WO2020124394A1 - 过渡金属硫属化物纳米片层材料及其制备方法、电池负极材料、二次电池及其应用 - Google Patents

过渡金属硫属化物纳米片层材料及其制备方法、电池负极材料、二次电池及其应用 Download PDF

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WO2020124394A1
WO2020124394A1 PCT/CN2018/121865 CN2018121865W WO2020124394A1 WO 2020124394 A1 WO2020124394 A1 WO 2020124394A1 CN 2018121865 W CN2018121865 W CN 2018121865W WO 2020124394 A1 WO2020124394 A1 WO 2020124394A1
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transition metal
sodium
potassium
carbon
chloride
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French (fr)
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唐永炳
童小玉
欧学武
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of molybdenum
    • C01G39/06—Sulfides
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • 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

Definitions

  • the present application belongs to the technical field of transition metal chalcogenides, and in particular relates to a transition metal chalcogenide nanosheet material and preparation method thereof, battery negative electrode materials, secondary batteries and applications thereof.
  • Graphene-like layered materials refer to inorganic compounds with a layered crystal structure similar to graphite, mainly including metal chalcogenides, silene, germane, boron nitride, etc.
  • metal chalcogenides including transition metal sulfides, transition metal selenides, and transition metal tellurides
  • transition metal chalcogenides are considered to be ideal materials for battery anodes due to their large interlayer spacing and high specific capacity.
  • Transition metal chalcogenides such as MoS 2 , MoSe 2 , VS 2 , WS 2 , WSe 2 , SnS 2 etc., in lithium ion batteries, sodium ion batteries, potassium ion batteries, calcium ion batteries, magnesium ion batteries, zinc ion batteries and Dual ion batteries and other fields have shown excellent electrochemical performance.
  • the layered material synthesis methods currently used mainly include chemical vapor deposition and hydrothermal synthesis.
  • the yield of chemical vapor deposition is limited, it is difficult to apply on a large scale, and is not suitable for industrial applications; the size, thickness and morphology of the layered material obtained by the hydrothermal synthesis method are difficult to control. Therefore, there is an urgent need to develop new methods for synthesizing layered materials for preparing layered materials with a few-layer structure.
  • Patent CN105460921B in the prior art first uses carbon nanotubes in concentrated acid and potassium permanganate to prepare graphene oxide nanoribbons, and then combines the molybdenum selenide with the graphene nanosheets by hydrothermal reaction to prepare the molybdenum selenide nanosheets .
  • the method has complicated operation steps, takes a long time, and requires the use of concentrated sulfuric acid and other chemical reagents, which is dangerous to operate, and the carbon nanotubes are expensive and difficult to promote.
  • Patent CN106816602A prepared a molybdenum diselenide/carbon composite material, using silica nanoparticles as a template, and then etching silicon dioxide with hydrofluoric acid or hot concentrated alkali.
  • the first object of the present application is to provide a method for preparing a transition metal chalcogenide nanosheet material, which can overcome the above problems or at least partially solve the above technical problems.
  • the second object of the present application is to provide the transition metal chalcogenide nanosheet material obtained by the above preparation method.
  • the transition metal chalcogenide nanosheet material has high purity, uniform sheet structure size, uniform thickness and thin thickness. Controllable appearance.
  • the third object of the present application is to provide a battery anode material including the above transition metal chalcogenide nanosheet material, which can relieve the bulk material volume caused by intercalation/deintercalation of ions during charge and discharge Expansion pulverization, thereby improving battery performance.
  • the fourth object of the present application is to provide a secondary battery including the above battery negative electrode material.
  • the secondary battery including the above battery negative electrode material has a high specific capacity and excellent cycle performance.
  • the fifth object of the present application is to provide the application of the above secondary battery in electronic equipment, electric tools or electric vehicles.
  • a method for preparing a transition metal chalcogenide nanosheet material including the following steps:
  • the raw material includes a chalcogen precursor and a transition metal precursor
  • the raw material in the method further includes a carbon material to obtain a carbon-coated transition metal chalcogenide nanosheet material.
  • the chalcogen element precursor includes a chalcogen element monomer and/or a chalcogen element-containing compound
  • the chalcogen element monomer includes at least one of sulfur, selenium or tellurium, preferably sulfur;
  • the chalcogen element-containing compound includes thiourea, thiol, ammonium sulfide, sodium sulfide, potassium sulfide, ammonium sulfite, sodium sulfite, potassium sulfite, ammonium persulfate, sodium persulfate, potassium persulfate, selenium Urea, selenol, ammonium selenide, sodium selenide, potassium selenide, ammonium selenite, sodium selenite, potassium selenite, ammonium perselenoate, sodium perselenoate, potassium perselenoate, tellurium urea, At least one of tellurol, ammonium telluride, sodium telluride, potassium telluride, ammonium tellurite, sodium tellurite, potassium tellurite, ammoniumaulate, sodium shovelate, or potassium conditionerlate, Preferred are thiourea, thiol, ammonium sulfide
  • the chalcogen element precursor is in the form of a chalcogen element precursor solution
  • the solvent of the chalcogen element precursor solution includes at least one of water, ethanol, dimethylamine, diethylamine, hydrazine hydrate, sodium borohydride, dimethylformamide or tetrahydrofuran.
  • the transition metal precursor includes at least one of soluble molybdenum source, tungsten source, vanadium source, tin source, cobalt source, iron source, zinc source or antimony source;
  • the molybdenum source includes molybdate, dimolybdate, tetramolybdate, pentamolybdate, heptamolybdate, octamolybdate, paramolybdate, phosphomolybdate, and tetrasulfomolybdenum.
  • the tungsten source includes at least one of phosphotungstate, tetrathiotungstate, tungstate or tungsten trioxide;
  • the vanadium source includes at least one of vanadate, vanadium sulfate or vanadyl oxalate;
  • the tin source includes at least one of stannate, tin chloride, tin oxalate, tin sulfate or tin nitrate;
  • the source of cobalt includes at least one of cobalt carbonate, cobalt nitrate, cobalt sulfate or cobalt chloride;
  • the iron source includes at least one of ferric chloride, ferric nitrate or ferric sulfate;
  • the zinc source includes at least one of zinc chloride, zinc nitrate or zinc sulfate;
  • the antimony source includes at least one of antimony chloride, antimony nitrate, antimony sulfate or antimonate.
  • the soluble salt includes a soluble salt of a main group metal, preferably at least one of chloride, bromide, sulfate, nitrate, phosphate or carbonate;
  • the chloride salt includes at least one of sodium chloride, potassium chloride, barium chloride, calcium chloride, magnesium chloride or aluminum chloride, preferably sodium chloride and/or potassium chloride;
  • the bromide salt includes at least one of sodium bromide, potassium bromide, barium bromide, calcium bromide, magnesium bromide or aluminum bromide;
  • the sulfate salt includes at least one of sodium sulfate, potassium sulfate, magnesium sulfate or aluminum sulfate;
  • the nitrate includes at least one of sodium nitrate, potassium nitrate, barium nitrate, calcium nitrate, magnesium nitrate or aluminum nitrate;
  • the phosphate includes at least one of sodium phosphate, potassium phosphate, calcium phosphate, aluminum phosphate or magnesium phosphate;
  • the carbonate includes sodium carbonate and/or potassium carbonate
  • the carbon material includes a carbon element and/or a carbon-containing compound
  • the carbon simple substance includes graphite, expanded graphite, graphene, mesophase carbon microsphere graphite, acetylene carbon black, glassy carbon, carbon-carbon composite material, activated carbon, hard carbon, carbon black, carbon nanotube, carbon nanofiber Or at least one of mesoporous carbon;
  • the carbon-containing compound includes glucose, sucrose, starch, polyoxyethylene, polyethylene glycol, glycerin, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxymethyl propyl cellulose, polyethylene At least one of alcohol, polypropylene, phenol resin, or epoxy resin.
  • the molar ratio of the transition metal in the transition metal precursor to the chalcogen in the chalcogen precursor is 0.3-1:1, preferably 0.35-0.8:1;
  • the molar ratio of the soluble salt to the transition metal in the transition metal precursor is 100-1000:1, preferably 200-500:1, further preferably 300:1;
  • the molar ratio of the chalcogen element in the chalcogen element precursor to the carbon element in the carbon material is 1:1-10, preferably 1:2-8.
  • the sintering temperature is 400-800°C, preferably 550-650°C;
  • the sintering time is 1-3h, preferably 2h;
  • the sintered gas atmosphere is a mixed gas of hydrogen and protective gas
  • the protective gas includes nitrogen and/or argon;
  • the volume fraction of hydrogen is 1%-10%, preferably 5%-8%.
  • a transition metal chalcogenide nanosheet material obtained by the above preparation method is provided.
  • a battery anode material which includes the above transition metal chalcogenide nanosheet material.
  • a secondary battery including the above-mentioned battery negative electrode material
  • the secondary battery includes a lithium ion battery, a sodium ion battery, a potassium ion battery, a calcium ion battery, a magnesium ion battery or a zinc ion battery;
  • the secondary battery includes a lithium-based dual-ion battery, a sodium-based dual-ion battery, a potassium-based dual-ion battery, a calcium-based dual-ion battery, a magnesium-based dual-ion battery, or a zinc-based dual-ion battery.
  • the application of the above-mentioned secondary battery in electronic equipment, electric tools or electric vehicles is provided.
  • the present application provides a method for preparing a transition metal chalcogenide nanosheet material.
  • the chalcogen element precursor and the transition metal precursor are dissolved in an aqueous solution of a soluble salt, the water is removed to obtain a solid, and then sintered to obtain a transition metal sulfur Belongs to the chemical nanosheet material.
  • the preparation method uses soluble salts as a template agent, which is cheap, environmentally friendly, easy to remove in post-processing, and the thickness of the obtained transition metal chalcogenide nanosheet material is thinner.
