CN114715858B - Preparation method of copper vanadium selenide solid solution, negative electrode material and sodium ion battery - Google Patents

Preparation method of copper vanadium selenide solid solution, negative electrode material and sodium ion battery Download PDF

Info

Publication number
CN114715858B
CN114715858B CN202210350491.7A CN202210350491A CN114715858B CN 114715858 B CN114715858 B CN 114715858B CN 202210350491 A CN202210350491 A CN 202210350491A CN 114715858 B CN114715858 B CN 114715858B
Authority
CN
China
Prior art keywords
vanadium
sulfur
copper
solid solution
selenide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210350491.7A
Other languages
Chinese (zh)
Other versions
CN114715858A (en
Inventor
梁军
高明慧
李莉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ningxia University
Original Assignee
Ningxia University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ningxia University filed Critical Ningxia University
Priority to CN202210350491.7A priority Critical patent/CN114715858B/en
Publication of CN114715858A publication Critical patent/CN114715858A/en
Application granted granted Critical
Publication of CN114715858B publication Critical patent/CN114715858B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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
    • H01M2004/027—Negative electrodes
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The preparation method of the sulfur-vanadium-copper selenide solid solution comprises the steps of placing a sulfur-vanadium-copper precursor and excessive selenium powder in a closed reaction space protected by inert gas, calcining at a preset temperature system to obtain sulfur-vanadium-copper selenide, taking the sulfur-vanadium-copper synthesized by hydrothermal reaction as the precursor, and selenizing the precursor to obtain the sulfur-vanadium-copper selenide solid solution, wherein the sulfur-vanadium-copper selenide solid solution has the advantages of low required temperature, short time, low energy consumption, low cost and the like.

