CN115594229A - Nano high-entropy oxide material, preparation method thereof and lithium-sulfur battery positive electrode material - Google Patents
Nano high-entropy oxide material, preparation method thereof and lithium-sulfur battery positive electrode material Download PDFInfo
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- CN115594229A CN115594229A CN202211273282.3A CN202211273282A CN115594229A CN 115594229 A CN115594229 A CN 115594229A CN 202211273282 A CN202211273282 A CN 202211273282A CN 115594229 A CN115594229 A CN 115594229A
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- entropy oxide
- oxide material
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Images
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- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
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- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The application belongs to the technical field of materials, and particularly relates to a nano high-entropy oxide material, a preparation method thereof and a lithium-sulfur battery positive electrode material. The method comprises the following steps: dissolving precursors of at least five transition metals in a solvent to prepare a metal precursor solution; mixing the metal precursor solution with an organic ligand containing an organic functional group, a surfactant and an auxiliary bridging ligand, and performing solvothermal reaction to form coordination connection to obtain an organic metal framework template material; and calcining the organic metal framework template material in an oxygen atmosphere at the temperature of below 1000 ℃ to obtain the nano high-entropy oxide material. The calcining temperature is low, the energy consumption is low, the process is simple, the prepared high-entropy oxide has single phase, good crystallinity, small particle size and uniform distribution, and has abundant metal catalytic active sites, and the utilization rate of active sulfur can be improved; meanwhile, the shuttle effect of polysulfide can be inhibited, and the electrochemical performance of the battery is improved.
Description
Technical Field
The application belongs to the technical field of materials, and particularly relates to a nano high-entropy oxide material, a preparation method thereof and a lithium-sulfur battery positive electrode material.
Background
The development of new energy automobiles and new energy storage systems is a solid technical support for meeting energy and environmental challenges, promoting energy transformation in China and realizing strategic goals of carbon peak reaching and carbon neutralization. Most of the existing energy storage systems in the market mainly comprise lead-acid batteries, lithium ion batteries and flow batteries, and the existing energy storage systems in the market have certain disadvantages in the aspects of energy density, safety, price and the like, and cannot meet the requirements of further development of the market. Therefore, it is of great strategic importance to develop a novel lithium ion secondary battery having high performance, low cost and environmental friendliness. In view of its many advantages, such as high theoretical capacity (1675 mAh/g) and energy density (2500 Wh/kg), low cost and abundant sulfur resources, and good overcharge resistance, lithium sulfur batteries are considered to be one of the most potential energy storage systems to meet future energy storage needs. However, the complicated multi-electron conversion, the "shuttle effect" caused by the dissolution of lithium polysulfide, and the insulation property between sulfur and lithium polysulfide present in the charging and discharging processes of the lithium-sulfur battery become the bottleneck of the development of the lithium-sulfur battery. In addition, the problems result in low specific capacity, poor cycle performance, low coulombic efficiency and poor rate performance of the lithium-sulfur battery, and the practical application and further marketization of the lithium-sulfur battery are restricted.
In order to alleviate and solve the above problems, the majority of researchers mainly adopt two main strategies: (1) The sulfur is put into the mesoporous/microporous conductive carbon material, the utilization rate of the sulfur is improved, meanwhile, a physical limited domain is formed by utilizing the physical adsorption effect of the porous carbon carrier, the shuttle effect of polysulfide is reduced, but the acting force between the nonpolar carbon material and polar lithium polysulfide is weaker, and the improvement on the cycle performance of the lithium-sulfur battery is limited. (2) The 'shuttle effect' of polysulfide is inhibited by chemical confinement effect by utilizing the strong chemical adsorption between non-carbon-based carrier (mainly transition metal oxide such as titanium dioxide, manganese dioxide, magnesium oxide and the like) and polysulfide. The high-entropy oxide has abundant metal active sites, can be used as a catalyst for lithium polysulfide conversion, and improves the utilization rate of active sulfur; meanwhile, the lithium-sulfur battery has strong chemical adsorption effect on polysulfide, can form a chemical confinement, inhibits the shuttle effect of lithium polysulfide, and is favorable for improving the electrochemical performance of the lithium-sulfur battery. However, the existing high-entropy oxide is generally prepared by preparing a precursor by methods such as high-energy ball milling, spray drying and the like, and then sintering the precursor by a high-temperature solid-phase method, and the sintering temperature is generally higher than 1000 ℃, so that the process is complex, the energy consumption is high, the particle size of the material is large, and the application of the material in the anode of a lithium-sulfur battery is not facilitated.
Disclosure of Invention
The application aims to provide a nanometer high-entropy oxide material, a preparation method thereof and a lithium-sulfur battery anode material, and aims to solve the problems that the existing high-entropy oxide is high in preparation temperature, high in energy consumption, complex in process and not beneficial to application of the high-entropy oxide material in a lithium-sulfur battery anode to a certain extent.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a method for preparing a nano high-entropy oxide material, comprising the following steps:
dissolving precursors of at least five transition metals in a solvent to prepare a metal precursor solution;
mixing the metal precursor solution with an organic ligand containing an organic functional group, a surfactant and an auxiliary bridging ligand, and performing solvothermal reaction to form coordination connection to obtain an organic metal framework template material;
and calcining the organic metal framework template material in an oxygen atmosphere at the temperature of below 1000 ℃ to obtain the nano high-entropy oxide material.
In a second aspect, the application provides a nano high-entropy oxide material prepared by the method, the nano high-entropy oxide material is formed by stacking layered single-phase metal oxide crystalline solid solutions, and transition metal elements are uniformly dispersed in the solid solutions.
In a third aspect, the present application provides a positive electrode material for a lithium-sulfur battery, which is prepared from the following raw material components: the nanometer high-entropy oxide material prepared by the method or the nanometer high-entropy oxide material, the sulfur source and the conductive agent.
According to the preparation method of the nanometer high-entropy oxide material provided by the first aspect of the application, at least five precursors of transition metals are prepared into a metal precursor solution, then the metal precursor solution is mixed with an organic ligand, a surfactant and the auxiliary bridging ligand, through solvothermal reaction, a reactant is promoted to be dissolved in a solvent, metal nodes are exposed from the metal precursor, and the metal precursor, the organic ligand and the auxiliary bridging ligand are subjected to coordination connection to form a three-dimensional metal-organic framework structure, namely the organic metal framework template material. And then the organic metal framework template material is calcined, so that the calcining temperature is obviously reduced, the energy consumption is reduced, and the process is simplified. Oxidizing and removing the organic ligand and the auxiliary bridging ligand in the organic metal framework template material in a medium-high temperature oxygen atmosphere at the temperature of below 1000 ℃; meanwhile, the metal precursor is oxidized to form a single-phase metal oxide crystal solid solution with stable entropy, and the transition metal elements are uniformly dispersed in the solid solution to obtain the nano high-entropy oxide material with single phase, good crystallinity, small particle size and uniform distribution. The prepared nano high-entropy oxide material contains highly dispersed transition metal elements, has extremely rich active sites, can be used as a catalyst for lithium polysulfide conversion in the positive electrode of a lithium-sulfur battery, and improves the utilization rate of active sulfur; meanwhile, the lithium sulfide battery cathode has strong chemical adsorption effect on polysulfide, can form a chemical confinement, and inhibits the shuttling of lithium polysulfide in the lithium sulfur battery cathode. Therefore, the shuttle effect of the lithium-sulfur battery can be inhibited and the electrochemical performance of the battery can be improved when the lithium-sulfur battery is applied to the positive electrode material of the lithium-sulfur battery.
