-TiO3) Garnet structure (e.g. Li)7La3Zr2O12) The electrolyte conductivity of the oxides is low, and although the conductivity can be improved by different doping modifications, the commercial cost is improved by the noble elements such as Zr and La with high content, which is not beneficial to the popularization and application of commercialization. The polymer solid electrolyte (such as PEO and the like) has the characteristics of good flexibility, good compatibility with positive and negative electrode interfaces and the like, but the application of the polymer solid electrolyte is limited due to the lower ionic conductivity and poor mechanical property. In 2004, Avila, Ruiz and Barahona et al synthesized NiPS incorporating Li3The ionic conductivity of the material was investigated by compounding the material with PEO, and it was found that, after compounding with Li and PEO, the ionic conductivity was 0.13uS/cm in comparison with the original NiPS3Higher by a factor of 2 (literature: Manriquez V, Barahona P, Ruiz D, et al. interaction of polyethylene oxide PEO in layered MPS3 (M = Ni, Fe) materials [ J ] - ]]Materials Research Bulletin, 2005, 40(3): 475-. The low ionic conductivity and high crystal boundary resistance limit the application of many solid electrolytes in solid batteries at present, so the organic-inorganic composite electrolyte has the characteristics of high ionic conductivity, flexibility, good mechanical property and good compatibility of positive and negative electrodes.
Disclosure of Invention
In order to solve or improve the technical problem of low conductivity of the electrolyte material, the invention provides a high-entropy inorganic electrolyte material with a chemical formula A x D x1-E, wherein x is more than 0 and less than 1, A is selected from at least one metal element in IA and/or IIA, D is selected from at least five metal elements in IIIB, IVB, VB, VIB, VIIB, VIII, IB or IIB groups, and E is selected from at least one element in VIA or VIIA.
In some embodiments, a is selected from at least one metal element of the elements Li, Na, K, Mg or Ca; and/or D is at least five metal elements selected from Ag, Au, Co, Cr, Cu, Fe, Hf, Mn, Mo, Nb, Ni, Pd, Rh, Ru, Sc, Ta, Ti, V, W, Y, Zn or Zr; and/or, E is selected from at least one element of O, S, Se or Te.
In some embodiments, the particle size of the high entropy inorganic electrolyte material is between 0.1 μm and 200 μm, preferably between 0.1 μm and 75 μm.
Another aspect of the present invention provides a composite electrolyte material comprising: the high-entropy inorganic electrolyte material, the polymer material and the metal salt.
In some embodiments, the high-entropy inorganic electrolyte material has a mass content of 30% to 80%, more preferably, 60% to 70%; and/or the polymeric material comprises a mixture of one or more of PEO, PPO, PAN, PMMA, PVDF or ePPO, or alternatively, comprises one or more of graft or block copolymers PEO-PAN, P (VDF-HFP), PEO-PAN, PEO-PMMA, PEO-PVDF, PMMA-PAN, PAN-PVDF, PEO-PAN-PMMA, PEO-PVDF-PMMA or PAN-PMMA-PVDF; and/or, the metal salt is lithiumThe salt, preferably the lithium salt, is selected from LiN (SO)2CF3)2、LiTFSI、LiClO4、LiSO2CF3、LiFSI、LiB(C2O4)2、LiPF6Or a combination of at least two of the LiI.
In another aspect, the present invention further provides a method for preparing a high-entropy inorganic electrolyte material, comprising the steps of:
the material preparation step: according to the chemical general formula A of the high-entropy inorganic electrolyte material x D x1-E the stoichiometric ratio of the elements determines the required amount of the raw material containing the elements, where 0 <x＜1；
Sintering: and mixing and sintering the raw materials to obtain the high-entropy inorganic electrolyte material.
In some embodiments, in the step of compounding, the raw material of a and/or D uses a simple substance, an oxide or a carbonate containing the element a and/or D; and/or the molar ratio of A to D is (1 to 3) x:(1-x)，0＜x＜1。
In some embodiments, the preparation method of the present invention further comprises grinding and mixing the raw materials, preferably by ball milling; more preferably, the ball milling rotating speed is 200 to 1000 revolutions/min, and the ball milling time is 0.5 to 5 hours; and/or, before sintering, pressing each raw material into a block, preferably, the pressing pressure is 20MPa to 2000 MPa; and/or the sintering temperature is 600-1500 ℃, and the heat preservation time is 6-20 hours.