Description

Preparation method of copper vanadium selenide solid solution, negative electrode material and sodium ion battery
Technical Field
The application relates to the technical field of battery material preparation, in particular to a preparation method of a sulfur-vanadium-copper selenide solid solution, a negative electrode material and a sodium ion battery.
Background
With the unprecedented development of society, the demand for energy in various countries is increasing. Traditional fossil energy and resources have failed to meet the demands of modern human society. The use of new clean energy sources such as wind energy, solar energy, geothermal energy and tidal energy is greatly restricted by conditions, so the development of certain energy storage devices to store these energy sources is an important subject. The basis for the use and development of new energy sources is therefore the development of high-performance energy storage and conversion devices, i.e. chemical power sources. The sodium ion battery is a secondary rechargeable battery, the working principle is similar to that of a lithium ion battery, electric energy storage and release are mainly realized by moving sodium ions between an anode and a cathode, the sodium ion battery is a good substitute when the energy density requirement is low because the sodium salt raw material is abundant, the sodium salt is cheap and easy to obtain, the sodium salt is characterized in that low-concentration electrolyte is allowed to be used, the cost of the sodium ion battery is far less than that of the lithium ion battery and the lithium iron phosphate battery, the sodium ion battery has no overdischarge characteristic, the sodium ion battery can be discharged to zero volt and the like.
Solid solutions are homogeneously mixed solid solutions formed by dissolving other constituent atoms (solute atoms) in a crystal lattice using a certain constituent element as a solvent, and retain the crystal structure type of the solvent. The formation of solid solutions can form a large number of defects in the substrate material, and the existence of the defects in the material can significantly influence the transportation, storage and reaction properties of electrons and ions in the solid, at interfaces and on the surface, so that the specific capacity of the substrate material is improved. The presence of defects can provide more ion transport channels, improving the conductivity of the material. The presence of defects also may provide additional lithium storage sites, as well as increase the specific capacity of the base material. The transition metal sulfide has the advantages of good conductivity, higher theoretical specific capacity, low price, environmental friendliness and the like. The current methods for synthesizing solid solutions of transition metal sulfides are: high temperature solid phase method, electrochemical deposition method, chemical vapor deposition method (CVD), etc. Without exception, these synthetic methods have disadvantages of long synthesis time, high synthesis cost, and the like.
Disclosure of Invention
In view of the above, there is a need to provide a method for preparing a solid solution of vanadium copper selenide.
It is also necessary to propose a negative electrode material.
There is also a need to propose a sodium ion battery.
A method for preparing a sulfur-vanadium-copper selenide solid solution comprises the steps of placing a sulfur-vanadium-copper precursor and excessive selenium powder into a closed reaction space protected by inert gas, and calcining at a preset temperature system to obtain the sulfur-vanadium-copper selenide.
Preferably, the preparation method of the sulfur vanadium copper precursor comprises the following steps:
step 201: adding sodium orthovanadate, copper chloride and thioacetamide into an alkaline solution to form a mixed solution, wherein the molar quantity of vanadium atoms, the ratio of the molar quantity of copper atoms to the molar quantity of sulfur atoms in the mixed solution is 1:3:4;
step 202: stirring the mixed solution for a preset time, and reacting at 180-200 ℃ for 6-10 hours to obtain brown precipitate;
step 203: and separating the brown precipitate, and drying to obtain the precursor vanadium copper sulfide.
Preferably, in step 202, the mixed solution is magnetically stirred for 2 to 3 hours.
Preferably, the mass ratio of the vanadium copper sulfide to the selenium powder is 3:1.
Preferably, the temperature system is specifically: preserving heat for 1-2 hours at 450-500 ℃.
Preferably, the temperature is raised from room temperature to 450-500 ℃ at a heating rate of 3-5 ℃/min.
Preferably, the temperature system is specifically: the temperature is raised from room temperature to 500 ℃ at a heating rate of 5 ℃/min, and then the temperature is kept at 500 ℃ for 1 hour.
Preferably, the copper vanadium selenide is a solid solution.
A negative electrode material is prepared by a preparation method of a sulfur-vanadium-copper selenide solid solution.
A sodium ion battery includes a battery anode made of an anode material.
Compared with the prior art, the application has the beneficial effects that:
the sulfur vanadium copper synthesized by the hydrothermal reaction is used as a precursor, and then the precursor is selenized to obtain the solid solution of the sulfur vanadium copper selenide, which has the advantages of low required temperature, short time, low energy consumption, low cost and the like.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of a solid solution of copper vanadium sulfur selenide.
Fig. 2 is a partial magnified view of an X-ray powder diffraction pattern of a solid solution of vanadium copper selenide.
FIG. 3 is an X-ray photoelectron spectroscopy analysis of a solid solution of copper vanadium selenide.
Fig. 4 is an EDS elemental analysis chart of a copper vanadium sulfur selenide solid solution.
Detailed Description
In order to more clearly illustrate the technical solution of the embodiments of the present application, the following will further describe the combined embodiments.
The embodiment of the application provides a preparation method of a sulfur-vanadium-copper selenide solid solution, which is characterized in that a sulfur-vanadium-copper precursor and excessive selenium powder are placed in a closed reaction space protected by inert gas and calcined at a preset temperature system to obtain the sulfur-vanadium-copper selenide.
Compared with the prior art, the application has the beneficial effects that:
the sulfur vanadium copper synthesized by the hydrothermal reaction is used as a precursor, and then the precursor is selenized to obtain the solid solution of the sulfur vanadium copper selenide, which has the advantages of low required temperature, short time, low energy consumption, low cost and the like.
Further, the preparation method of the sulfur vanadium copper precursor comprises the following steps:
step 201: adding sodium orthovanadate, copper chloride and thioacetamide into an alkaline solution to form a mixed solution, wherein the molar quantity of vanadium atoms, the ratio of the molar quantity of copper atoms to the molar quantity of sulfur atoms in the mixed solution is 1:3:4;