The nano high-entropy oxide material prepared by the method is stacked by layered single-phase metal oxide crystalline solid solutions, and transition metal elements are dispersed in the solid solutions. The nanometer high-entropy oxide material has the advantages of single phase, good crystallinity, small particle size, uniform distribution and abundant metal catalytic active sites, can be used for rapidly catalytically converting polysulfide, inhibiting the shuttle effect of polysulfide, and is beneficial to improving the discharge capacity and the cycle life of a lithium-sulfur battery when being applied to the lithium-sulfur battery.
The lithium-sulfur battery positive electrode material provided by the third aspect of the application is prepared by taking the nanometer high-entropy oxide material, the sulfur source and the conductive agent as raw materials, and the nanometer high-entropy oxide material doped in the lithium-sulfur battery positive electrode material has abundant metal catalytic active sites, has a rapid catalytic conversion effect on polysulfide, can inhibit the shuttle effect of the polysulfide, and improves the discharge capacity and cycle life of the lithium-sulfur battery.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings used in the embodiments or the description of the prior art will be briefly described below. It is obvious that the drawings in the following description are only some embodiments of the application, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is a schematic flow chart of a method for preparing a nanometer high-entropy oxide material provided by an embodiment of the application;
FIG. 2 is an SEM image of a nanometer high-entropy oxide material provided in example 1 of the present application;
FIG. 3 is a TEM image of a nano high-entropy oxide material provided in example 1 of the present application;
fig. 4 is an XRD chart of the nano high-entropy oxide material, elemental sulfur and the lithium sulfur battery cathode material provided in example 1 of the present application;
fig. 5 is a cycle performance curve of the positive electrode material of the lithium-sulfur battery provided in example 1 of the present application at a current density of 0.5C;
fig. 6 is a first-turn charge-discharge curve diagram of the positive electrode material of the lithium-sulfur battery provided in example 1 of the present application;
fig. 7 is a graph of rate performance of the positive electrode material for a lithium-sulfur battery provided in example 1 of the present application.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (one) of a, b, or c," or "at least one (one) of a, b, and c," may each represent: a, b, c, a-b (i.e. a and b), a-c, b-c, or a-b-c, wherein a, b, and c can be single or multiple respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the examples of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components according to the examples of the present application is scaled up or down within the scope disclosed in the examples of the present application. Specifically, the mass in the examples of the present application may be in units of mass known in the chemical industry, such as μ g, mg, g, and kg.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
As shown in fig. 1, a first aspect of the embodiments of the present application provides a method for preparing a nano high-entropy oxide material, which includes the following steps:
s10, dissolving precursors of at least five transition metals in a solvent to prepare a metal precursor solution;
s20, mixing the metal precursor solution with an organic ligand containing an organic functional group, a surfactant and an auxiliary bridging ligand, and performing solvothermal reaction to form coordination connection to obtain an organic metal framework template material;
s30, calcining the organic metal framework template material in an oxygen atmosphere at the temperature of below 1000 ℃ to obtain the nano high-entropy oxide material.
According to the preparation method of the nanometer high-entropy oxide material provided by the first aspect of the embodiment of the application, after a precursor of at least five transition metals is prepared into a metal precursor solution, the metal precursor solution is mixed with an organic ligand, a surfactant and an auxiliary bridging ligand, through solvothermal reaction, a reactant is promoted to be dissolved in a solvent, a metal node is exposed from the metal precursor, and the metal precursor is in coordination connection with the organic ligand and the auxiliary bridging ligand to form a three-dimensional metal-organic framework structure, namely an organic metal framework template material. And then the organic metal framework template material is calcined, so that the calcining temperature is obviously reduced, the energy consumption is reduced, and the process is simplified. The organic ligand and the auxiliary bridging ligand in the organic metal framework template material can be oxidized and removed in a medium-high temperature oxygen atmosphere at the temperature of below 1000 ℃, meanwhile, the metal precursor is oxidized to form a single-phase metal oxide crystal solid solution with stable entropy, and the transition metal elements are uniformly dispersed in the solid solution, so that the nano high-entropy oxide material with single phase, good crystallinity, small particle size and uniform distribution is obtained. The prepared nano high-entropy oxide material contains highly dispersed transition metal elements, has extremely rich active sites, can be used as a catalyst for lithium polysulfide conversion in the positive electrode of a lithium-sulfur battery, and improves the utilization rate of active sulfur; meanwhile, the lithium sulfide battery cathode has strong chemical adsorption effect on polysulfide, can form a chemical confinement, and inhibits the shuttling of lithium polysulfide in the lithium sulfur battery cathode. Therefore, the shuttle effect of the lithium-sulfur battery can be inhibited and the electrochemical performance of the battery can be improved when the lithium-sulfur battery is applied to the positive electrode material of the lithium-sulfur battery.
In some embodiments, in step S10, at least five precursors of transition metals are dissolved in a solvent to prepare a metal precursor solution. The nano high-entropy oxide material prepared by the embodiment of the application is an oxide with a single structure obtained by mutual solid solution of five or more main metal elements according to a certain proportion. The preparation of the metal precursor solution can be that precursors of five or more than five transition metals are mixed and dissolved in a solvent at the same time to form a mixed metal precursor solution; or respectively dissolving precursors of five or more transition metals in a solvent to respectively prepare metal precursor solutions of the corresponding transition metals.
In some preferred embodiments, it is preferable to separately dissolve precursors of different transition metals in a solvent to separately prepare metal precursor solutions of different transition metals, considering that the precursors of different transition metals have different dissolution properties.
In some embodiments, the transition metal is selected from at least five of nickel, cobalt, copper, magnesium, zinc, titanium, manganese, iron; the transition metal elements selected in the embodiment of the application can be matched with each other to form coordination, so that a stable metal organic framework precursor can be formed. And, these transition metal elements are applied to the positive electrode material of the lithium-sulfur battery, and may perform different functions, such as: transition metal elements such as magnesium, nickel, cobalt and the like have catalytic conversion effect on polysulfide, and are beneficial to improving the utilization rate of active sulfur materials; transition metal elements such as zinc and the like have an adsorption effect on polysulfide, can form a chemical confinement, and inhibit shuttle of lithium polysulfide in the positive electrode of the lithium-sulfur battery, so that the cycle performance of the electrode material is improved. Therefore, through the synergistic effect of five or more transition metal elements, the metal organic framework precursor coordination structure with stable structure is favorably formed, and the application efficiency of the nano high-entropy oxide material in the lithium-sulfur battery is favorably improved.