Still another aspect of the present invention includes a method for preparing a composite electrolyte material, comprising the steps of:
(1) dispersing a high-entropy inorganic electrolyte material, a polymer material and a metal salt in an organic solvent, mixing and stirring to obtain a mixture, and dripping the mixture on a substrate;
(2) and removing the solvent in the mixture, and removing the matrix to obtain the composite electrolyte material.
Still another aspect of the present invention includes a battery containing the high-entropy inorganic electrolyte material or composite electrolyte material of the present invention.
The invention has the beneficial technical effects that a high-entropy metal oxide material (high-entropy inorganic electrolyte material) is found to have excellent conductivity, and can replace oxide electrolyte materials in the prior art, so that the technical problem of low conductivity of the electrolyte material is solved or improved, wherein the high-entropy metal oxide material (high-entropy inorganic electrolyte material) comprises at least one metal element (A) and at least five or more main group metals or transition metal elements (D), wherein ions of the A metal element can be used as ion conduction intermediaries in a battery for providing A ion conduction, for example, the A metal element is Li, and corresponding ions are Li+Is an ion-conducting mediator (via Li) in lithium-based batteries+Energy storage is realized by conduction at the positive and negative electrodes of the battery), so that the high-entropy inorganic electrolyte material has specific ion conductivity; similarly, the A metal element can also be Na, K, Zn, Mg, Ca and other elements, and the obtained high-entropy inorganic electrolyte material is used for a corresponding battery; d contains more than five metal atoms, and due to different atomic sizes of different metal elements, lattice distortion is generated in the crystal structure of the material, the electronic structure of the material is influenced, and a high entropy effect is generated to change the ionic conductivity.
Aiming at the technical problem of poor mechanical property of an inorganic electrolyte material, the invention compounds the high-entropy inorganic electrolyte material with a polymer material to prepare the composite electrolyte material with high ionic conductivity and flexibility.
The terms abbreviated in the present invention have the following meanings:
PEO polyethylene oxide;
PAN polyacrylonitrile;
PMMA polymethyl methacrylate;
PVDF polyvinylidene fluoride;
PHFP polyhexafluoropropene;
ePO polyoxypropylene;
LiTFSI bis (trifluoromethanesulfonylimide).
Drawings
FIG. 1 TEM and element distribution diagrams of a high-entropy inorganic electrolyte material in example 1 of the present invention.
Fig. 2 XRD spectrum of the high-entropy inorganic electrolyte material in example 1 of the present invention.
Fig. 3 is a graph of the conductivity of the high entropy inorganic electrolyte material at different contents (mass fractions) in PEO in example 9 of the present invention.
FIG. 4 impedance spectra of a high-entropy inorganic electrolyte material and a PEO composite electrolyte in example 9 of the present invention.
FIG. 5 Li/composite electrolyte/LiFePO of high-entropy inorganic electrolyte material and PEO composite electrolyte in example 9 of the present invention4Full cell efficiency/specific capacity cycling profile.
FIG. 6 Li/composite electrolyte/LiFePO of high-entropy inorganic electrolyte material and PEO composite electrolyte in example 9 of the present invention4Voltage/capacity curves for different cycle times of the full cell.
Fig. 7 Li/composite electrolyte/Li symmetric battery polarization overpotential cycling curves of the high-entropy inorganic electrolyte material and the PEO composite electrolyte in example 9 of the present invention.
Fig. 8 shows Li/composite electrolyte/Li full cell rate/coulombic efficiency curves of high-entropy inorganic electrolyte material and PEO composite electrolyte, pure PEO in example 9 of the present invention.
Detailed Description
The technical solution of the present invention will be described below by way of specific examples. It is to be understood that one or more of the steps referred to in the present application do not exclude the presence of other methods or steps before or after the combination of steps, or that other methods or steps may be intervening between those steps specifically referred to. It should also be understood that these examples are intended only to illustrate the invention and are not intended to limit the scope of the invention. Unless otherwise indicated, the numbering of the method steps is only for the purpose of identifying the method steps, and is not intended to limit the arrangement order of each method or the scope of the implementation of the present invention, and changes or modifications of the relative relationship thereof may be regarded as the scope of the implementation of the present invention without substantial technical change.
The raw materials and apparatuses used in the examples are not particularly limited in their sources, and may be purchased from the market or prepared according to a conventional method well known to those skilled in the art.