  • the preparation method greatly shortens the synthesis period, has the characteristics of simple and easy to implement, controllable, and high yield.
  • the experimental operation is simple and suitable for large-scale production.
  • the transition metal chalcogenide nanosheet material prepared by this method has high purity, uniform sheet structure size, uniform thickness, fewer layers, and controllable morphology. It can be used in the negative electrode of the battery to relieve the charge and discharge process. As the intercalation/deintercalation of ions causes volume expansion and pulverization to improve the performance of the battery, it will show a higher specific capacity and excellent cycle performance. In addition, compared with traditional graphite anodes, transition metal chalcogenides have the advantages of large layer spacing and high theoretical capacity.
  • the transition metal chalcogenide nanosheet material prepared by this method can be used as the negative electrode material of lithium ion battery, sodium ion battery, potassium ion battery, calcium ion battery, magnesium ion battery, zinc ion battery and dual ion battery, which can alleviate
  • the bulk material is pulverized due to the volume expansion caused by the intercalation/deintercalation of ions during the charging and discharging process, thereby improving the performance of the battery, making the battery have a high specific capacity and excellent cycle performance.
  • Example 1 is a scanning electron micrograph of the molybdenum diselenide nanosheet material in Example 1 of the present application;
  • Example 2 is an X-ray diffraction pattern of the molybdenum diselenide nanosheet material in Example 1 of the present application;
  • Example 3 is a scanning electron microscope image of carbon-coated molybdenum diselenide nanosheet material in Example 2 of the present application;
  • FIG. 4 is the electrochemical performance of a half-cell assembled from tungsten diselenide nanosheets obtained in Example 7 of this application.
  • the numerical range “a-b” represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers.
  • the numerical range “400-800” means that all real numbers between “400-800” have been listed in this article, and "400-800” is just an abbreviated representation of these numerical combinations.
  • the forms of the "lower limit” and the upper limit disclosed in the “range” of this application may be one or more lower limits and one or more upper limits, respectively.
  • each reaction or operation step may be performed sequentially or in order.
  • the reaction methods herein are performed sequentially.
  • a method for preparing a transition metal chalcogenide nanosheet material including the following steps:
  • the raw materials include chalcogen precursors and transition metal precursors.
  • the preparation method uses soluble salts as a template agent, which is cheap, environmentally friendly, easy to remove in post-processing, and the thickness of the obtained transition metal chalcogenide nanosheet material is thinner. Compared with the traditional silica template method and hydrothermal method, the preparation method greatly shortens the synthesis period, has the characteristics of simple and easy to implement, controllable, and high yield. The experimental operation is simple and suitable for large-scale production.
  • the transition metal chalcogenide nanosheet material can be written as M x R y , where M is at least one of the transition metals molybdenum, tungsten, vanadium, tin, cobalt, iron, zinc, or antimony, and R is At least one of sulfur, selenium or tellurium, the values of x and y can make the algebraic sum of the positive and negative valences of the elements in MxRy zero.
  • M may be one of the transition metals, or two, for example, MoSe 2 , MoWSe 4, etc.
  • the method for removing water is not limited.
  • the water can be removed by freeze drying or steam drying.
  • the temperature should be reduced, for example, the temperature can be reduced to room temperature, and then washed with water.
  • the salt template can be removed by water washing, and then dried after washing to obtain the transition metal chalcogenide nanosheet material.
  • the existence form of the chalcogen precursor is not limited, and may exist in the form of a chalcogen element monomer, for example, it may be monomer sulfur, monomer selenium or monomer tellurium, or it may be a chalcogen element-containing compound
  • a chalcogen element monomer for example, it may be monomer sulfur, monomer selenium or monomer tellurium, or it may be a chalcogen element-containing compound
  • thiourea, thiol ammonium sulfide, sodium sulfide, potassium sulfide, ammonium sulfite, sodium sulfite, potassium sulfite, ammonium persulfate, sodium persulfate, potassium persulfate, selenium urea, selenol , Ammonium selenide, sodium selenide, potassium selenide, ammonium selenite, sodium selenite, potassium selenite, ammonium perseleno
  • the chalcogen element precursor may exist in the form of a chalcogen element precursor solution; the solvent of the chalcogen element precursor solution is not limited as long as it can dissolve the chalcogen element precursor.
  • the solvent of the chalcogen element precursor solution may be water, ethanol, dimethylamine, diethylamine, hydrazine hydrate, sodium borohydride, dimethylformamide, tetrahydrofuran, or the like.
  • the dissolution form of the transition metal precursor is not limited, and it may be a transition metal precursor solid, that is, the transition metal precursor solid is directly added to the aqueous solution of the soluble salt, or it may be an aqueous solution of the transition metal precursor, that is, the aqueous solution of the transition metal precursor is added to the soluble Salt solution.
  • the type of the transition metal precursor is not limited, and may be a soluble source of molybdenum, tungsten, vanadium, tin, cobalt, iron, zinc, or antimony.
  • the source of molybdenum includes but is not limited to molybdate, Dimolybdate, tetramolybdate, pentamolybdate, heptamolybdate, octamolybdate, paramolybdate, phosphomolybdate, tetrathiomolybdate or molybdenum trioxide
  • tungsten sources include but not Limited to phosphotungstate, tetrathiotungstate, tungstate or tungsten trioxide
  • vanadium sources include but are not limited to vanadate, vanadium sulfate or vanadyl oxalate
  • tin sources include but are not limited to stannate, chloride Tin, tin oxalate, tin sulfate or
  • mobdate dimolybdate, tetramolybdate, pentamolybdate, heptamolybdate, octamolybdate, paramolybdate, phosphomolybdate, tetrathiomolybdate Salts, phosphotungstates, tetrathiotungstates, tungstates, vanadates, stannates or antimonates, etc.
  • the molybdate can be sodium molybdate, molybdenum Potassium acid, lithium molybdate, aluminum molybdate, iron molybdate, cadmium molybdate, manganese molybdate, magnesium molybdate, zinc molybdate, calcium molybdate, ammonium molybdate.
  • ammonium molybdate may be ammonium molybdate without bound water, or ammonium molybdate with bound water, for example, may be molybdenum tetrahydrate Ammonium acid.
  • the "soluble salt” is not limited, for example, it may be a soluble salt of a main group metal, for example, chloride, bromide, sulfate, nitrate, phosphate or carbonate
  • chloride includes but is not limited to chlorine Sodium chloride, potassium chloride, barium chloride, calcium chloride, magnesium chloride or aluminum chloride
  • bromide salts include but are not limited to sodium bromide, potassium bromide, barium bromide, calcium bromide, magnesium bromide or bromide
  • Aluminum sulfate includes but not limited to sodium sulfate, potassium sulfate, magnesium sulfate or aluminum sulfate
  • nitrate includes but not limited to sodium nitrate, potassium nitrate, barium nitrate, calcium nitrate, magnesium nitrate or aluminum nitrate
  • phosphate includes but not limited to Sodium phosphate, potassium phosphate, calcium phosphate, aluminum phosphate or magnesium phosphate
  • the form of existence of the raw material is not limited, and it may be a solid or a solution as long as it can be dissolved in an aqueous solution of a soluble salt. Since the raw materials include chalcogen precursors and transition metal precursors, the order and manner of adding chalcogen precursors and transition metal precursors to the aqueous solution of soluble salts are not limited.
  • the chalcogen precursors is added to the soluble salt aqueous solution; it may be a solution of the chalcogen precursor and the transition metal precursor added to the soluble salt solution in sequence; it may be a solution of the chalcogen precursor and the transition metal precursor added to the soluble at the same time In the saline solution; it may be that the solution of the transition metal precursor and the chalcogen precursor is added to the soluble salt solution in sequence; it may be that the solution of the chalcogen precursor and the solution of the transition metal precursor are added to the soluble salt solution in sequence .
  • the container for placing the solid during sintering is not limited.
  • an alumina ceramic boat may be used to place the solid and then sintering.
  • the instrument for sintering is not limited, for example, a high-temperature tube furnace can be used for sintering.
  • the raw material in the method further includes a carbon material to obtain a carbon-coated transition metal chalcogenide nanosheet material.
  • the carbon-coated transition metal chalcogenide nanosheet material can be written as M x R y @C, where M is the transition metal of molybdenum, tungsten, vanadium, tin, cobalt, iron, zinc, or antimony. At least one, R is at least one of sulfur, selenium, or tellurium, and the values of x and y can make the algebraic sum of the positive and negative valences of each element in M x R y be zero.
  • a transition metal M may be one, two may be, for example, may be MoSe 2 @ C, MoWSe 4 @C like.
  • the sheet material and the carbon material are compounded to obtain different composite structures, and chalcogenide materials containing various transition metals can be synthesized.
  • carbon materials which may be simple carbon or carbon-containing compounds
  • simple carbon includes but is not limited to graphite, expanded graphite, graphene, mesophase carbon microsphere graphite, acetylene carbon black, glassy carbon, carbon Carbon composites, activated carbon, hard carbon, carbon black, carbon nanotubes, carbon nanofibers or mesoporous carbon
  • carbon-containing compounds include but are not limited to glucose, sucrose, starch, polyoxyethylene, polyethylene glycol, glycerin, Carboxymethyl cellulose, hydroxyethyl cellulose, hydroxymethyl propyl cellulose, polyvinyl alcohol, polypropylene, phenolic resin or epoxy resin.
  • the chalcogen monomer is sulfur;
  • the chalcogen-containing compounds include thiourea, thiol, ammonium sulfide, sodium sulfide, potassium sulfide, ammonium sulfite, sodium sulfite, potassium sulfite, ammonium persulfate , Sodium persulfate, potassium persulfate, selenium urea, sodium selenium, tellurium or sodium tellurium.
  • the transition metal chalcogenide nanoplate material obtained by the monomer sulfur or the chalcogen element-containing compound has the advantages of more uniform size and thinner layer.