In some embodiments, the precursor form of the transition metal comprises at least one of a nitrate, a phosphate, a sulfate, a chloride; precursor forms of the transition metals of the embodiments of the present application include, but are not limited to, any soluble metal salts, such as nitrates, phosphates, sulfates, chlorides, and the like. In some preferred embodiments, the precursor form of the transition metal employs a nitrate; nitrate precursors of transition metals are easier to dissolve in an organic solvent to form a uniform precursor solution, which is beneficial to forming a metal organic framework material with a three-dimensional structure through solvothermal reaction, and the transition metal elements are uniformly dispersed in a high-entropy oxide to finally form uniform nano solid solution active sites, thereby playing roles in catalytic conversion and anchoring on sulfides; the problems that partial sulfate and phosphate are not well dissolved, chloride is easy to volatilize in the calcining process, and the heating unit is greatly damaged by decomposed and released chlorine and the like are solved.
In some embodiments, precursors of transition metals are selected from any five of nickel nitrate hexahydrate, cobalt nitrate hexahydrate, copper nitrate hexahydrate, magnesium nitrate hexahydrate, zinc nitrate hexahydrate, titanium nitrate hexahydrate, manganese nitrate hexahydrate, and iron nitrate nonahydrate, respectively dissolved in a solvent, and sonicated to obtain nitrate precursor solutions of five or more transition metals, respectively.
In some embodiments, the purity of the precursor of the transition metal is more than 98%, and the high-purity precursor material is selected, so that the introduction of impurity components can be reduced, the purity of the nano high-entropy oxide material is improved, and the interference of the impurity components on the performance of the product is reduced. In some embodiments, the nickel nitrate hexahydrate, cobalt nitrate hexahydrate, copper nitrate hexahydrate, magnesium nitrate hexahydrate, zinc nitrate hexahydrate, titanium nitrate hexahydrate, manganese nitrate hexahydrate, and iron nitrate nonahydrate are each greater than or equal to 98% pure.
In some embodiments, the concentration of the metal precursor solution is 0.1 to 5mmol/L, which facilitates the formation of a uniform precursor solution of the metal precursor in the solvent, and simultaneously facilitates the formation of the metal organic framework material having a three-dimensional structure through solvothermal reaction, and realizes the uniform dispersion of the transition metal element in the high-entropy oxide solid solution. In some embodiments, the concentration of the metal precursor solution includes, but is not limited to, 0.1 to 1mmol/L, 1 to 2mmol/L, 2 to 3mmol/L, 3 to 4mmol/L, 4 to 5mmol/L, and the like.
In some embodiments, the step of preparing the metal precursor solution comprises: precursors of the five transition metals are respectively dissolved in a solvent to respectively prepare metal precursor solutions of the five transition metals. In some embodiments, the molar ratio of the precursors of the five transition metals is (0.15 to 0.25): (0.15 to 0.25): (0.15 to 0.25): (0.15 to 0.25): (0.15-0.25). Five transition metal precursors with equal molar ratio or approximate equal molar ratio are used as raw materials, a three-dimensional metal organic framework is formed through subsequent solvothermal reaction coordination, then the transition metal elements are uniformly dispersed in the high-entropy oxide solid solution through medium-high temperature calcination treatment, and finally uniform nano solid solution active sites are formed, so that the nano high-entropy oxide material with single phase, good crystallinity, small particle size and uniform distribution is obtained.
In some embodiments, the solvent comprises at least one of dimethylformamide, ethanol, diethylformamide, methanol, propanol, isopropanol; the adopted solvents are small solvent molecules, so that the solvent has good solubility on precursors of transition metals, organic ligands and auxiliary bridging ligands, unsaturated metal centers can be combined with the unsaturated metal centers to meet the coordination requirement, and the solvent molecules can be removed through subsequent heating or vacuum treatment, so that unsaturated metal sites are exposed.
In some embodiments, the solvent is selected from a mixed solvent of dimethylformamide and ethanol; the mixed solvent has better dissolving and dispersing performances on precursors of transition metals, organic ligands and auxiliary bridging ligands. In some embodiments, the solvent is selected from a mixed solvent of dimethylformamide and ethanol in a volume ratio of (1-10): 1. In some embodiments, the volume ratio of dimethylformamide to ethanol includes, but is not limited to (1-3): 1. (3-5): 1. (5-8): 1. (8-10): 1, etc.
In some specific embodiments, any five of nickel nitrate hexahydrate, cobalt nitrate hexahydrate, copper nitrate hexahydrate, magnesium nitrate hexahydrate, zinc nitrate hexahydrate, titanium nitrate hexahydrate, manganese nitrate hexahydrate and iron nitrate nonahydrate, all of which have a purity of 98% or more, are dissolved in a dimethylformamide/ethanol mixed solution in a volume ratio of (1-10): 1, and subjected to ultrasonic treatment to obtain precursor solutions of five transition metals in a range of 0.1-5 mmol/L, respectively; and the molar ratio of the precursors of the five transition metals is (0.15-0.25): (0.15 to 0.25): (0.15 to 0.25): (0.15 to 0.25): (0.15-0.25).
In some embodiments, the step S20 of mixing the metal precursor solution with the organic ligand having an organic functional group, the surfactant and the auxiliary bridging ligand includes: adding an organic ligand and a surfactant into a reaction vessel, respectively adding metal precursor solutions of different transition metals, preparing an auxiliary bridging ligand into a solution, adding the solution into the reaction vessel, and sealing for ultrasonic dispersion treatment. The metal precursor solutions of different transition metals are respectively added, so that the agglomeration and precipitation among the metal precursors are favorably avoided, in addition, the auxiliary bridging ligand is prepared into a solution and then added into the reaction container, and the solution with uniform dissolution and dispersion is favorably formed by each raw material component in the reaction system, so that each raw material component is favorably and fully contacted in the subsequent solvent thermal reaction, and the uniform and stable coordination connection is realized.
In some embodiments, the auxiliary bridging ligand is prepared into a solution with a concentration of 0.1 to 0.5mmol/L and then added into the reaction vessel, and the mass ratio of the organic ligand to the auxiliary bridging ligand is (1 to 3): 10. the adopted solvent is at least one of dimethylformamide, ethanol, diethylformamide, methanol, propanol and isopropanol, and is further a mixed solvent of dimethylformamide and ethanol with the volume ratio of (1-10): 1, so that the solvent has better solubility. In some embodiments, the concentration of the auxiliary bridging ligand is selected from, but not limited to, 0.1-0.2 mmol/L, 0.2-0.3 mmol/L, 0.3-0.4 mmol/L, 0.4-0.5 mmol/L, etc.