Example 1
This example was carried out to prepare a high-entropy inorganic electrolyte material Li 0.5 （Mg0.2Co0.2Ni0.2Cu0.2Zn0.2）0.5O，xThe preparation method of the high-entropy solid electrolyte material by direct sintering is illustrated by =0.5, and the preparation method comprises the following steps:
(1) the material preparation step: weighing raw materials of lithium carbonate, magnesium oxide, cobaltous oxide, nickelous oxide, copper oxide and zinc oxide according to the molar ratio of Li to Mg to Co to Ni to Cu to Zn =5:1:1:1:1 (in the embodiment, the raw material of lithium carbonate can be replaced by lithium oxide);
(2) grinding: putting the raw materials into a planetary ball mill for ball milling and mixing, wherein the ball milling speed is 600rpm and the ball milling time is 1h according to the ball material mass ratio of 20: 1;
(3) a pressing step: and pressing the ball-milled mixed raw materials into blocks by using a die under the pressure of 300 MPa.
(4) Sintering: and (3) preserving the heat of the pressed block for 12 hours (air atmosphere) at 1000 ℃ in a tube furnace, then quenching the block by air, and then putting the block into a 200-mesh agate mortar for grinding and sieving to obtain the powder of the high-entropy inorganic electrolyte material, wherein the particle size of the obtained powder is less than 75 microns.
The TEM test of the obtained powder shows that the prepared material has an obvious polycrystalline structure and uniform distribution of Mg, Co, Ni, Cu, Zn and O elements as shown in figure 1. The XRD test structure is shown in FIG. 2, which shows that the product prepared is a single-phase crystal structure (rock salt type crystal).
In some embodiments of the present invention, the,xand the high-entropy inorganic electrolyte material with different lithium contents can be obtained by proportioning different elements at other values between 0 and 1.
Example 2
This example provides another method for preparing a high-entropy inorganic electrolyte material, which is similar to that of example 1, except that in the blending step: weighing raw materials of lithium oxide, magnesium oxide, cobaltous oxide, nickelous oxide, copper oxide and zinc oxide according to the molar ratio of Li to Mg to Co to Ni to Cu to Zn = (5-15) to 1:1:1: 1. The maximum doping of the metallic lithium element in the high entropy metal oxide is achieved by adding an excess of lithium oxide.
In a specific example, raw materials were weighed in a molar ratio of Li: Mg: Co: Ni: Cu: Zn = 10:1:1:1:1: 1.
Example 3
This example provides another method for preparing a high-entropy inorganic electrolyte material, Na x （Mg0.2Co0.2Ni0.2Cu0.2Zn0.2） x1-O，x=0.5, similar to example 1, except that a is a metallic sodium element and the raw material containing a is sodium carbonate.
Example 4
This example provides another method for preparing a high-entropy inorganic electrolyte material, Li x （Mg0.2Co0.2Ni0.2Cu0.2Zn0.2） x1-S，x=0.2, similar to example 1, except that, in the compounding step: weighing raw materials of lithium carbonate, magnesium oxide, cobaltous oxide, nickel protoxide, copper oxide, zinc oxide and sulfur powder according to the molar ratio of Li to Mg to Co to Ni to Cu to Zn to S =2 to 1.6 to 1; in the sintering step: keeping the pressed block in a tube furnace at 1200 ℃ for 12 hours (argon atmosphere or vacuum degree is less than 10)-3Pa）。
Example 5
This example provides another method for preparing a high-entropy inorganic electrolyte material, Li x （Mg0.2Co0.2Ni0.2Cu0.2Zn0.2） x1-Cl2Similar to example 1, except that in the compounding step: weighing raw materials of lithium chloride, magnesium chloride, cobaltous chloride, nickelous chloride and chlorous according to the molar ratio of Li to Mg to Co to Ni to Cu to Zn =5:1:1:1:1Copper and zinc chloride, and in the sintering step: keeping the pressed block in a tube furnace at 1500 ℃ for 12 hours (argon atmosphere or vacuum degree less than 10)-3Pa）。
Example 6
This example provides another method for preparing a high-entropy inorganic electrolyte material, Li x （Ti0.2V0.2Cr0.2Nb0.2Ta0.2） x1-S0.5Se0.5，x=0.1, similar to example 1, except that, in the compounding step: weighing raw materials of lithium metal, titanium powder, vanadium powder, niobium powder, tantalum powder, sulfur powder and selenium powder according to the molar ratio of Li to Ti to V to Cr to Nb to Ta to S to Se =1:1.8 to 5, and sintering the raw materials: the pressed block was kept in a tube furnace at 1000 ℃ for 6 hours (argon atmosphere).