step 202: stirring the mixed solution for a preset time, and reacting at 180-200 ℃ for 6-10 hours to obtain brown precipitate;
step 203: and separating the brown precipitate, and drying to obtain the precursor vanadium copper sulfide.
And (3) centrifugally separating the brown precipitate, and drying the separated solid brown precipitate for 8-10 hours to obtain brown powdery precursor vanadium copper sulfide.
Preferably, in step 202, the mixed solution is subjected to hydrothermal reaction at 180-200 ℃ for 6-10 hours to obtain vanadium copper sulfide serving as a selenizing precursor, and the method has the advantage of short synthesis time.
Further, in step 202, the mixed solution is magnetically stirred for 2 to 3 hours.
Preferably, the sodium orthovanadate is soluble solid sodium orthovanadate, the stirred mixed solution is transferred into an autoclave, the autoclave is lined with polytetrafluoroethylene lining, and the autoclave is sealed.
Preferably, the sulfur, vanadium and copper are mixed with selenium powder to form prefabricated mixed powder.
Further, the mass ratio of the sulfur, vanadium and copper to the selenium powder is 3:1.
Further, the temperature system specifically comprises: preserving heat for 1-2 hours at 450-500 ℃.
Further, the temperature is raised from room temperature to 450-500 ℃ at a heating rate of 3-5 ℃/min.
Further, the temperature system specifically comprises: the temperature is raised from room temperature to 500 ℃ at a heating rate of 5 ℃/min, and then the temperature is kept at 500 ℃ for 1 hour.
Further, the copper vanadium selenide is a solid solution.
The embodiment of the application provides a negative electrode material which is prepared by a preparation method of a sulfur-vanadium-copper selenide solid solution.
The embodiment of the application provides a sodium ion battery, which comprises a battery cathode made of a cathode material.
Sodium ion battery with anode made of selenium sulfur vanadium copper solid solution in 1Ag -1 At high current density, the capacity after 1000 cycles is still kept at 550mAhg -1 Shows excellent cycle stability.
The application is further illustrated by the following examples and comparative examples, which are given solely for the purpose of illustrating the application in detail and are not intended to limit the scope of the application in any way.
Example 1: 2g of TEOA is taken and added into a beaker of 18mL of distilled water, 1mmol of sodium orthovanadate, 0.5mmol of copper chloride and 4mmol of thioacetamide are sequentially added, magnetic stirring is carried out for 3 hours, brown precipitate is obtained, the brown precipitate is repeatedly centrifuged with ethanol for several times, solid precipitate is obtained, the solid precipitate is separated, and the solid precipitate is dried at 60 ℃ for 8 hours, so that brown powdery precursor copper vanadium sulfate is obtained. And (3) placing 1 mole part of precursor sulfur vanadium copper and 3 mole parts of selenium powder at two ends of a quartz boat for flattening, placing the quartz boat in a sealed tube furnace, calcining under the protection of nitrogen gas, and heating at a heating rate of 5 ℃/min from room temperature to 500 ℃, keeping the temperature for calcining for 1 hour, and cooling to room temperature to obtain the sulfur vanadium copper selenide solid solution.
The prepared solid solution of the vanadium copper selenide contains three solutes, and other elements are not added at will to any selenide or sulfide, so that the solid solution of the application can be formed.
For example, applicant has previously studied to find that: in most cases, vulcanization with Prussian blue-like compounds results in a mixture of bimetallic sulfides and sulfides, e.g. Ni 3 [Fe(CN) 6 ] 2 NiFe is obtained after direct vulcanization 2 S 4 And NiS, rather than forming a solid solution of nickel iron sulfide.
The X-ray diffraction analysis of the sulfur-vanadium-copper selenide solid solution prepared in the example 1 is carried out, and as shown in an X-ray powder diffraction diagram of the sulfur-vanadium-copper selenide solid solution in the figure 1, only one set of XRD diffraction peaks corresponding to CuVSSe are shown in the product. As shown in the enlarged partial X-ray powder diffraction pattern of the solid solution of copper vanadium selenide of FIG. 2, after the solid solution is formed, one element in the crystal lattice is replaced by another, then the crystal cell is referred to asThe number will change while the peak position of the XRD (i.e. 20 degrees) will shift. The copper vanadium sulfur selenide solid solution produced in example 1 is not a simple mixture. X-ray photoelectron spectroscopy of the copper vanadium selenide solid solution obtained in example 1, as shown in FIG. 3, the peak at 932.68eV is attributed to Cu2p 3/2 952.43eV is ascribed to Cu2p 1/2 Indicating that copper elements are present in the material; peaks at 514.15eV, 517.06eV, 521.7eV are ascribed to V2p 3/2 524.34eV is assigned to V2p 1/2 Indicating that vanadium element exists in the material; the peak at 163.04eV is attributed to S2p 3/2 161.80eV is ascribed to S2p 1/2 Indicating that elemental sulfur is present in the material; peaks at 54.97eV, 54.06eV are ascribed to Se2p 3/2 Indicating that selenium exists in the material; we can find that Se element is indeed present in the sample. Fig. 4 shows EDS elemental analysis diagram of the solid solution of sulfur, vanadium and copper selenide, which illustrates the inclusion of four elements, selenium, sulfur, vanadium and copper. From the analysis of fig. 1, 2, 3 and 4, it is determined that the solid solution of vanadium copper selenide was successfully synthesized.
Example 2: the product obtained in example 1 was subjected to an experiment in terms of battery performance, the assembly process was carried out in a glove box filled with high purity argon gas, the water content and the oxygen content were both lower than 0.lpppm, the copper foil coated with vanadium copper selenide was used as the positive electrode, the high purity sodium sheet was used as the negative electrode, and the electrolyte was 1M NaCF 3 SO 3 in diglyme=100 vol%. And (3) assembling the battery, packaging in a glove box by using a sealing machine, standing for 6 hours at room temperature, and testing the performance of the battery. The test results show that: at 1Ag -1 At high current density, the capacity after 1000 cycles is still kept at 550mAhg -1 The coulomb efficiency reaches more than 98%, and the excellent cycle stability performance is shown.
The steps in the method of the embodiment of the application can be sequentially adjusted, combined and deleted according to actual needs.
The foregoing disclosure is illustrative of the preferred embodiments of the present application, and is not to be construed as limiting the scope of the application, as it is understood by those skilled in the art that all or part of the above-described embodiments may be practiced with equivalents thereof, which fall within the scope of the application as defined by the appended claims.