In some embodiments, the mass ratio of the metal precursor, the organic ligand, the surfactant and the auxiliary bridging ligand in the metal precursor solution is (15-30): 1-2): 5-15: (2-6); in other embodiments, the molar ratio of the metal precursor, the organic ligand, the surfactant and the auxiliary bridging ligand in the metal precursor solution is (50-100): 5-15): 0.2-1): 3-8. Wherein the organic ligand is used for providing electrons and is combined with the central atom of the transition metal through a coordination bond to form a coordination compound; the auxiliary bridging ligand is matched with the organic ligand for use, and the topological structure and the pore structure of the metal organic framework are jointly regulated and controlled; the surfactant reduces the surface tension of the raw material components, and is beneficial to the mutual contact and coordination of the components to form a three-dimensional metal organic framework precursor structure. The mass ratio of the metal precursor, the organic ligand, the surfactant and the auxiliary bridging ligand fully ensures that the transition metal precursor is exposed out of metal nodes and is in coordination connection with the organic ligand and the auxiliary bridging ligand in the subsequent solvothermal reaction process to form a three-dimensional metal-organic framework structure, and the stability of the metal-organic framework structure is ensured.
In some embodiments, the organic ligand comprising an organofunctional group comprises at least one of a hydroxyl-containing organometallic framework ligand, a carboxyl-containing organometallic framework ligand, an amide-containing organometallic framework ligand, an amine-containing organometallic framework ligand, a pyridyl-containing organometallic framework ligand. The organic ligand contains organic functional groups, and the functional organic sites of the organic ligand can be used as active sites of Lewis acid or alkali. Wherein the organic functional group comprises at least one of hydroxyl, carboxyl, amido and pyridyl. In some embodiments, the carboxyl-containing organometallic framework ligands include, but are not limited to, carboxylates such as: carboxylates, tricarboxylates, tetracarboxylates, hexacarboxylates, octacarboxylic acids, and the like. In some embodiments, the organometallic framework ligands containing pyridyl groups include, but are not limited to, bipyridyl. The organic functional group contained in the organic ligand of the above embodiments of the present application can act as the active site of the lewis acid or base. In the subsequent solvothermal reaction, the preparation method is favorable for obtaining the metal organic framework structure material with the three-dimensional structure, and provides a good precursor for the subsequent preparation of the nanometer high-entropy oxide material. In some preferred embodiments, the organic ligand is selected from bipyridine.
In some embodiments, the surfactant comprises at least one of a nonionic surfactant, a cationic surfactant, an anionic surfactant; the surfactants can reduce the surface tension of raw material components, and are beneficial to the mutual contact and coordination of the components to form a three-dimensional metal organic framework precursor structure.
In some embodiments, the nonionic surfactant comprises at least one of polyvinylpyrrolidone, poloxamer (Pluronic F127), polyether P123 (Pluronic P123), span 80 (Span 80), polyethylene glycol dodecyl ether, polyethylene glycol dialkyl ester, polyethylene glycol dilaurate, polyethylene glycol 2-ethylhexyl ether, sorbitan alkyl ester. In some embodiments, the cationic surfactant comprises at least one of cetyltrimethylammonium chloride, octadecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, didodecyldimethylammonium bromide, hexadecyltrimethylammonium bromide. In some embodiments, the anionic surfactant comprises at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, lithium dodecyl sulfate, sodium octyl sulfate, sodium decyl sulfate, sodium 1-butane sulfonate, sodium butylnaphthalene sulfonate. In some particularly preferred embodiments, the surfactant is selected from polyvinylpyrrolidone.
In some embodiments, the ancillary bridging ligands include at least one of porphyrin ligands, sulfonic acid-containing organometallic framework ligands, phosphoric acid-containing organometallic framework ligands, carboxylic acid nitrogen-containing mixed organometallic framework ligands. The auxiliary bridging ligands can be matched with organic ligands for use, and the topological structure and the pore structure of the metal organic framework are jointly regulated and controlled. In some particularly preferred embodiments, the ancillary bridging ligand is selected from tetrakis (4-carboxyphenyl) porphyrin.
In some embodiments, the conditions of the solvothermal reaction include: reacting for 12 to 48 hours at the temperature of between 60 and 140 ℃; under the condition of solvothermal reaction, the dissolution of reactants in a reaction solvent is promoted, so that a transition metal precursor is exposed out of a metal node and is in coordination connection with an organic ligand and an auxiliary bridging ligand to form a three-dimensional metal-organic framework structure. The reaction temperature range can ensure the good dissolution of reactants in a reaction solvent and the construction of a metal organic framework material. If the reaction temperature is too high, the accumulation rate of the metal organic framework is too high, the structure is easy to distort, the metal organic framework material with stable structure and uniform metal site distribution is not easy to form, the uniformity and the physical phase purity of the subsequent high-entropy nanometer oxide material are influenced, and the problem of high energy consumption is also brought. If the reaction temperature is too low, the reaction is not favorable for promoting the transition metal precursor to expose metal nodes, and is also not favorable for the transition metal, the organic ligand and the auxiliary bridging ligand to perform coordination connection to form a three-dimensional metal-organic framework structure. In some embodiments, the temperature of the solvothermal reaction includes, but is not limited to, 60 to 80 ℃,80 to 100 ℃, 100 to 120 ℃, 120 to 140 ℃, and the like, and the reaction time period includes, but is not limited to, 12 to 24 hours, 24 to 36 hours, 36 to 48 hours, and the like.
In some specific embodiments, after adding the organic ligand and the surfactant into a reaction vessel, respectively adding metal precursor solutions of different transition metals, preparing the auxiliary bridging ligand into a solution with a concentration of 0.1-0.5 mmol/L, adding into the reaction vessel, and sealing for ultrasonic dispersion treatment for 10-60 min; reacting for 12-48 hours at 60-140 ℃, centrifugally separating the product at the rotating speed of 4000-8000 r/min, washing the product with absolute ethyl alcohol, and drying at 50-100 ℃ for 5-24 hours to obtain the organic metal framework template material. Wherein the mass ratio of the transition metal precursor, the organic ligand, the surfactant and the auxiliary bridging ligand is (15-30) to (1-2) to (5-15) to (2-6).
In some embodiments, in step S30, the conditions for performing the calcination treatment on the organic metal framework template material in the oxygen atmosphere at a temperature of 1000 ℃ or less include: in oxygen atmosphere, heating to 450-1000 ℃ at the speed of 5-10 ℃/min, and then preserving heat for 10-24 hours. The oxygen atmosphere can be air or pure oxygen, the ligand organic matter is oxidized and removed through medium-high temperature treatment, meanwhile, the metal precursor is oxidized to form a single-phase metal oxide crystal solid solution with stable entropy, and the transition metal is uniformly distributed in the metal oxide crystal solid solution to form rich active sites. In some embodiments, the calcination temperature is 450-850 ℃, and the organic metal framework template material can be sintered at a lower temperature, so that the energy consumption is reduced, the process is simplified, and the production efficiency is improved. In some embodiments, the rate ramp includes, but is not limited to, 5-6 ℃/min, 6-7 ℃/min, 7-8 ℃/min, 8-9 ℃/min, 9-10 ℃/min, and the like, the calcination temperature includes, but is not limited to, 450-600 ℃, 600-850 ℃, 850-1000 ℃, and the like, and the holding time includes, but is not limited to, 10-15 hours, 15-20 hours, 20-24 hours, and the like.