Example 7
This example provides another method for preparing a high-entropy inorganic electrolyte material, Li x （V0.2Cr0.2Mn0.2Fe0.2Co0.2） x1-I2，x=0.7, similar to example 1, except that, in the compounding step: weighing raw materials of lithium metal, vanadium powder, chromium powder, manganese powder, iron powder, cobalt powder and iodine powder according to the molar ratio of Li to V to Cr to Mn to Fe to Co to I =7 to 0.6 to 20, and sintering the raw materials: the pressed block was kept in the tube furnace at 1000 ℃ for 10 hours (argon atmosphere).
Example 8
This example provides another method for preparing a high-entropy inorganic electrolyte material, Li x （Ti0.2V0.2Cr0.2Nb0.2Fe0.1Mn0.1） x1-O，x=0.3, similar to example 1, except that, in the compounding step: weighing raw materials of lithium carbonate, titanium dioxide, vanadium dioxide, chromium oxide, niobium dioxide, ferroferric oxide and manganese dioxide according to the molar ratio of Li to Ti to V to Cr to Nb to Fe to Mn =3:1.4:1.4:1.4: 0.7:0.7, and sintering the raw materials: the pressed block was kept at 1500 ℃ in a tube furnace for 20 hours (air atmosphere).
It should be noted that the invention is based on the material property change caused by the "high entropy effect", wherein, the kind of the element in D is preferably a metal or a transition metal element capable of forming a high entropy alloy material, and comprises: 22 transition metals (Ag, Au, Co, Cr, Cu, Fe, Hf, Mn, Mo, Nb, Ni, Pd, Rh, Ru, Sc, Ta, Ti, V, W, Y, Zn, Zr); 2 base metals (Al, Sn); 6 lanthanides (Dy, Gd, Lu, Nd, Tb, Tm); 3 metals (B, Ge, Si), among which, more preferably, comprising: al, Co, Cr, Cu, Fe, Mn, Ni and Ti, wherein the elements are present in more than 100 alloys, wherein the proportion of each of four elements (Co, Cr, Fe and Ni) in the high-entropy alloy is up to more than 70 percent, and in addition, the high-entropy alloy also comprises common refractory elements (Mo, Nb, V and Zr); more preferably, B is selected from the group consisting of transition metal elements of the fourth and fifth periods in groups VIIB, VIII, IB and IIB, including Fe, Co, Ni, Mn, Zn, V, Cd, Cu, Ag, Pd or Ru, which are capable of being in solid solution with each other; b may further include some main group metal elements capable of forming a solid solution with the transition metal element, such as In element In IIIA or Bi element In VA.
Example 9
This example provides a composite electrolyte material and a method for preparing the same, and illustrates that the high-entropy inorganic electrolyte material prepared in example 1 is compounded with PEO in different contents as electrolytes, and the contents of the high-entropy inorganic electrolyte material are 0%, 20%, 30%, 40%, 50%, 60%, 70%, and 80%, respectively.
Adding part of lithium salt LiTFSI into anhydrous acetonitrile, then adding PEO with the molecular weight of 600000 into the mixed solution, stirring for 4 hours by using magnetons to dissolve the PEO, then adding high-entropy inorganic electrolysis according to a proportion, and stirring for 12 hours by using the magnetons. The mass ratio of each component is as follows: PEO accounts for 5% of anhydrous acetonitrile; PEO high entropy inorganic electrolyte material =1: m, m =0%, 20%, 30%, 40%, 50%, 60%, 70%, 80%; PEO: LiTFSI = 1.89. And dripping the dispersion liquid on a polytetrafluoroethylene sheet (matrix), volatilizing at room temperature until the surface is dry, drying in a vacuum oven at 60 ℃ for 12 hours, and removing the matrix to obtain the composite electrolyte material.