  • the chloride salt is sodium chloride and/or potassium chloride.
  • Sodium chloride and/or potassium chloride as a template agent are inexpensive, environmentally friendly, easy to remove in post-processing, and have high solubility of sodium chloride and/or potassium chloride, which is beneficial to the preparation of sheet materials with uniform size of nanosheets .
  • the molar ratio of the transition metal in the transition metal precursor to the chalcogen in the chalcogen precursor is 0.3-1:1.
  • the molar ratio of transition metal in the transition metal precursor to chalcogen in the chalcogen precursor is 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8: 1. 0.9:1 or 1:1.
  • the purity of the obtained transition metal chalcogenide nanosheet material is higher. If the proportion of the transition metal is too high or too low, the raw material reaction will be incomplete, and the yield of the sheet-forming structural material will be reduced.
  • the molar ratio of the transition metal in the transition metal precursor to the chalcogen in the chalcogen precursor is 0.35-0.8:1.
  • the molar ratio of soluble salt to chalcogen in the chalcogen precursor is 100-1000:1.
  • the molar ratio of soluble salt to chalcogen in the chalcogen precursor is 100:1, 150:1, 200:1, 250:1, 300:1, 350:1, 400:1.
  • the resulting transition metal chalcogenide nanosheet material has a smaller size and a thinner layer.
  • the molar ratio of soluble salt to transition metal in the transition metal precursor is 200-500:1.
  • the molar ratio of soluble salt to transition metal in the transition metal precursor is 300:1;
  • the obtained transition metal chalcogenide nanosheet material has a better sheet structure and size.
  • the molar ratio of chalcogen in the chalcogen precursor to carbon in the carbon material is 1:1-10.
  • the molar ratio of chalcogen in the chalcogen precursor to carbon in the carbon material is 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10.
  • the molar ratio of chalcogen in the chalcogen precursor to carbon in the carbon material is 1:2-8.
  • the resulting transition metal chalcogenide nanosheet material structure is better.
  • the sintering temperature is 400-800°C and the sintering time is 1-3h.
  • the sintering temperature is 550-650°C and the sintering time is 2h.
  • transition metal chalcogenide nanosheet materials By rationally adjusting and optimizing the sintering temperature and time, it is beneficial to obtain transition metal chalcogenide nanosheet materials with excellent properties.
  • the sintered gas atmosphere is a mixture of hydrogen and protective gas.
  • the type of shielding gas is not limited, for example, it may be nitrogen or argon.
  • the volume fraction of hydrogen is 1%-10%, preferably 5%-8%.
  • the transition metal chalcogenide nanosheet material is obtained.
  • a transition metal chalcogenide nanosheet material obtained by the above preparation method is provided.
  • the transition metal chalcogenide nanosheet material prepared by the above method has high purity, uniform sheet structure size, uniform thickness, and controllable morphology. It can be used in the negative electrode of the battery and can relieve the insertion of ions during the charging and discharging process.
  • the volume expansion pulverization caused by the layer/deintercalation to improve the performance of the battery will show a higher specific capacity and excellent cycle performance.
  • transition metal chalcogenides compared with traditional graphite anodes, transition metal chalcogenides have the advantages of large interlayer distance and high theoretical capacity.
  • a battery negative electrode material including the above transition metal chalcogenide nanosheet material.
  • Battery anode materials including transition metal chalcogenide nanosheet materials can be used as lithium-ion batteries, sodium-ion batteries, potassium-ion batteries, calcium-ion batteries, magnesium-ion batteries, zinc-ion batteries, and dual-ion batteries to relieve the block
  • the bulk material is pulverized due to the volume expansion caused by the intercalation/deintercalation of ions during the charging and discharging process, thereby improving the performance of the battery, so that the battery has a high specific capacity and excellent cycle performance.
  • a secondary battery including the above-mentioned battery negative electrode material
  • secondary batteries include lithium ion batteries, sodium ion batteries, potassium ion batteries, calcium ion batteries, magnesium ion batteries, or zinc ion batteries; or, secondary batteries include lithium-based dual ion batteries, sodium-based dual ion batteries, potassium-based batteries Dual-ion battery, calcium-based dual-ion battery, magnesium-based dual-ion battery or zinc-based dual-ion battery.
  • the secondary battery including the above battery negative electrode material has a high specific capacity and excellent cycle performance.
  • the structural shape of the secondary battery is not limited, and may be a button battery, a column battery or a soft-pack battery.
  • the application of the above secondary battery in an electronic device, a power tool, or an electric vehicle is provided.
  • Power tools use secondary batteries as driving power to move moving parts, including but not limited to electric drills, etc.
  • electronic equipment uses secondary batteries as operating power to perform various functions, including but not limited to mobile phones, laptops, desktop computers or electronic Watches, etc.
  • electric vehicles are electric vehicles that rely on secondary batteries as the driving power source, including but not limited to electric vehicles
  • large energy storage devices use secondary batteries as energy storage units, including but not limited to substations or wind turbines, etc. .
  • a method for preparing a transition metal chalcogenide nanosheet material including the following steps:
  • the Ar/H 2 mixed gas is introduced into the tube furnace to remove the air in the tube.
  • the temperature was increased to 600°C at a heating rate of 5°C/min, and the temperature was maintained for 2 hours.
  • the carrier gas flow rate is 150sccm. After the heat preservation is completed, it is naturally cooled to room temperature.
  • FIGS. 1 and 2 The scanning electron micrograph and X-ray diffraction pattern of the obtained molybdenum diselenide nanosheet material are shown in FIGS. 1 and 2. It can be seen from FIG. 1 that the prepared nanosheet sheet is thin and uniform in size. It can be seen from FIG. 2 that the synthesized nanosheet is molybdenum diselenide.
  • a battery negative electrode material comprising the above-mentioned molybdenum diselenide nanosheet material.
  • a lithium ion battery including the above-mentioned battery negative electrode material.
  • a preparation method of transition metal chalcogenide nanosheet material includes the following steps:
  • Ammonium heptamolybdate tetrahydrate (molybdenum element in ammonium heptamolybdate tetrahydrate is 1 mmol) was dissolved in 10 mL of water, and then added to the above selenium powder solution.
  • Glucose (molar amount of element C is 8 mmol) is added to the solution, and 50 ml of saturated saline (25° C.) is continuously added to the solution, stirred and heated until the liquid is evaporated to dryness.
  • the Ar/H 2 mixed gas is introduced into the tube furnace to remove the air in the tube.
  • the temperature was increased to 600°C at a heating rate of 5°C/min, and the temperature was maintained for 2 hours.
  • the carrier gas flow rate is 150sccm. After the heat preservation is completed, it is naturally cooled to room temperature.
  • the scanning electron micrograph of the obtained carbon-coated molybdenum diselenide nanosheet material is shown in FIG. 3. It can be seen from FIG. 3 that the surface of the synthesized molybdenum diselenide nanosheets is covered with carbon layer.
  • a preparation method of transition metal chalcogenide nanosheet material includes the following steps:
  • Ammonium sulfide (2 mmol of sulfur in ammonium sulfide) was dissolved in 10 mL of water, and then added to the above blue molybdenum oxide solution.
  • the Ar/H 2 mixed gas is introduced into the tube furnace to remove the air in the tube.
  • the temperature was increased to 650°C at a heating rate of 5°C/min, and the temperature was maintained for 2 hours.
  • the carrier gas flow rate is 150sccm. After the heat preservation is completed, it is naturally cooled to room temperature.
  • a preparation method of transition metal chalcogenide nanosheet material includes the following steps:
  • the Ar/H 2 mixed gas is introduced into the tube furnace to remove the air in the tube.
  • the temperature was increased to 600°C at a heating rate of 5°C/min, and the temperature was maintained for 2 hours.
  • the carrier gas flow rate is 150sccm. After the heat preservation is completed, it is naturally cooled to room temperature.
  • Examples 5-11 are different from Example 1 in that the types of transition metal precursors are different. The details are shown in Table 1.
  • Example 1 Ammonium heptamolybdate tetrahydrate
  • Example 5 Sodium molybdate
  • Example 6 Molybdenum trioxide
  • Example 7 Ammonium paratungstate
  • Example 8 Vanadyl oxalate
  • Example 9 Tin sulfate
  • Example 10 Cobalt chloride
  • Example 11 Zinc chloride
  • Examples 12-15 are different from Example 1 in the kind of chalcogen precursors. The details are shown in Table 2.
  • a Chalcogenide precursor Transition metal chalcogenide nanosheet material Example 1 Selenium powder Molybdenum diselenide Example 12 Tellurium powder Molybdenum telluride Example 13 Sulphur powder Molybdenum disulfide Example 14 Thiourea Molybdenum disulfide Example 15 Sodium sulfide Molybdenum disulfide
  • Example 16-19 The difference between Examples 16-19 and Example 1 is that the types of soluble salts of the main group metals are different, as shown in Table 3.
  • Examples 20-24 differ from Example 1 in that the amounts of soluble salts of chalcogen precursors, transition metal precursors and main group metals are shown in Table 4.
  • a preparation method of transition metal chalcogenide nanosheet material includes the following steps:
  • the Ar/H 2 mixed gas is introduced into the tube furnace to remove the air in the tube.
  • the temperature was increased to 600°C at a heating rate of 5°C/min, and the temperature was maintained for 2 hours.
  • the carrier gas flow rate is 150sccm. After the heat preservation is completed, it is naturally cooled to room temperature.
  • Table 5 shows the sheet thickness and sheet size of the materials obtained in Examples 1-24 and Comparative Example 1.