In some embodiments, a method for preparing a nano high-entropy oxide material comprises the following steps:
s11, respectively dissolving any five of nickel nitrate hexahydrate, cobalt nitrate hexahydrate, copper nitrate hexahydrate, magnesium nitrate hexahydrate, zinc nitrate hexahydrate, titanium nitrate hexahydrate, manganese nitrate hexahydrate and ferric nitrate nonahydrate with the purity of more than or equal to 98% in a dimethyl formamide/ethanol mixed solution with the volume ratio of (1-10): 1, and performing ultrasonic treatment to respectively obtain precursor solutions of five transition metals of 0.1-5 mmol/L; and the molar ratio of the precursors of the five transition metals is (0.15-0.25): (0.15 to 0.25): (0.15-0.25): (0.15 to 0.25): (0.15-0.25).
S21, adding an organic ligand and a surfactant into a reaction vessel, respectively adding metal precursor solutions of different transition metals, preparing an auxiliary bridging ligand into a solution with the concentration of 0.1-0.5 mmol/L, adding the solution into the reaction vessel, and sealing for ultrasonic dispersion treatment for 10-60 min; reacting for 12-48 hours at 60-140 ℃, centrifugally separating the product at the rotating speed of 4000-8000 r/min, washing the product with absolute ethyl alcohol, and drying at 50-100 ℃ for 5-24 hours to obtain the organic metal framework template material. Wherein the mass ratio of the transition metal precursor, the organic ligand, the surfactant and the auxiliary bridging ligand is (15-30) to (1-2) to (5-15) to (2-6).
S31, heating the organic metal framework template material to 450-1000 ℃ at the speed of 5-10 ℃/min in the atmosphere of introducing air or pure oxygen, and then preserving the heat for 10-24 hours to obtain the black nano high-entropy oxide material.
In a second aspect, the present application provides a nano high-entropy oxide material prepared by the above method, the nano high-entropy oxide material is formed by stacking layered single-phase metal oxide crystalline solid solutions, and transition metal elements are uniformly dispersed in the solid solutions.
The nano high-entropy oxide material prepared by the method is formed by stacking layered single-phase metal oxide crystal solid solutions, and the transition metal element is uniformly dispersed in the solid solutions. The nanometer high-entropy oxide material has the advantages of single phase, good crystallinity, small particle size, uniform distribution and abundant metal catalytic active sites, can be used for rapidly catalytically converting polysulfide, inhibiting the shuttle effect of polysulfide, and is beneficial to improving the discharge capacity and the cycle life of a battery when being applied to a lithium-sulfur battery.
In some embodiments, the nanometer high-entropy oxide material has the particle size of 100-500 nm, small particle size, large specific surface area, uniform particle size distribution and high uniformity. In some embodiments, the particle size of the nano high-entropy oxide material includes, but is not limited to, 100 to 200nm, 200 to 300nm, 300 to 400nm, 400 to 500nm, and the like.
In a third aspect of the embodiments of the present application, a positive electrode material for a lithium-sulfur battery is provided, where raw material components for preparing the positive electrode material for the lithium-sulfur battery include: the nanometer high-entropy oxide material prepared by the method or the nanometer high-entropy oxide material, the sulfur source and the conductive agent.
The positive electrode material of the lithium-sulfur battery provided by the third aspect of the embodiment of the application is prepared by taking the nanometer high-entropy oxide material, the sulfur source and the conductive agent as raw materials. The nano high-entropy oxide material doped in the lithium-sulfur battery anode material has rich metal catalytic active sites, has a rapid catalytic conversion effect on polysulfide, can inhibit the shuttle effect of the polysulfide, and improves the discharge capacity and cycle life of the lithium-sulfur battery.
In some embodiments, the mass ratio of the nano high-entropy oxide material, the sulfur source and the conductive agent is (5-15): (65-75): (15-30); the nanometer high-entropy oxide material plays a role in catalytic conversion and anchoring polysulfide in a lithium-sulfur battery cathode material system, and does not provide battery discharge capacity. The higher content of the nano high-entropy oxide can reduce the specific capacity of the lithium-sulfur battery anode material, thereby reducing the energy density of the battery; the conductive agent can provide a channel for electron transmission and migration in the anode of the lithium-sulfur battery, so that the charge and discharge efficiency of the battery is improved.
In some embodiments, the sulfur source is selected from sulfur powder; the elemental sulfur has higher active sulfur content than other sulfur-containing compounds, and is favorable for improving the specific capacity of the anode material of the lithium-sulfur battery.
In some embodiments, the conductive agent comprises at least one of ketjen black, acetylene black, conductive carbon black, carbon fibers, carbon nanotubes, conductive graphite, graphene; furthermore, keqin black is preferred, and has high conductivity, low cost and excellent comprehensive performance.
In some embodiments, the step of preparing the lithium sulfur battery positive electrode material comprises: mixing a nano high-entropy oxide material, a sulfur source and a conductive agent, putting the mixture into a high-pressure reaction kettle, heating the mixture to 155-300 ℃ at a speed of 0.5-10 ℃/min in an inert atmosphere, and filling sulfur for 1-24 hours in an oxygen-isolated manner; in the heating reaction process, sulfur molecules can be mixed with the nano high-entropy oxide material and the conductive agent to reach the level of micron, nano and even molecular, and finally the high-performance lithium-sulfur battery positive electrode material is obtained. The sulfur carrier is filled with sulfur, two processes of steam adsorption embedding and melting embedding are carried out, and the sulfur powder is rapidly melted due to the fact that the temperature rising rate is too high; the sulfur in a molten state has high viscosity, is easy to block nano high-entropy oxide particles and medium micropores among the particles, is not beneficial to sulfur steam entering pore channels of the medium micropores, cannot achieve the mixing of micron, nano or even molecular level between the active sulfur material and the nano high-entropy oxide, and is not beneficial to the capacity exertion of the active sulfur material. If the heat preservation temperature is too high, more energy electric energy is needed to keep the temperature of the reaction kettle, which is not beneficial to energy conservation. If the temperature rise rate is too slow or the heat preservation temperature is too low, the reaction efficiency is low, and the sulfur filling effect of the sulfur carrier is poor.
In some embodiments, the lithium sulfur battery positive electrode material provided in the above embodiments of the present application is applied to a lithium sulfur battery to obtain a lithium sulfur battery.