The ionic conductivity test method is as follows:
the ion conductivity test is carried out by using two stainless steel sheets to sandwich electrolyte, and the test method is that the initial potential is 0V, the sweep speed of 5mV/s, and the frequency is 0.1 Hz-10 Hz6EIS testing was performed in the Hz range and then the ionic conductivity σ = l/(S × R) was calculated according to the formula, where l is the electrolyte thickness, S is the electrolyte cross-sectional area, and R represents the charge transfer resistance, and fig. 3 shows the ionic conductivity at each temperature, and we found that before the content of 70%, the ionic conductivity increased with increasing content of the high-entropy inorganic electrolyte material, and then the ionic conductivity began to decrease. The ionic conductivity can reach 1 x 10 under the condition that the content of the high-entropy inorganic electrolyte material is 70 percent at 60 DEG C-3S/cm. According to the invention, the composite electrolyte material contains the high-entropy inorganic electrolyte material with the mass content of 30-80%, and has better performance, preferably, the high-entropy inorganic electrolyte material with the mass content of 60-80%, and more preferably, 70%.
Fig. 4 is a graph of impedance for different PEO ratios and different lithium contents in the composite electrolyte material. Among them, the lithium-free high-entropy metal oxide as a comparative sample means a high-entropy metal oxide containing no metallic lithium element, and the production method thereof is similar to that of the high-entropy inorganic electrolyte material of example 1 except that a component containing no metallic lithium, whose chemical formula is represented by (Mg)0.2Co0.2Ni0.2Cu0.2Zn0.2) And O. As can be seen from fig. 4, the impedance of the high-entropy inorganic electrolyte material containing metallic lithium is significantly lower than that of the composite electrolyte containing pure PEO and lithium-free high-entropy metal oxide, which indicates that the addition of metallic lithium element to the high-entropy metal oxide has a crucial role in improving the ionic conductivity, and the composite electrolyte material of the present invention has an excellent ability of conducting lithium ions, wherein the mass content of the high-entropy inorganic electrolyte material is better than that of the sample with the content of 40% when the mass content is 70%.
In order to verify the electrochemical performance of the composite electrolyte material of the invention as a solid electrolyte of a secondary lithium battery, the high-entropy solid electrolyte of the invention was assembled into a CR-2032 type button-type counter cell (hereinafter, referred to as a symmetrical cell of the invention) in which the thickness of the electrolyte was controlled to 0.1mm (hereinafter, the thickness was uniform), and pure PEO was used as a control sample under the same conditions. The high-entropy solid electrolyte is a CR-2032 button type full cell (hereinafter, referred to as the full cell of the invention) assembled by taking a lithium sheet as a negative electrode and lithium iron phosphate as a positive electrode.
The electrochemical test of the full-cell is carried out under the condition of room temperature and the current density of 0.1C, and the obtained test result is shown in figure 5, it can be seen that after 110 cycles of charge and discharge, the specific capacity can be maintained at 147.7mAh/g, and figure 6 is a capacity-voltage curve of different cycle times, and it can be seen that the charge and discharge curves from the 20 th cycle to the 100 th cycle are almost overlapped, the voltage platform of charge and discharge is stable, and the voltage difference between the charge and discharge platforms is small, which indicates that the polarization potential of the electrode in the cell is small, and further indicates that the composite electrolyte material of the invention has excellent lithium ion conduction effect and cycle stability. The inventive symmetric cell was compared to a comparative pure PEO symmetric cell at 0.05mA/cm2The electrochemical test is carried out under the current density, and the obtained test result is shown in fig. 7, so that the polarization potential of the symmetrical battery containing the composite electrolyte material is stabilized at about 40mV, and the polarization potential of a pure PEO symmetrical battery is compared at about 100 mV-200 mV under the same condition, which shows that the composite electrolyte material has excellent cycle stability and the function of inhibiting the growth of lithium dendrites when being used as the electrolyte material of the lithium battery.
In order to verify the rate performance of the composite electrolyte material of the present invention as a solid electrolyte of a secondary lithium battery, we tested the rate performance of the full cell of the present invention and a comparative sample pure PEO full cell, as shown in fig. 8, the full cell of the present invention performed better at the same rate. Further illustrating the excellent electrochemical performance of the composite electrolyte material of the present invention as a solid electrolyte.
In some embodiments, the mass percent of the metal salt in the composite electrolyte material is between 1-50 wt.%.
In some embodiments, the polymer material in the composite electrolyte material may also be selected from a mixture of one or more of PPO, PAN, PMMA, PVDF, or ePPO, or alternatively, a graft or block copolymer of one or more of PEO-PAN, P (VDF-HFP), PEO-PAN, PEO-PMMA, PEO-PVDF, PMMA-PAN, PAN-PVDF, PEO-PAN-PMMA, PEO-PVDF-PMMA, or PAN-PMMA-PVDF; the technical problem of poor mechanical property of the inorganic electrolyte material is solved by compounding the inorganic electrolyte material with a polymer material, so that the composite electrolyte material with high ionic conductivity and flexibility is obtained.