  • Example 1 25nm 558nm
  • Example 2 10nm 600nm
  • Example 3 25nm 845nm
  • Example 4 25nm 779nm
  • Example 5 28nm 680nm
  • Example 6 32nm 760nm
  • Example 7 25nm 770nm
  • Example 8 38nm 480nm
  • Example 9 25nm 580nm
  • Example 10 30nm 670nm
  • Example 11 25nm 480nm
  • Example 12 28nm 490nm
  • Example 13 18nm 780nm
  • Example 14 15nm 560nm
  • Example 15 10nm 450nm
  • Example 16 20nm 650nm
  • Example 17 30nm 670nm
  • Example 18 25nm 675nm
  • Example 19 28nm 579nm
  • Example 20 26nm 550nm
  • Example 21 28nm 520nm
  • Example 22 18nm 460nm
  • Example 23 17nm 430nm
  • Example 24 10nm 389nm Comparative Example 1 1 ⁇ m 3 ⁇ m
  • the thickness of the transition metal chalcogenide nanosheet material obtained by the salt template method in the examples of the present application is relatively small, only 10-38 nm, and the thickness of the sheet is all below 40 nm, which is much smaller than the comparative example 1 ⁇ m, and the aspect ratio of the sheet (sheet size/layer thickness) is much larger than that of Comparative Example 1.
  • the assembled half-cells were tested for electrochemical performance under the constant current charge and discharge conditions of 0.2 A/g current.
  • the electrochemical performance obtained is shown in Table 6.
  • the transition metal chalcogenide nanosheet material obtained in Examples 1-24 has a discharge specific capacity of 230-390mAh ⁇ g -1 at 50 turns. , The Coulomb efficiency reaches 89.0%-99.5%; due to the better conductivity of the carbon-coated nanosheets, the carbon-coated transition metal chalcogenide nanosheet material obtained in Example 2 has a discharge specific capacity of 390mAh in 50 cycles ⁇ G -1 , Coulomb efficiency reaches 99.5%, with better performance.
  • the half-cell assembled from the tungsten diselenide nanosheets obtained in Example 7 was tested for electrochemical performance.
  • the test conditions were constant current charge and discharge at a current of 0.2 A/g.
  • the electrochemical performance obtained is shown in FIG. 4. It can be seen from FIG. 4 that the tungsten diselenide nanosheets synthesized by this method have a higher capacity in sodium ion batteries, and have good cycle stability, reduced capacity decay, high coulombic efficiency, and higher than bulk tungsten diselenide. The electrochemical performance has been greatly improved.

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Abstract

本申请提供了一种过渡金属硫属化物纳米片层材料及其制备方法，以及作为电池负极材料、二次电池及其应用，属于过渡金属硫属化物技术领域。本申请提供了一种过渡金属硫属化物纳米片层材料的制备方法，将原料溶于可溶性盐的水溶液中，除去水分得到固体，然后烧结固体，水洗后得到过渡金属硫属化物纳米片层材料；其中，原料包括硫属元素前驱体和过渡金属前驱体。该制备方法采用可溶性盐作为模板剂，价格低廉，环境友好，后处理中易除去，且得到的过渡金属硫属化物纳米片层材料片层厚度更薄。该制备方法相较于传统的二氧化硅模板法、水热法，大大缩短了合成周期，具有简单易行、可控、产率高的特点，实验操作简单，适用于规模化的生产。

Description

过渡金属硫属化物纳米片层材料及其制备方法、电池负极材料、二次电池及其应用 技术领域
本申请属于过渡金属硫属化物技术领域，具体涉及一种过渡金属硫属化物纳米片层材料及其制备方法、电池负极材料、二次电池及其应用。
背景技术
随着石墨烯的发现，近年来，类石墨烯层状材料引起了人们的极大关注。类石墨烯层状材料是指具有与石墨类似层状晶体结构的无机化合物，主要包括金属硫属化物、硅烯、锗烯、氮化硼等。在能量储存方面，过渡金属硫属化合物(包括过渡金属硫化物，过渡金属硒化物以及过渡金属碲化物)由于层间距大，比容量高，被认为是电池负极的理想材料。过渡金属硫属化物如MoS 2，MoSe 2，VS 2，WS 2，WSe 2，SnS 2等，在锂离子电池、钠离子电池、钾离子电池、钙离子电池、镁离子电池、锌离子电池以及双离子电池等领域都表现出优异的电化学性能。
然而，对于块体层状材料，在充放电过程中，随着离子的嵌入/脱嵌，将会导致其发生严重的粉化，进而引起电池循环性能降低。因此，制备出少层的纳米片层结构对提高负极层状材料的电化学性能显得极为重要。
目前所采用的层状材料合成方法主要包括化学气相沉积和水热合成。化学气相沉积的产率有限，难以大规模的应用，不适于工业上的应用；水热合成方法得到的层状材料的尺寸厚度形貌难以控制。因此，急需开发新的合成层状材料的方法，用于制备具有少层结构的层状材料。
现有技术中专利CN105460921B首先利用碳纳米管在浓酸和高锰酸钾中处理制备氧化石墨烯纳米带，再通过水热反应使硒化钼与石墨烯纳米片复合制备了硒化钼纳米片。该方法操作步骤繁琐，耗时长，且需要采用浓硫酸等化学试剂，操作危险，而且碳纳米管价格昂贵，难以推广使用。专利CN106816602A中制备了一种二硒化钼/碳复合材料，利用二氧化硅纳米粒子为模板剂，然后用氢氟酸或者热浓碱刻蚀二氧化硅，此方法操作复杂，且氢氟酸具有强腐蚀性，对人体危害极大。专利CN108043428A中利用两步水热法合成硫化物，该方案操作复杂，耗时长。
鉴于此，特提出本申请。
发明内容
本申请的第一个目的在于提供一种过渡金属硫属化物纳米片层材料的制备方法，能够克服上述问题或者至少部分地解决上述技术问题。
本申请的第二个目的在于提供上述制备方法得到的过渡金属硫属化物纳米片层材料，该过渡金属硫属化物纳米片层材料纯度高，片层结构尺寸均一，厚度均匀，厚度较薄，形貌可控。
本申请的第三个目的在于提供一种电池负极材料，包括上述过渡金属硫属化物纳米片层材料，能够缓解块体材料在充放电过程中随着离子的插层/脱嵌所造成的体积膨胀粉化，从而提高电池的性能。
本申请的第四个目的在于提供一种二次电池，包括上述电池负极材料，包括上述电池负极材料的二次电池具有高的比容量以及优异的循环性能。
本申请的第五个目的在于提供上述二次电池在电子设备、电动工具或电动车辆中的应用。