In some specific embodiments, the above-mentioned lithium-sulfur battery positive electrode material and a binder such as polyvinylidene fluoride (PVDF) are mixed according to a mass ratio, then fully ground and mixed, an appropriate amount of solvent such as N-methylpyrrolidone (NMP) is added dropwise to disperse and mix to prepare a positive electrode slurry, the positive electrode slurry is uniformly coated on a current collector such as an aluminum foil, and vacuum drying treatment (for example, drying temperature is 60 ℃, drying time is 8 hours) is performed to obtain a positive electrode sheet. Then mixing with a negative pole piece such as a metal lithium sheet and a battery diaphragm such as a polypropylene microporous membrane, wherein the battery diaphragm contains 1wt% of LiNO 3 And electrolyte such as 1mol/L LiTFSI (lithium bis (trifluoromethanesulfonylimide)/DOL (cyclic ether 1,3 dioxolane) and DME (ethylene glycol dimethyl ether) (the volume ratio is 1:1) are assembled into the lithium-sulfur battery in a glove box.
In order to make the details and operation of the above-mentioned embodiments of the present application clearly understandable to those skilled in the art, and to make the advanced performance of the nano high-entropy oxide material, the preparation method and the application thereof in the embodiments of the present application significantly manifest, the above-mentioned technical solutions are exemplified by a plurality of embodiments below.
Example 1
A nanometer high-entropy oxide material is prepared by the following steps:
1. weighing Ni (NO) with purity of 98% 3 ) 2 ·6H 2 O(0.015mmol，4.45mg)、Zn(NO 3 ) 2 ·6H 2 O (0.015mmol, 4.55mg) and Co (NO) of 99% purity 3 ) 2 ·6H 2 O(0.015mmol，4.41mg)、Cu(NO 3 ) 2 ·3H 2 O(0.015mmol，3.66mg)、Mg(NO 3 ) 2 ·6H 2 O (0.015mmol, 3.89mg) powder is respectively added into 6ml of dimethylformamide/ethanol mixed solution with the volume ratio of 3/1 for ultrasonic treatment for 25min to respectively form uniform nitrate precursor solution.
2. 1.59mg of 98% pure organic ligand bipyridine and 10mg of surfactant polyvinylpyrrolidone were weighed and put into a glass bottle having a volume of 50 ml. And (3) respectively dripping the nitrate precursor solution into a glass bottle to form a solution A.
3. 4.08mg of 98% pure tetrakis (4-carboxyphenyl) porphyrin was weighed and dissolved in 10ml of a 3/1 volume dimethylformamide/ethanol mixed solution to form 0.5mmol/L solution B.
4. And (3) dripping the solution B into the solution A, sealing, carrying out ultrasonic treatment for 25min, then putting the solution B into an oven, carrying out solvothermal constant-temperature reaction for 24h at the temperature of 80 ℃, cooling to room temperature, carrying out centrifugal separation on the reaction liquid at 8000r/min, washing for 3 times by using absolute ethyl alcohol, removing a surfactant, and then drying the obtained material in the oven at the constant temperature of 60 ℃ for 12h to obtain the red organic metal framework template material.
4. Calcining the organic metal framework template material at 850 ℃ for 10h under the condition of introducing oxygen, and slowly cooling to room temperature to obtain black nano high-entropy oxide (Ni) 0.2 Co 0.2 Cu 0.2 Mg 0.2 Zn 0.2 ) O (noted HEO 850); the calcining equipment adopts a tubular furnace, the calcining crucible adopts an alumina crucible, and the temperature rise rate of the tubular furnace is 10 ℃/min.
A lithium sulfur positive electrode material, prepared by the steps of:
mixing a nanometer high-entropy oxide material HEO850, sulfur powder and Keqin black according to the weight ratio of 10:70:20, ball milling for 6 hours in a ball mill at the rotating speed of 300r/min, fully mixing and then placing in a high-pressure reaction kettle. Then, vacuumizing the interior of the high-pressure reaction kettle, introducing inert gas, and discharging oxygen in the high-pressure reaction kettle; heating to 155 ℃ at the heating rate of 1 ℃/min, preserving the heat for 12h, and naturally cooling to room temperature to obtain the lithium-sulfur battery cathode material (recorded as HEO 850/S/KB).
A lithium sulfur battery prepared by the steps of:
the lithium-sulfur battery positive electrode material HEO850/S/KB and polyvinylidene fluoride (PVDF) are fully ground and mixed according to the mass ratio of 9:1, then a proper amount of N-methyl pyrrolidone (NMP) is dropwise added to be dispersed and mixed to prepare slurry, the slurry is uniformly coated on an aluminum foil, and vacuum drying treatment is carried out (the drying temperature is 60 ℃ and the drying time is 8 hours) to obtain the positive electrode piece. Taking a metal lithium sheet as a negative pole piece, taking a polypropylene microporous membrane Celgard2400 as a battery diaphragm and containing 1wt% of LiNO 3 And 1mol/L of LiTFSI/DOL: DME (volume ratio of 1:1) is used as an electrolyte. And (3) finishing assembling the CR-2025 button cell in a glove box in an argon environment to obtain the lithium-sulfur battery.
Example 2
A nano high-entropy oxide material, which differs from example 1 in that: in the step 4, the organic metal framework template material is calcined for 10 hours at 1000 ℃ under the condition of introducing oxygen, and is slowly cooled to the room temperature;
the other preparation steps and conditions are the same as those of the example 1, and the prepared black nano high-entropy oxide is (Ni) 0.2 Co 0.2 Cu 0.2 Mg 0.2 Zn 0.2 ) O (noted as HEO 1000).
A lithium sulfur positive electrode material and a lithium sulfur battery, which are different from example 1 in that: the nano high-entropy oxide material HEO1000 prepared in example 2 is adopted to replace the nano high-entropy oxide material HEO850 in example 1.
Example 3
A nano high-entropy oxide material, which differs from example 1 in that: weighing Ni (NO) with purity of 98% in step 1 3 ) 2 ·6H 2 O(0.0188mmol，5.56mg)、Zn(NO 3 ) 2 ·6H 2 O (0.0141mmol, 4.27mg) and Co (NO) of 99% purity 3 ) 2 ·6H 2 O(0.0141mmol，4.14mg)、Cu(NO 3 ) 2 ·3H 2 O(0.0141mmol，3.43mg)、Mg(NO 3 ) 2 ·6H 2 O (0.0141mmol, 3.64mg) powder was added to 7.5ml, 5.625ml, 5.64mg625ml and 5.625ml of dimethyl formamide/ethanol mixed solution with the volume ratio of 3/1 are subjected to ultrasonic treatment for 25min to form uniform nitrate precursor solution.
The other preparation steps and conditions are the same as those of the example 1, and the prepared black nano high-entropy oxide is (Ni) 0.25 Co 0.1875 Cu 0.1875 Mg 0.1875 Zn 0.1875 ) O (noted as HEO 850-1).