In some embodiments, the solvent used to dissolve the polymeric material includes, without limitation, one or more of acetonitrile, acetone, tetrahydrofuran, ethanol, or dimethylformamide.
In some embodiments, a is selected from Na element, and the metal salt added in the preparation of the composite electrolyte material is selected from sodium salt, and the resulting electrolyte material is used in a sodium-based battery. Similarly, A is selected from K, Ca and Mg elements, and the metal salt is selected from potassium salt, calcium salt or magnesium salt, respectively, and the obtained electrolyte material is used for potassium-based, calcium-based or magnesium-based batteries respectively.
The above embodiments are provided only to illustrate some embodiments of the technical features of the present invention, and the present invention includes embodiments not limited thereto, and it will be apparent to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept of the present invention, and the scope of the present invention should be determined by the claims.
Claims (10)
1. A high-entropy inorganic electrolyte material is characterized in that the chemical formula is A x D x1-E, wherein 0 <x< 1, A is selected from at least one metal element in IA and/or IIA, D is selected from at least five metal elements in IIIB, IVB, VB, VIB, VIIB, VIII, IB or IIB groups, and E is selected from at least one element in VIA or VIIA.
2. The high-entropy inorganic electrolyte material as claimed in claim 1, wherein a is at least one metal element selected from Li, Na, K, Mg, or Ca elements;
and/or D is at least five metal elements selected from Ag, Au, Co, Cr, Cu, Fe, Hf, Mn, Mo, Nb, Ni, Pd, Rh, Ru, Sc, Ta, Ti, V, W, Y, Zn or Zr;
and/or, E is selected from at least one element of O, S, Se or Te.
3. A high-entropy inorganic electrolyte material as claimed in claim 1 or 2, characterized in that its particle size is between 0.1 μm and 200 μm.
4. A composite electrolyte material, comprising: the high-entropy inorganic electrolyte material, the polymer material, and the metal salt according to any one of claims 1 to 3.
5. The composite electrolyte material according to claim 4, characterized in that the mass content of the high-entropy inorganic electrolyte material is 30% to 80%;
and/or the polymeric material comprises a mixture of one or more of PEO, PPO, PAN, PMMA, PVDF or ePPO, or the polymeric material comprises one or more of graft or block copolymers PEO-PAN, P (VDF-HFP), PEO-PAN, PEO-PMMA, PEO-PVDF, PMMA-PAN, PAN-PVDF, PEO-PAN-PMMA, PEO-PVDF-PMMA or PAN-PMMA-PVDF;
and/or the metal salt is a lithium salt.
6. A method for producing a high-entropy inorganic electrolyte material as claimed in any one of claims 1 to 3, characterized by comprising the steps of:
the material preparation step: according to the chemical general formula A of the high-entropy inorganic electrolyte material x D x1-E the stoichiometric ratio of the elements determines the required amount of the raw material containing the elements, where 0 <x＜1；
Sintering: and mixing and sintering the raw materials to obtain the high-entropy inorganic electrolyte material.
7. The production method according to claim 6, wherein in the compounding step, the raw material containing A is a simple substance, an oxide or a carbonate containing the element A; the raw material containing D uses a simple substance, an oxide or a carbonate containing the element D;
and/or the molar ratio of A to D is (1 to 3) x:(1-x)，0＜x＜1。
8. The method of claim 6, further comprising grinding and mixing the raw materials;
and/or, before sintering, pressing each raw material into a block;
and/or the sintering temperature is 600-1500 ℃, and the heat preservation time is 6-20 hours.
9. A method for producing the composite electrolyte material according to claim 4 or 5, characterized by comprising the steps of:
(1) dispersing a high-entropy inorganic electrolyte material, a polymer material and a metal salt in an organic solvent, mixing and stirring to obtain a mixture, and dripping the mixture on a substrate;
(2) and removing the solvent in the mixture, and removing the matrix to obtain the composite electrolyte material.
10. A battery, comprising: the high-entropy inorganic electrolyte material of any one of claims 1 to 3, or the composite electrolyte material of claim 4 or 5.
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