根据本申请第一个方面，提供了一种过渡金属硫属化物纳米片层材料的制备方法，包括以下步骤：
将原料溶于可溶性盐的水溶液中，除去水分得到固体，然后烧结固体，水洗后得到过渡金属硫属化物纳米片层材料；
其中，所述原料包括硫属元素前驱体和过渡金属前驱体；
优选地，所述方法中的原料还包括碳材料，得到碳包覆的过渡金属硫属化物纳米片层材料。
优选地，所述硫属元素前驱体包括硫属元素单体和/或含硫属元素的化合物；
优选地，所述硫属元素单体包括硫、硒或碲中的至少一种，优选为硫；
优选地，所述含硫属元素的化合物包括硫脲、硫醇、硫化铵、硫化钠、硫化钾、亚硫酸铵、亚硫酸钠、亚硫酸钾、过硫酸铵、过硫酸钠、过硫酸钾、硒脲、硒醇、硒化铵、硒化钠、硒化钾、亚硒酸铵、亚硒酸钠、亚硒酸钾、过硒酸铵、过硒酸钠、过硒酸钾、碲脲、碲醇、碲化铵、碲化钠、碲化钾、亚碲酸铵、亚碲酸钠、亚碲酸钾、过碲酸铵、过碲酸钠或过碲酸钾中的至少一种，优选为硫脲、硫醇、硫化铵、硫化钠、硫化钾、亚硫酸铵、亚硫酸钠、亚硫酸钾、过硫酸铵、过硫酸钠、过硫酸钾、硒脲、硒酸钠、碲脲或碲酸钠中的至少一种。
优选地，所述硫属元素前驱体以硫属元素前驱体溶液的形式存在；
优选地，所述硫属元素前驱体溶液的溶剂包括水、乙醇、二甲胺、二乙胺、水合肼、硼氢化钠、二甲基甲酰胺或四氢呋喃中的至少一种。
优选地，所述过渡金属前驱体包括可溶性的钼源、钨源、钒源、锡源、钴源、铁源、锌源或锑源中的至少一种；
优选地，所述钼源包括钼酸盐、二钼酸盐、四钼酸盐、五钼酸盐、七钼酸盐、八钼酸 盐、仲钼酸盐、磷钼酸盐、四硫钼酸盐或三氧化钼中的至少一种；
优选地，所述钨源包括磷钨酸盐、四硫代钨酸盐、钨酸盐或三氧化钨中的至少一种；
优选地，所述钒源包括钒酸盐、硫酸钒或草酸氧钒中的至少一种；
优选地，所述锡源包括锡酸盐、氯化锡、草酸锡、硫酸锡或硝酸锡中的至少一种；
优选地，所钴源述包括碳酸钴、硝酸钴、硫酸钴或氯化钴中的至少一种；
优选地，所述铁源包括氯化铁、硝酸铁或硫酸铁中的至少一种；
优选地，所述锌源包括氯化锌、硝酸锌或硫酸锌中的至少一种；
优选地，所述锑源包括氯化锑、硝酸锑、硫酸锑或锑酸盐中的至少一种。
优选地，所述可溶性盐包括主族金属的可溶性盐，优选为氯化盐、溴化盐、硫酸盐、硝酸盐、磷酸盐或碳酸盐中的至少一种；
优选地，所述氯化盐包括氯化钠、氯化钾、氯化钡、氯化钙、氯化镁或氯化铝中的至少一种，优选为氯化钠和/或氯化钾；
优选地，所述溴化盐包括溴化钠、溴化钾、溴化钡、溴化钙、溴化镁或溴化铝中的至少一种；
优选地，所述硫酸盐包括硫酸钠、硫酸钾、硫酸镁或硫酸铝中的至少一种；
优选地，所述硝酸盐包括硝酸钠、硝酸钾、硝酸钡、硝酸钙、硝酸镁或硝酸铝中的至少一种；
优选地，所述磷酸盐包括磷酸钠、磷酸钾、磷酸钙、磷酸铝或磷酸镁中的至少一种；
优选地，所述碳酸盐包括碳酸钠和/或碳酸钾；
优选地，所述碳材料包括碳单质和/或含碳化合物；
优选地，所述碳单质包括石墨、膨胀石墨、石墨烯、中间相碳微球石墨、乙炔炭黑、玻璃碳、碳碳复合材料、活性炭、硬碳、炭黑、碳纳米管、碳纳米纤维或介孔碳中的至少一种；
优选地，所述含碳化合物包括葡萄糖、蔗糖、淀粉、聚氧乙烯、聚乙二醇、丙三醇、羧甲基纤维素、羟乙基纤维素、羟甲基丙基纤维素、聚乙烯醇、聚丙烯、酚醛树脂或环氧树脂中的至少一种。
优选地，所述过渡金属前驱体中过渡金属与硫属元素前驱体中硫属元素的摩尔比为0.3-1：1，优选为0.35-0.8：1；
优选地，所述可溶性盐与过渡金属前驱体中过渡金属的摩尔比为100-1000：1，优选为200-500：1，进一步优选为300：1；
优选地，所述硫属元素前驱体中硫属元素与碳材料中碳元素的摩尔比为1：1-10，优选为1：2-8。
优选地，所述烧结的温度为400-800℃，优选为550-650℃；
和/或，所述烧结的时间为1-3h，优选为2h；
优选地，所述烧结的气体氛围为氢气与保护气体的混合气；
优选地，所述保护气体包括氮气和/或氩气；
优选地，所述氢气的体积分数为1％-10％，优选为5％-8％。
根据本申请第二个方面，提供了上述制备方法得到的过渡金属硫属化物纳米片层材料。
根据本申请第三个方面，提供了一种电池负极材料，包括上述过渡金属硫属化物纳米片层材料。
根据本申请第四个方面，提供了一种二次电池，包括上述电池负极材料；
其中，所述二次电池包括锂离子电池、钠离子电池、钾离子电池、钙离子电池、镁离子电池或锌离子电池；
或者，所述二次电池包括锂基双离子电池、钠基双离子电池、钾基双离子电池、钙基双离子电池、镁基双离子电池或锌基双离子电池。
根据本申请第五个方面，提供了上述二次电池在电子设备、电动工具或电动车辆中的应用。
本申请提供了一种过渡金属硫属化物纳米片层材料的制备方法，将硫属元素前驱体、过渡金属前驱体溶于可溶性盐的水溶液中，除去水分得到固体，然后烧结，得到过渡金属硫属化物纳米片层材料。该制备方法采用可溶性盐作为模板剂，价格低廉，环境友好，后处理中易除去，且得到的过渡金属硫属化物纳米片层材料片层厚度更薄。该制备方法相较于传统的二氧化硅模板法、水热法，大大缩短了合成周期，具有简单易行、可控、产率高的特点，实验操作简单，适用于规模化的生产。
利用该方法制备得到的过渡金属硫属化物纳米片层材料纯度高，片层结构尺寸均一，厚度均匀，层数较少，形貌可控，应用于电池负极中，将能够缓解充放电过程中随着离子的插层/脱嵌而造成体积膨胀粉化从而提高电池的性能，将表现出较高的比容量和优异的循环性能。另外，相较于传统石墨负极，过渡金属硫属化物具有层间距大、理论容量高的优点。
利用该方法制备得到的过渡金属硫属化物纳米片层材料可作为锂离子电池、钠离子电池、钾离子电池、钙离子电池、镁离子电池、锌离子电池以及双离子电池的负极材料，能够缓解块体材料在充放电过程中随着离子的插层/脱嵌所造成体积膨胀粉化，从而提高电池的性能，使得电池具有高的比容量以及优异的循环性能。
附图说明
为了更清楚地说明本申请具体实施方式或现有技术中的技术方案，下面将对具体实施 方式或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图是本申请的一些实施方式，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本申请实施例1二硒化钼纳米片层材料的扫描电镜图；
图2为本申请实施例1二硒化钼纳米片层材料的X射线衍射图；
图3为本申请实施例2碳包覆二硒化钼纳米片层材料的扫描电镜图；
图4为本申请实施例7得到的二硒化钨纳米片组装得到的半电池的电化学性能。
具体实施方式
下面将结合实施例及附图对本申请的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施例仅用于说明本申请，而不应视为限制本申请的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
需要说明的是：
本申请中，如果没有特别的说明，本文所提到的所有实施方式以及优选实施方法可以相互组合形成新的技术方案。
本申请中，如果没有特别的说明，本文所提到的所有技术特征以及优选特征可以相互组合形成新的技术方案。
本申请中，如果没有特别的说明，所涉及的各组分或其优选组分可以相互组合形成新的技术方案。
本申请中，除非有其他说明，数值范围“a-b”表示a到b之间的任意实数组合的缩略表示，其中a和b都是实数。例如数值范围“400-800”表示本文中已经全部列出了“400-800”之间的全部实数，“400-800”只是这些数值组合的缩略表示。
本申请所公开的“范围”以下限和上限的形式，可以分别为一个或多个下限，和一个或多个上限。
本申请中，除非另有说明，各个反应或操作步骤可以顺序进行，也可以按照顺序进行。优选地，本文中的反应方法是顺序进行的。
除非另有说明，本文中所用的专业与科学术语与本领域熟练人员所熟悉的意义相同。此外，任何与所记载内容相似或均等的方法或材料也可应用于本申请中。
根据本申请第一个方面，提供了一种过渡金属硫属化物纳米片层材料的制备方法，包括以下步骤：
将原料溶于可溶性盐的水溶液中，除去水分得到固体，然后烧结固体，水洗后得到过渡金属硫属化物纳米片层材料；
其中，原料包括硫属元素前驱体和过渡金属前驱体。
该制备方法采用可溶性盐作为模板剂，价格低廉，环境友好，后处理中易除去，且得到的过渡金属硫属化物纳米片层材料片层厚度更薄。该制备方法相较于传统的二氧化硅模板法、水热法，大大缩短了合成周期，具有简单易行、可控、产率高的特点，实验操作简单，适用于规模化的生产。
需要说明的是，过渡金属硫属化物纳米片层材料可记为M xR y，其中M为过渡金属钼、钨、钒、锡、钴、铁、锌或锑中的至少一种，R为硫、硒或碲中的至少一种，x、y的取值能够使得MxRy中各元素的正负化合价的代数和为零。M可以是过渡金属中的一个，也可以是两个，例如，可以是MoSe 2、MoWSe 4等。
对于除去水分的方式不作限定，例如，可以采取冷冻干燥或蒸干的方式除去水分。
可以理解的是，烧结固体后，应进行降温，例如，可降温至室温，然后进行水洗，水洗能够除去盐模板，水洗后经干燥，即可得到过渡金属硫属化物纳米片层材料。