A lithium sulfur cathode material and a lithium sulfur battery, differing from example 1 in that: the nanometer high-entropy oxide material HEO850-1 prepared in example 3 is adopted to replace the nanometer high-entropy oxide material HEO850 in example 1.
Example 4
A nano high-entropy oxide material, which differs from example 1 in that: weighing Ni (NO) with purity of 98% in step 1 3 ) 2 ·6H 2 O(0.0188mmol，5.56mg)、Zn(NO 3 ) 2 ·6H 2 O (0.0141mmol, 4.27mg) and Co (NO) of 99% purity 3 ) 2 ·6H 2 O(0.0141mmol，4.14mg)、Cu(NO 3 ) 2 ·3H 2 O(0.0141mmol，3.43mg)、Mg(NO 3 ) 2 ·6H 2 O (0.0141mmol, 3.64mg) powder is respectively added into 7.5ml, 5.625ml and 5.625ml of dimethylformamide/ethanol mixed solution with the volume ratio of 3/1 for ultrasonic treatment for 25min to form uniform nitrate precursor solution;
in the step 4, the organic metal framework template material is calcined for 10 hours at 1000 ℃ under the condition of introducing oxygen, and is slowly cooled to the room temperature.
The other preparation steps and conditions are the same as those of the example 1, and the prepared black nano high-entropy oxide is (Ni) 0.25 Co 0.1875 Cu 0.1875 Mg 0.1875 Zn 0.1875 ) O (marked as HEO 1000-1).
A lithium sulfur positive electrode material and a lithium sulfur battery, which are different from example 1 in that: the nanometer high-entropy oxide material HEO1000-1 prepared in example 4 is adopted to replace the nanometer high-entropy oxide material HEO850 in example 1.
Example 5
A kind ofA nano high entropy oxide material, which differs from example 1 in that: weighing Ni (NO) with purity of 98% in step 1 3 ) 2 ·6H 2 O(0.0113mmol，3.34mg)、Zn(NO 3 ) 2 ·6H 2 O (0.0159mmol, 4.84mg) and Co (NO) of 99% purity 3 ) 2 ·6H 2 O(0.0159mmol，4.69mg)、Cu(NO 3 ) 2 ·3H 2 O(0.0159mmol，3.89mg)、Mg(NO 3 ) 2 ·6H 2 O (0.0159mmol, 4.12mg) powder is added into 4.5ml, 6.375ml and 6.375ml of dimethyl formamide/ethanol mixed solution with the volume ratio of 3/1 respectively for ultrasonic treatment for 25min to form uniform nitrate precursor solution.
The other preparation steps and conditions are the same as those of the example 1, and the prepared black nano high-entropy oxide is (Ni) 0.15 Co 0.2125 Cu 0.2125 Mg 0.2125 Zn 0.2125 ) O (noted as HEO 850-2).
A lithium sulfur positive electrode material and a lithium sulfur battery, which are different from example 1 in that: the nanometer high-entropy oxide material HEO850-2 prepared in example 5 is adopted to replace the nanometer high-entropy oxide material HEO850 in example 1.
Example 6
A nano high-entropy oxide material, which differs from example 1 in that: weighing Ni (NO) with purity of 98% in step 1 3 ) 2 ·6H 2 O(0.0113mmol，3.34mg)、Zn(NO 3 ) 2 ·6H 2 O (0.0159mmol, 4.84mg) and Co (NO) of 99% purity 3 ) 2 ·6H 2 O(0.0159mmol，4.69mg)、Cu(NO 3 ) 2 ·3H 2 O(0.0159mmol，3.89mg)、Mg(NO 3 ) 2 ·6H 2 O (0.0159mmol, 4.12mg) powder is respectively added into 4.5ml, 6.375ml and 6.375ml of dimethyl formamide/ethanol mixed solution with the volume ratio of 3/1 for ultrasonic treatment for 25min to form uniform nitrate precursor solution;
in the step 4, the organic metal framework template material is calcined for 10 hours at 1000 ℃ under the condition of introducing oxygen, and is slowly cooled to the room temperature.
The other preparation steps and conditions are the same as those of the example 1, and the prepared black nano high-entropy oxide is (Ni) 0.15 Co 0.2125 Cu 0.2125 Mg 0.2125 Zn 0.2125 ) O (note as HEO 1000-2).
A lithium sulfur positive electrode material and a lithium sulfur battery, which are different from example 1 in that: the nano high-entropy oxide material HEO1000-2 prepared in example 6 is used for replacing the nano high-entropy oxide material HEO850 in example 1.
Comparative example 1
A lithium sulfur positive electrode material, prepared by the steps of:
mixing sulfur powder and ketjen black according to a weight ratio of 70:30, ball milling for 6 hours in a ball mill at the rotating speed of 300r/min, fully mixing and then placing the mixture into a high-pressure reaction kettle. Then, vacuumizing the interior of the high-pressure reaction kettle, introducing inert gas, and discharging oxygen in the high-pressure reaction kettle; heating to 155 ℃ at the heating rate of 1 ℃/min, preserving heat for 12h, and naturally cooling to room temperature to obtain the lithium-sulfur battery cathode material (marked as S/KB).
A lithium sulfur battery prepared by the steps of:
the lithium-sulfur battery positive electrode material S/KB and polyvinylidene fluoride (PVDF) are fully ground and mixed according to the mass ratio of 9:1, then a proper amount of N-methyl pyrrolidone (NMP) is dropwise added to be dispersed and mixed to prepare slurry, the slurry is uniformly coated on an aluminum foil, and vacuum drying treatment (the drying temperature is 60 ℃ and the drying time is 8 hours) is carried out to obtain the positive electrode piece. A metal lithium sheet is taken as a cathode pole piece, a polypropylene microporous membrane Celgard2400 is taken as a battery diaphragm, and the battery diaphragm contains 1wt% of LiNO 3 And 1mol/L of LiTFSI/DOL DME (volume ratio of 1:1) is used as the electrolyte. And (3) assembling the CR-2025 button cell in a glove box in an argon environment to obtain the lithium-sulfur battery.
Further, in order to verify the advancement of the examples of the present application, the following performance tests were respectively performed on the examples and comparative examples:
1. the morphology observation is carried out on the nanometer high-entropy oxide material HEO850 prepared in the example 1, as shown in a scanning electron microscope SEM and a transmission electron microscope TEM of figures 2 and 3 of attached drawings, the particle diameter is about 300nm, the particles are small and uniform, the presentation of metal active sites is facilitated, and the catalytic conversion efficiency of polysulfide is improved.
2. X-ray powder diffraction tests are respectively carried out on the nano high-entropy oxide material HEO850 prepared in example 1, and elemental sulfur and lithium sulfur battery positive electrode material (HEO 850/S/KB), as shown in an XRD chart of fig. 4, an XRD diffraction peak of the HEO850 is relatively sharp and has no impurity peak, which indicates that the prepared nano high-entropy oxide material HEO850 has high crystallinity and high phase purity, and is a single molten salt phase nano material with high crystallinity.