对硫属元素前驱体的存在形式不作限定，可以是以硫属元素单体的形式存在，例如，可以是单体硫、单体硒或单体碲，也可以是以含硫属元素的化合物的形式存在，例如，可以是硫脲、硫醇、硫化铵、硫化钠、硫化钾、亚硫酸铵、亚硫酸钠、亚硫酸钾、过硫酸铵、过硫酸钠、过硫酸钾、硒脲、硒醇、硒化铵、硒化钠、硒化钾、亚硒酸铵、亚硒酸钠、亚硒酸钾、过硒酸铵、过硒酸钠、过硒酸钾、碲脲、碲醇、碲化铵、碲化钠、碲化钾、亚碲酸铵、亚碲酸钠、亚碲酸钾、过碲酸铵、过碲酸钠或过碲酸钾。
硫属元素前驱体可以硫属元素前驱体溶液的形式存在；对硫属元素前驱体溶液的溶剂不作限定，只要能够使得硫属元素前驱体溶解即可。例如，可以是水、乙醇、二甲胺、二乙胺、水合肼、硼氢化钠、二甲基甲酰胺或四氢呋喃等。
对过渡金属前驱体溶解形式不作限定，可以是过渡金属前驱体固体，即直接将过渡金属前驱体固体加入可溶性盐的水溶液中，也可以是过渡金属前驱体水溶液，即将过渡金属前驱体水溶液加入可溶性盐的水溶液中。
对过渡金属前驱体的种类不作限定，可以是可溶性的钼源、钨源、钒源、锡源、钴源、铁源、锌源或锑源，其中，钼源包括但不限于钼酸盐、二钼酸盐、四钼酸盐、五钼酸盐、七钼酸盐、八钼酸盐、仲钼酸盐、磷钼酸盐、四硫钼酸盐或三氧化钼，钨源包括但不限于磷钨酸盐、四硫代钨酸盐、钨酸盐或三氧化钨，钒源包括但不限于钒酸盐、硫酸钒或草酸氧钒，锡源包括但不限于锡酸盐、氯化锡、草酸锡、硫酸锡或硝酸锡，钴源包括但不限于碳酸钴、硝酸钴、硫酸钴或氯化钴，铁源包括但不限于氯化铁、硝酸铁或硫酸铁，锌源包括但不限于氯化锌、硝酸锌或硫酸锌，锑源包括但不限于氯化锑、硝酸锑、硫酸锑或锑酸盐。
需要说明的是，对“钼酸盐、二钼酸盐、四钼酸盐、五钼酸盐、七钼酸盐、八钼酸盐、仲钼酸盐、磷钼酸盐、四硫钼酸盐、磷钨酸盐、四硫代钨酸盐、钨酸盐、钒酸盐、锡酸盐或锑酸盐等”中盐的种类不作限定，例如，钼酸盐可以是钼酸钠、钼酸钾、钼酸锂、钼酸铝、钼酸铁、钼酸镉、钼酸锰、钼酸镁、钼酸锌、钼酸钙、钼酸铵。此外，对其是否含有结合水以及结合水的多少不作限定，例如，钼酸铵可以是不含结合水的钼酸铵，也可以是含有结合水的钼酸铵，例如，可以是四水合钼酸铵。
对“可溶性盐”不作限定，例如，可以是主族金属的可溶性盐，例如，氯化盐、溴化盐、硫酸盐、硝酸盐、磷酸盐或碳酸盐，氯化盐包括但不限于氯化钠、氯化钾、氯化钡、氯化钙、氯化镁或氯化铝，溴化盐包括但不限于溴化钠、溴化钾、溴化钡、溴化钙、溴化镁或溴化铝，硫酸盐包括但不限于硫酸钠、硫酸钾、硫酸镁或硫酸铝，硝酸盐包括但不限于硝酸钠、硝酸钾、硝酸钡、硝酸钙、硝酸镁或硝酸铝，磷酸盐包括但不限于磷酸钠、磷酸钾、磷酸钙、磷酸铝或磷酸镁，碳酸盐包括但不限于碳酸钠或碳酸钾。
“将原料溶于可溶性盐的水溶液中”中对于原料的存在形式不作限定，可以是固体，也可以是溶液，只要能够溶解在可溶性盐的水溶液中即可。鉴于原料包括硫属元素前驱体和过渡金属前驱体，将硫属元素前驱体和过渡金属前驱体加入可溶性盐的水溶液中的顺序和方式不作限定，例如，可以是依次将硫属元素前驱体、过渡金属前驱体加入可溶性盐水溶液中；可以是依次将硫属元素前驱体的溶液、过渡金属前驱体加入可溶性盐水溶液中；可以是同时将硫属元素前驱体的溶液、过渡金属前驱体加入可溶性盐水溶液中；可以是依次将过渡金属前驱体、硫属元素前驱体的溶液加入可溶性盐水溶液中；可以是同时依次将硫属元素前驱体的溶液、过渡金属前驱体的溶液加入可溶性盐水溶液中。
对于烧结时放置固体的容器不作限定，例如，可以采用氧化铝瓷舟放置固体，然后进行烧结。
对于烧结用的仪器不作限定，例如，可以采用高温管式炉进行烧结。
在一种实施方式中，方法中的原料还包括碳材料，得到碳包覆的过渡金属硫属化物纳米片层材料。
需要说明的是，碳包覆的过渡金属硫属化物纳米片层材料可记为M xR y@C，其中M为过渡金属钼、钨、钒、锡、钴、铁、锌或锑中的至少一种，R为硫、硒或碲中的至少一种，x、y的取值能够使得M xR y中各元素的正负化合价的代数和为零。M可以是过渡金属中的一个，也可以是两个，例如，可以是MoSe 2@C、MoWSe 4@C等。
同时将片层材料与碳材料进行复合，获得不同的复合结构，能够合成含有多种过渡金属的硫属化物材料。
对于碳材料的存在形式不作限定，可以是碳单质，也可以是含碳化合物；碳单质包括 但不限于石墨、膨胀石墨、石墨烯、中间相碳微球石墨、乙炔炭黑、玻璃碳、碳碳复合材料、活性炭、硬碳、炭黑、碳纳米管、碳纳米纤维或介孔碳；含碳化合物包括但不限于葡萄糖、蔗糖、淀粉、聚氧乙烯、聚乙二醇、丙三醇、羧甲基纤维素、羟乙基纤维素、羟甲基丙基纤维素、聚乙烯醇、聚丙烯、酚醛树脂或环氧树脂。
在一种实施方式中，硫属元素单体为硫；含硫属元素的化合物包括硫脲、硫醇、硫化铵、硫化钠、硫化钾、亚硫酸铵、亚硫酸钠、亚硫酸钾、过硫酸铵、过硫酸钠、过硫酸钾、硒脲、硒酸钠、碲脲或碲酸钠中的至少一种。
单体硫或上述含硫属元素的化合物得到的过渡金属硫属化物纳米片层材料具有尺寸更均匀以及片层更薄的优点。
在一种实施方式中，氯化盐为氯化钠和/或氯化钾。
氯化钠和/或氯化钾作为模板剂，价格低廉，环境友好，后处理中易除去，且氯化钠和/或氯化钾溶解度高，有利于制备纳米片尺寸均一的片层结构材料。
在一种实施方式中，过渡金属前驱体中过渡金属与硫属元素前驱体中硫属元素的摩尔比为0.3-1：1。
典型但非限制性的，过渡金属前驱体中过渡金属与硫属元素前驱体中硫属元素的摩尔比为0.3：1、0.4：1、0.5：1、0.6：1、0.7：1、0.8：1、0.9：1或1：1。
过渡金属前驱体中过渡金属与硫属元素前驱体中硫属元素的摩尔比在0.3-1：1范围内时，得到的过渡金属硫属化物纳米片层材料纯度更高。过渡金属比例过高或过低均会导致原料反应不完全，降低片成结构材料的产率。
在一种实施方式中，过渡金属前驱体中过渡金属与硫属元素前驱体中硫属元素的摩尔比为0.35-0.8：1。
在一种实施方式中，可溶性盐与硫属元素前驱体中硫属元素的摩尔比为100-1000：1。
典型但非限制性的，可溶性盐与硫属元素前驱体中硫属元素的摩尔比100：1、150：1、200：1、250：1、300：1、350：1、400：1、450：1、500：1、550：1、600：1、650：1、700：1、750：1、800：1、850：1、900：1、950：1或1000：1。
可溶性盐与过渡金属前驱体中过渡金属的摩尔比在100-1000：1范围内时，得到的过渡金属硫属化物纳米片层材料尺寸更小且片层较薄。
在一种实施方式中，可溶性盐与过渡金属前驱体中过渡金属的摩尔比为200-500：1。
在一种实施方式中，可溶性盐与过渡金属前驱体中过渡金属的摩尔比为300：1；
可溶性盐与过渡金属前驱体中过渡金属的摩尔比为300：1时，得到的过渡金属硫属化物纳米片层材料具有更佳的片层结构和尺寸大小。
在一种实施方式中，硫属元素前驱体中硫属元素与碳材料中碳元素的摩尔比为1：1-10。
典型但非限制性的，硫属元素前驱体中硫属元素与碳材料中碳元素的摩尔比为1：1、1：2、1：3、1：4、1：5、1：6、1：7、1：8、1：9或1：10。
在一种实施方式中，硫属元素前驱体中硫属元素与碳材料中碳元素的摩尔比为1：2-8。
硫属元素前驱体中硫属元素与碳材料中的碳元素的摩尔比在1：2-8范围内时，得到的过渡金属硫属化物纳米片层材料结构更佳。
在一种实施方式中，烧结的温度为400-800℃，烧结的时间为1-3h。
在一种实施方式中，烧结的温度为550-650℃，烧结的时间为2h。
通过合理调整和优化烧结的温度和时间，有利于得到性能优异的过渡金属硫属化物纳米片层材料。
在一种实施方式中，烧结的气体氛围为氢气与保护气体的混合气。
在保护气体氛围中利用氢气还原，得到最终的过渡金属硫属化物纳米片层材料。
对于保护气体的种类不作限定，例如，可以是氮气或氩气。
在一种实施方式中，氢气的体积分数为1％-10％，优选为5％-8％。
通过合理调整和优化氢气的体积分数，利用氢气还原，得到过渡金属硫属化物纳米片层材料。
根据本申请第二个方面，提供了上述制备方法得到的过渡金属硫属化物纳米片层材料。
利用上述方法制备得到的过渡金属硫属化物纳米片层材料纯度高，片层结构尺寸均一，厚度均匀，形貌可控，应用于电池负极中，将能够缓解充放电过程中随着离子的插层/脱嵌所造成体积膨胀粉化从而提高电池的性能，将表现出较高的比容量和优异的循环性能。另外，相比较于传统石墨负极，过渡金属硫属化物具有层间距大、理论容量高的优点。
根据本申请第三个方面，提供了一种电池负极材料，包括上述过渡金属硫属化物纳米片层材料。
包括过渡金属硫属化物纳米片层材料的电池负极材料应用于可作为锂离子电池、钠离子电池、钾离子电池、钙离子电池、镁离子电池、锌离子电池以及双离子电池中，能够缓解块体材料在充放电过程中随着离子的插层/脱嵌所造成体积膨胀粉化，从而提高电池的性能，使得电池具有高的比容量以及优异的循环性能。
根据本申请第四个方面，提供了一种二次电池，包括上述电池负极材料；
其中，二次电池包括锂离子电池、钠离子电池、钾离子电池、钙离子电池、镁离子电池或锌离子电池；或者，二次电池包括锂基双离子电池、钠基双离子电池、钾基双离子电池、钙基双离子电池、镁基双离子电池或锌基双离子电池。
包括上述电池负极材料的二次电池具有高的比容量以及优异的循环性能。
对二次电池的结构形状不作限定，可为扣式电池、柱状电池或软包电池。
根据本申请第五个方面，提供了上述二次电池在电子设备、电动工具或电动车辆中的应用。
电动工具是使用二次电池作为驱动电源来移动移动部件，包括但不限于电钻等；电子设备是二次电池作为操作的电源执行各种功能，包括但不限于手机、笔记本电脑、台式电脑或电子手表等；电动车辆是依靠二次电池作为驱动电源运行的电动车辆，包括但不限于电动车等；大型储能设备是使用二次电池作为储能单元，包括但不限于变电站或风力发电机组等。
使用本申请二次电池的电动工具、电子设备、电动车辆或大型储能设备可以获得相同的效果。
下面将结合实施例和对比例对本申请的技术方案进行进一步地说明。
实施例1
1、一种过渡金属硫属化物纳米片层材料的制备方法，包括以下步骤：
(1)将2mmol的硒粉分散在8mL的水合肼中，并加热至85℃，持续1小时，硒粉充分溶解。
将四水合七钼酸铵(四水合七钼酸铵中钼元素为1mmol)溶于10mL的水中，然后加入上述硒粉溶液中。
向溶液中加入50ml饱和食盐水(25℃)，搅拌并加热至液体蒸干。
(2)在管式炉中，将装有硒-水合肼、钼酸铵、NaCl的混合固体置于氧化铝瓷舟中，放置在管式炉加热区的中部位置。
(3)加热前，先向管式炉中通入Ar/H 2混合气体，排除管内的空气。再以5℃/min加热速率升温至600℃，并保温2小时。保温过程中以150sccm载气流量。保温结束后，自然冷却到室温。
(4)水洗除去产物中的氯化钠颗粒，干燥后得到二硒化钼纳米片层材料。
得到的二硒化钼纳米片层材料的扫描电镜图和X射线衍射图如图1和图2所示。由图1可知制备的纳米片片层较薄，尺寸均一。由图2可知合成的纳米片为二硒化钼。
2、一种电池负极材料，包括上述二硒化钼纳米片层材料。
3、一种锂离子电池，包括上述电池负极材料。
实施例2
一种过渡金属硫属化物纳米片层材料的制备方法，包括以下步骤：
(1)将2mmol的硒粉分散在8mL的水合肼中，并加热至85℃，持续1小时，硒粉充分溶解。
将四水合七钼酸铵(四水合七钼酸铵中钼元素为1mmol)溶于10mL的水中，然后加 入上述硒粉溶液中。
向溶液中加入葡萄糖(C元素的摩尔量为8mmol)，继续向溶液中加入50ml饱和食盐水(25℃)，搅拌并加热至液体蒸干。
(2)在管式炉中，将装有硒-水合肼、钼酸铵、葡萄糖、NaCl的混合固体置于氧化铝瓷舟中，放置在管式炉加热区的中部位置。
(3)加热前，先向管式炉中通入Ar/H 2混合气体，排除管内的空气。再以5℃/min加热速率升温至600℃，并保温2小时。保温过程中以150sccm载气流量。保温结束后，自然冷却到室温。
(4)水洗除去产物中的氯化钠颗粒，干燥后得到碳包覆二硒化钼纳米片层材料。
得到的碳包覆二硒化钼纳米片层材料的扫描电镜图如图3所示。由图3可知合成的二硒化钼纳米片表面有碳层包覆。
实施例3
一种过渡金属硫属化物纳米片层材料的制备方法，包括以下步骤：
(1)将1mmol的钼粉分散在乙醇中，然后向上述溶液中加入适量过氧化氢溶液(30％)，搅拌至钼粉溶解，得到蓝色氧化钼溶液。
将硫化铵(硫化铵中硫元素为2mmol)溶于10mL的水中，然后加入上述蓝色氧化钼溶液中。
向溶液中加入50ml饱和氯化钾水溶液(25℃)，搅拌并加热至液体蒸干得到黑色固体。
(2)在管式炉中，将上述固体置于氧化铝瓷舟中，放置在管式炉加热区的中部位置。
(3)加热前，先向管式炉中通入Ar/H 2混合气体，排除管内的空气。再以5℃/min加热速率升温至650℃，并保温2小时。保温过程中以150sccm载气流量。保温结束后，自然冷却到室温。
(4)水洗除去产物中的氯化钾颗粒，干燥后得到二硫化钼纳米片层材料。
实施例4
一种过渡金属硫属化物纳米片层材料的制备方法，包括以下步骤：
(1)将1mmol的碲粉分散在10mL的水合肼中，并加热至100℃，持续1小时，碲粉充分溶解。
将氯化锰(氯化锰中锰元素为1mmol)溶于10mL的水中，然后加入上述碲粉溶液中。
向溶液中加入50ml饱和食盐水(25℃)，搅拌并加热至液体蒸干。
(2)在管式炉中，将装有碲-水合肼、氯化锰、NaCl的混合固体置于氧化铝瓷舟中，放置在管式炉加热区的中部位置。
(3)加热前，先向管式炉中通入Ar/H 2混合气体，排除管内的空气。再以5℃/min加 热速率升温至600℃，并保温2小时。保温过程中以150sccm载气流量。保温结束后，自然冷却到室温。
(4)水洗除去产物中的氯化钠颗粒，干燥后得到二碲化锰纳米片层材料。
实施例5-11
实施例5-11与实施例1的不同之处在于，过渡金属前驱体的种类不同。具体如表1所示。
表1过渡金属前驱体
  过渡金属前驱体
实施例1 四水合七钼酸铵
实施例5 钼酸钠
实施例6 三氧化钼
实施例7 仲钨酸铵
实施例8 草酸氧钒
实施例9 硫酸锡
实施例10 氯化钴
实施例11 氯化锌
实施例12-15
实施例12-15与实施例1的不同之处在于，硫属元素前驱体的种类不同。具体如表2所示。
表2硫属元素前驱体
  硫属元素前驱体 过渡金属硫属化物纳米片层材料
实施例1 硒粉 二硒化钼
实施例12 碲粉 二碲化钼
实施例13 硫粉 二硫化钼
实施例14 硫脲 二硫化钼
实施例15 硫化钠 二硫化钼
实施例16-19
实施例16-19与实施例1的不同之处在于，主族金属的可溶性盐的种类不同，具体如表3所示。
表3主族金属的可溶性盐
  主族金属的可溶性盐
实施例1 氯化钠
实施例16 氯化钾
实施例17 氯化镁
实施例18 硫酸钠
实施例19 碳酸钠
实施例20-24
实施例20-24与实施例1的不同之处在于，硫属元素前驱体、过渡金属前驱体和主族金属的可溶性盐的用量，具体如表4所示。
表4用量
Figure PCTCN2018121865-appb-000001
对比例1
一种过渡金属硫属化物纳米片层材料的制备方法，包括以下步骤：
(1)将2mmol的硒粉分散在8mL的水合肼中，并加热至85℃，持续1小时，硒粉充分溶解。
将四水合七钼酸铵(四水合七钼酸铵中钼元素为1mmol)溶于10mL的水中，然后加入上述硒粉溶液中。搅拌并加热至液体蒸干。
(2)在管式炉中，将装有硒-水合肼、钼酸铵的混合固体置于氧化铝瓷舟中，放置在管式炉加热区的中部位置。
(3)加热前，先向管式炉中通入Ar/H 2混合气体，排除管内的空气。再以5℃/min加热速率升温至600℃，并保温2小时。保温过程中以150sccm载气流量。保温结束后，自然冷却到室温。
(4)水洗除去产物中的氯化钠颗粒，干燥后得到二硒化钼。
试验例1
实施例1-24和对比例1得到的材料的片层厚度和片层大小如表5所示。
表5片层厚度和片层大小
  片层厚度 片层大小
实施例1 25nm 558nm
实施例2 10nm 600nm
实施例3 25nm 845nm
实施例4 25nm 779nm
实施例5 28nm 680nm
实施例6 32nm 760nm
实施例7 25nm 770nm
实施例8 38nm 480nm
实施例9 25nm 580nm
实施例10 30nm 670nm
实施例11 25nm 480nm
实施例12 28nm 490nm
实施例13 18nm 780nm
实施例14 15nm 560nm
实施例15 10nm 450nm
实施例16 20nm 650nm
实施例17 30nm 670nm
实施例18 25nm 675nm
实施例19 28nm 579nm
实施例20 26nm 550nm
实施例21 28nm 520nm
实施例22 18nm 460nm
实施例23 17nm 430nm
实施例24 10nm 389nm
对比例1 1μm 3μm
由表5可知，本申请实施例采用盐模板法得到的过渡金属硫属化物纳米片层材料的片层厚度较小，仅为10-38nm，片层厚度都在40nm以下，远远小于对比例的1μm，且片层的长径比(片层大小/片层厚度)远远大于对比例1。
实验例2
为了测试实施例1-24和对比例1得到的材料的电化学性能，先将施例1-24和对比例1得到的材料用于组装半电池，半电池的制备具体为：
(1)制备电池极片：将0.7g实施例1-24和对比例1得到的材料、0.2g导电碳黑、0.1g聚偏氟乙烯加入到2mL的N-甲基吡咯烷酮中，充分研磨获得均匀浆料；然后将浆料均匀涂覆于铜箔表面，80℃真空干燥12小时。对干燥所得电极片裁切成直径为10mm的圆片，用油压机压实(10MPa,10s)，置于手套箱中作为电池正极备用。
(2)电池负极：市售的金属锂片。
(3)配制电解液：在手套箱中称取1.36g六氟磷酸锂加入到9ml碳酸乙烯酯：碳酸二甲酯：碳酸甲乙酯(v/v/v＝1:1:1)中，搅拌至六氟磷酸锂完全溶解，作为电解液备用。
(4)制备隔膜：将玻璃纤维纸裁切成直径为16mm的圆片，80℃真空干燥12h后置于手套箱中作为隔膜备用。
(5)电池组装：在氩气气氛的手套箱中，将上述制备好的正极、隔膜、负极依次紧密堆叠，滴加电解液使隔膜完全浸润，然后将上述堆叠部分封装入外壳，完成半电池的组装。
将组装得到的半电池进行电化学性能的测试，测试条件为0.2A/g电流下恒流充放电，得到的电化学性能如表6所示。
表6电化学性能
Figure PCTCN2018121865-appb-000002
Figure PCTCN2018121865-appb-000003