3. For the lithium sulfur batteries prepared in the examples and the comparative examples, the battery performance test was performed on a charge/discharge instrument, the voltage range of the battery test was 1.7V to 2.8V, and the test results are shown in table 1:
TABLE 1
From the test results, it can be seen that the lithium-sulfur batteries prepared according to examples 1 to 6 based on the nano high-entropy oxide material exhibit better capacity retention rate and higher average coulombic efficiency, compared to comparative example 1 in which the nano high-entropy oxide material is not added. In particular, the lithium-sulfur battery prepared in example 1 has a capacity retention rate of 91% or more after being cycled for 100 weeks at 0.5C, a capacity retention rate of 71% after 800 cycles, an average coulombic efficiency of 99.5%, a very high reversible specific capacity and excellent cycling stability (as shown in a cycling performance graph at 0.5C of fig. 5). And the first-circle discharge capacity of 0.1C at 25 ℃ can reach 1421mAh/g (as shown in a first-circle charge-discharge curve chart of 0.1C in attached figure 6), which is much higher than the specific capacity of the anode material of the conventional lithium ion battery. The discharge specific capacity under 1C is up to 930mAh/g, which is 65% of the discharge specific capacity of 0.1C, and the discharge performance is better (as shown in the rate performance graph of figure 7).
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A preparation method of a nanometer high-entropy oxide material is characterized by comprising the following steps:
dissolving precursors of at least five transition metals in a solvent to prepare a metal precursor solution;
mixing the metal precursor solution with an organic ligand containing an organic functional group, a surfactant and an auxiliary bridging ligand, and performing solvothermal reaction to form coordination connection to obtain an organic metal framework template material;
and calcining the organic metal framework template material in an oxygen atmosphere at the temperature of below 1000 ℃ to obtain the nano high-entropy oxide material.
2. The method for preparing a nano high-entropy oxide material according to claim 1, wherein the mass ratio of the metal precursor, the organic ligand, the surfactant and the auxiliary bridging ligand in the metal precursor solution is (15-30): 1-2): 5-15): 2-6;
and/or the transition metal is selected from at least five of nickel, cobalt, copper, magnesium, zinc, titanium, manganese and iron;
and/or the precursor form of the transition metal comprises at least one of nitrate, phosphate, sulfate and chloride;
and/or the solvent comprises at least one of dimethylformamide, ethanol, diethylformamide, methanol, propanol and isopropanol;
and/or the organic ligand containing organic functional groups comprises at least one of organic metal framework ligand containing hydroxyl, organic metal framework ligand containing carboxyl, organic metal framework ligand containing amido and organic metal framework ligand containing pyridyl;
and/or the surfactant comprises at least one of a nonionic surfactant, a cationic surfactant and an anionic surfactant;
and/or the auxiliary bridging ligand comprises at least one of porphyrin ligand, sulfonic acid-containing organometallic framework ligand, phosphoric acid-containing organometallic framework ligand and carboxylic acid nitrogen-containing mixed organometallic framework ligand.
3. A method for producing a nano high-entropy oxide material according to claim 2, wherein the solvent is selected from a mixed solvent of dimethylformamide and ethanol;
and/or the nonionic surfactant comprises at least one of polyvinylpyrrolidone, poloxamer, polyether P123, span 80, polyethylene glycol dodecyl ether, polyethylene glycol dialkyl ester, polyethylene glycol dilaurate, polyethylene glycol 2-ethylhexyl ether and sorbitan alkyl ester;
and/or the cationic surfactant comprises at least one of hexadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium bromide, didodecyl dimethyl ammonium bromide and hexadecyl trimethyl ammonium bromide;
and/or the anionic surfactant comprises at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, lithium dodecyl sulfate, sodium octyl sulfate, sodium decyl sulfate, sodium 1-butane sulfonate and sodium butyl naphthalene sulfonate.
4. A process for the preparation of a nano high entropy oxide material according to claim 3, wherein the organic ligand is selected from bipyridine;
and/or, the auxiliary bridging ligand is selected from tetrakis (4-carboxyphenyl) porphyrin;
and/or, the surfactant is selected from polyvinylpyrrolidone;
and/or the solvent is selected from a mixed solvent of dimethylformamide and ethanol with the volume ratio of (1-10) to 1;
and/or the concentration of the metal precursor solution is 0.1-5 mmol/L.
5. The method for preparing a nano high-entropy oxide material of any one of claims 1 to 4, wherein the step of preparing the metal precursor solution includes: respectively dissolving precursors of five transition metals in the solvent to respectively prepare precursor solutions of the five transition metals;
and/or, the solvothermal reaction conditions include: reacting for 12 to 48 hours at the temperature of between 60 and 140 ℃;
and/or, the conditions of the calcination treatment include: in oxygen atmosphere, heating to 450-1000 ℃ at the speed of 5-10 ℃/min, and then preserving heat for 10-24 hours.
6. The method for preparing a nano high-entropy oxide material of claim 5, wherein the mixing treatment step includes: adding the organic ligand and the surfactant into a reaction vessel, respectively adding the metal precursor solutions of different transition metals, preparing the auxiliary bridging ligand into a solution, adding the solution into the reaction vessel, sealing and performing ultrasonic dispersion treatment;
and/or the molar ratio of the precursors of the five transition metals is (0.15-0.25): (0.15 to 0.25): (0.15 to 0.25): (0.15 to 0.25): (0.15-0.25).
7. A nano high-entropy oxide material obtained by the method according to any one of claims 1 to 6, wherein the nano high-entropy oxide material is formed by stacking layered single-phase metal oxide crystalline solid solutions, and transition metal elements are uniformly dispersed in the solid solutions.
8. The nano high-entropy oxide material of claim 7, wherein the nano high-entropy oxide material has a particle size of 100 to 500nm.
9. The positive electrode material for the lithium-sulfur battery is characterized by comprising the following raw material components: a nano high-entropy oxide material prepared by the method according to any one of claims 1 to 6 or a nano high-entropy oxide material according to any one of claims 7 to 8, a sulfur source and a conductive agent.
10. The positive electrode material for a lithium-sulfur battery according to claim 9, wherein the mass ratio of the nano high-entropy oxide material, the sulfur source and the conductive agent is (5-15): (65-75): (15-30);
and/or, the sulfur source is selected from sulfur powder;
and/or the conductive agent comprises at least one of Ketjen black, acetylene black, conductive carbon black, carbon fiber, carbon nanotube, conductive graphite and graphene;
and/or, the step of preparing the lithium-sulfur battery positive electrode material comprises: and mixing the nano high-entropy oxide material, the sulfur source and the conductive agent, putting the mixture into a high-pressure reaction kettle, heating the mixture to 155-300 ℃ at the speed of 0.5-10 ℃/min in an inert atmosphere, and filling sulfur for 1-24 h in an oxygen-isolated manner to obtain the lithium-sulfur battery cathode material.
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