由表6可知，合成化合物纳米片片层越薄相应地电化学性能更好，实施例1-24得到的过渡金属硫属化物纳米片层材料50圈放电比容量达到230-390mAh·g -1，库伦效率达到89.0％-99.5％；进行碳包覆的纳米片由于具有更好的导电性能，实施例2得到的碳包覆的过渡金属硫属化物纳米片层材料50圈放电比容量达到390mAh·g -1，库伦效率达到99.5％，具有更好的性能。
实验例3
对实施例7得到的二硒化钨纳米片组装得到的半电池进行电化学性能的测试，测试条件为0.2A/g电流下恒流充放电，得到的电化学性能如图4所示。由图4可知，通过此方法合成的二硒化钨纳米片用于钠离子电池中有较高的容量，并且循环稳定性好，容量衰减少，库伦效率高，比块体二硒化钨的电化学性能有大幅度提高。
应当理解的是，上述制备方法的说明中未详细描述的内容，均是本领域技术人员容易想到的常用参数，因此可以省略对其的详细说明。
最后应说明的是：以上各实施例仅用以说明本申请的技术方案，而非对其限制；尽管参照前述各实施例对本申请进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本申请各实施例技术方案的范围。

Claims (10)

  1. 一种过渡金属硫属化物纳米片层材料的制备方法，其特征在于，包括以下步骤：
    将原料溶于可溶性盐的水溶液中，除去水分得到固体，然后烧结固体，水洗后得到过渡金属硫属化物纳米片层材料；
    其中，所述原料包括硫属元素前驱体和过渡金属前驱体；
    优选地，所述方法中的原料还包括碳材料，得到碳包覆的过渡金属硫属化物纳米片层材料。
  2. 根据权利要求1所述的制备方法，其特征在于，所述硫属元素前驱体包括硫属元素单体和/或含硫属元素的化合物；
    优选地，所述硫属元素单体包括硫、硒或碲中的至少一种，优选为硫；
    优选地，所述含硫属元素的化合物包括硫脲、硫醇、硫化铵、硫化钠、硫化钾、亚硫酸铵、亚硫酸钠、亚硫酸钾、过硫酸铵、过硫酸钠、过硫酸钾、硒脲、硒醇、硒化铵、硒化钠、硒化钾、亚硒酸铵、亚硒酸钠、亚硒酸钾、过硒酸铵、过硒酸钠、过硒酸钾、碲脲、碲醇、碲化铵、碲化钠、碲化钾、亚碲酸铵、亚碲酸钠、亚碲酸钾、过碲酸铵、过碲酸钠或过碲酸钾中的至少一种，优选为硫脲、硫醇、硫化铵、硫化钠、硫化钾、亚硫酸铵、亚硫酸钠、亚硫酸钾、过硫酸铵、过硫酸钠、过硫酸钾、硒脲、硒酸钠、碲脲或碲酸钠中的至少一种；
    优选地，所述硫属元素前驱体以硫属元素前驱体溶液的形式存在；
    优选地，所述硫属元素前驱体溶液的溶剂包括水、乙醇、二甲胺、二乙胺、水合肼、硼氢化钠、二甲基甲酰胺或四氢呋喃中的至少一种。
  3. 根据权利要求1所述的制备方法，其特征在于，所述过渡金属前驱体包括可溶性的钼源、钨源、钒源、锡源、钴源、铁源、锌源或锑源中的至少一种；
    优选地，所述钼源包括钼酸盐、二钼酸盐、四钼酸盐、五钼酸盐、七钼酸盐、八钼酸盐、仲钼酸盐、磷钼酸盐、四硫钼酸盐或三氧化钼中的至少一种；
    优选地，所述钨源包括磷钨酸盐、四硫代钨酸盐、钨酸盐或三氧化钨中的至少一种；
    优选地，所述钒源包括钒酸盐、硫酸钒或草酸氧钒中的至少一种；
    优选地，所述锡源包括锡酸盐、氯化锡、草酸锡、硫酸锡或硝酸锡中的至少一种；
    优选地，所钴源述包括碳酸钴、硝酸钴、硫酸钴或氯化钴中的至少一种；
    优选地，所述铁源包括氯化铁、硝酸铁或硫酸铁中的至少一种；
    优选地，所述锌源包括氯化锌、硝酸锌或硫酸锌中的至少一种；
    优选地，所述锑源包括氯化锑、硝酸锑、硫酸锑或锑酸盐中的至少一种。
  4. 根据权利要求1所述的制备方法，其特征在于，所述可溶性盐包括主族金属的可溶性盐，优选为氯化盐、溴化盐、硫酸盐、硝酸盐、磷酸盐或碳酸盐中的至少一种；
    优选地，所述氯化盐包括氯化钠、氯化钾、氯化钡、氯化钙、氯化镁或氯化铝中的至少一种，优选为氯化钠和/或氯化钾；
    优选地，所述溴化盐包括溴化钠、溴化钾、溴化钡、溴化钙、溴化镁或溴化铝中的至少一种；
    优选地，所述硫酸盐包括硫酸钠、硫酸钾、硫酸镁或硫酸铝中的至少一种；
    优选地，所述硝酸盐包括硝酸钠、硝酸钾、硝酸钡、硝酸钙、硝酸镁或硝酸铝中的至少一种；
    优选地，所述磷酸盐包括磷酸钠、磷酸钾、磷酸钙、磷酸铝或磷酸镁中的至少一种；
    优选地，所述碳酸盐包括碳酸钠和/或碳酸钾；
    优选地，所述碳材料包括碳单质和/或含碳化合物；
    优选地，所述碳单质包括石墨、膨胀石墨、石墨烯、中间相碳微球石墨、乙炔炭黑、玻璃碳、碳碳复合材料、活性炭、硬碳、炭黑、碳纳米管、碳纳米纤维或介孔碳中的至少一种；
    优选地，所述含碳化合物包括葡萄糖、蔗糖、淀粉、聚氧乙烯、聚乙二醇、丙三醇、羧甲基纤维素、羟乙基纤维素、羟甲基丙基纤维素、聚乙烯醇、聚丙烯、酚醛树脂或环氧树脂中的至少一种。
  5. 根据权利要求1-4任一项所述的制备方法，其特征在于，所述过渡金属前驱体中过渡金属与硫属元素前驱体中硫属元素的摩尔比为0.3-1：1，优选为0.35-0.8：1；
    优选地，所述可溶性盐与过渡金属前驱体中过渡金属的摩尔比为100-1000：1，优选为200-500：1，进一步优选为300：1；
    优选地，所述硫属元素前驱体中硫属元素与碳材料中碳元素的摩尔比为1：1-10，优选为1：2-8。
  6. 根据权利要求1-4任一项所述的制备方法，其特征在于，所述烧结的温度为400-800℃，优选为550-650℃；
    和/或，所述烧结的时间为1-3h，优选为2h；
    优选地，所述烧结的气体氛围为氢气与保护气体的混合气；
    优选地，所述保护气体包括氮气和/或氩气；
    优选地，所述氢气的体积分数为1％-10％，优选为5％-8％。
  7. 权利要求1-6任一项所述的制备方法得到的过渡金属硫属化物纳米片层材料。
  8. 一种电池负极材料，其特征在于，包括权利要求7所述的过渡金属硫属化物纳米片层材料。
  9. 一种二次电池，其特征在于，包括权利要求8所述的电池负极材料；
    其中，所述二次电池包括锂离子电池、钠离子电池、钾离子电池、钙离子电池、镁离子电池或锌离子电池；
    或者，所述二次电池包括锂基双离子电池、钠基双离子电池、钾基双离子电池、钙基双离子电池、镁基双离子电池或锌基双离子电池。
  10. 权利要求9所述的二次电池在电子设备、电动工具或电动车辆中的应用。
PCT/CN2018/121865 2018-12-18 2018-12-18 过渡金属硫属化物纳米片层材料及其制备方法、电池负极材料、二次电池及其应用 Ceased WO2020124394A1 (zh)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111704165A (zh) * 2020-08-04 2020-09-25 湘潭大学 一种六方MoTe2纳米片及制备方法
CN116730381A (zh) * 2023-05-19 2023-09-12 合肥精创科技有限公司 一步法制备金属硫化物超薄纳米片的方法及应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104966812A (zh) * 2014-12-01 2015-10-07 天津大学 三维多孔类石墨烯负载二硫化钼复合材料及制备方法
CN105140517A (zh) * 2015-09-14 2015-12-09 天津大学 一种非水溶性过渡金属二硫化物纳米片的制备方法
CN105280887A (zh) * 2015-09-14 2016-01-27 天津大学 一种锂离子电池负极的制作方法
CN106876702A (zh) * 2017-02-08 2017-06-20 大连理工大学 一种钠离子电池负极用煤沥青树脂基无定形碳包覆少层二硫化钼纳米盒子的制备方法及应用

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104966812A (zh) * 2014-12-01 2015-10-07 天津大学 三维多孔类石墨烯负载二硫化钼复合材料及制备方法
CN105140517A (zh) * 2015-09-14 2015-12-09 天津大学 一种非水溶性过渡金属二硫化物纳米片的制备方法
CN105280887A (zh) * 2015-09-14 2016-01-27 天津大学 一种锂离子电池负极的制作方法
CN106876702A (zh) * 2017-02-08 2017-06-20 大连理工大学 一种钠离子电池负极用煤沥青树脂基无定形碳包覆少层二硫化钼纳米盒子的制备方法及应用

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111704165A (zh) * 2020-08-04 2020-09-25 湘潭大学 一种六方MoTe2纳米片及制备方法
CN111704165B (zh) * 2020-08-04 2022-04-08 湘潭大学 一种六方MoTe2纳米片及制备方法
CN116730381A (zh) * 2023-05-19 2023-09-12 合肥精创科技有限公司 一步法制备金属硫化物超薄纳米片的方法及应用

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