Claims (8)

1. A preparation method of a sulfur-vanadium-copper selenide solid solution is characterized by comprising the following steps: placing the sulfur vanadium copper precursor and excessive selenium powder into a closed reaction space protected by inert gas, and calcining at a preset temperature system to obtain sulfur vanadium copper selenide; the preparation method of the sulfur vanadium copper precursor comprises the following steps:
step 201: adding sodium orthovanadate, copper chloride and thioacetamide into an alkaline solution to form a mixed solution, wherein the molar quantity of vanadium atoms, the ratio of the molar quantity of copper atoms to the molar quantity of sulfur atoms in the mixed solution is 1:3:4;
step 202: stirring the mixed solution for a preset time, and reacting at 180-200 ℃ for 6-10 hours to obtain brown precipitate;
step 203: and separating the brown precipitate, and drying to obtain the precursor vanadium copper sulfide.
2. The method for preparing the solid solution of vanadium copper selenide sulfur according to claim 1, wherein: in step 202, the mixed solution is magnetically stirred for 2 to 3 hours.
3. The method for preparing the solid solution of vanadium copper selenide sulfur according to claim 1, wherein: the mass ratio of the sulfur, vanadium and copper to the selenium powder is 3:1.
4. The method for preparing the solid solution of vanadium copper selenide sulfur according to claim 1, wherein: the temperature system is specifically as follows: preserving heat for 1-2 hours at 450-500 ℃.
5. The method for preparing the solid solution of vanadium copper selenide according to claim 4, wherein: the temperature is increased from room temperature to 450-500 ℃ at a heating rate of 3-5 ℃/min.
6. The method for preparing the solid solution of vanadium copper selenide sulfur according to claim 1, wherein: the temperature system is specifically as follows: the temperature is raised from room temperature to 500 ℃ at a heating rate of 5 ℃/min, and then the temperature is kept at 500 ℃ for 1 hour.
7. A negative electrode material characterized in that: prepared by the method for preparing the sulfur-vanadium-copper selenide solid solution according to claim 1.
8. A sodium ion battery characterized by: comprising a battery anode made of the anode material of claim 7.
CN202210350491.7A 2022-04-02 2022-04-02 Preparation method of copper vanadium selenide solid solution, negative electrode material and sodium ion battery Active CN114715858B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210350491.7A CN114715858B (en) 2022-04-02 2022-04-02 Preparation method of copper vanadium selenide solid solution, negative electrode material and sodium ion battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210350491.7A CN114715858B (en) 2022-04-02 2022-04-02 Preparation method of copper vanadium selenide solid solution, negative electrode material and sodium ion battery

Publications (2)

Publication Number Publication Date
CN114715858A CN114715858A (en) 2022-07-08
CN114715858B true CN114715858B (en) 2023-08-25

Family

ID=82242462

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210350491.7A Active CN114715858B (en) 2022-04-02 2022-04-02 Preparation method of copper vanadium selenide solid solution, negative electrode material and sodium ion battery

Country Status (1)

Country Link
CN (1) CN114715858B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102031565A (en) * 2010-10-15 2011-04-27 中国科学院安徽光学精密机械研究所 Polycrystal material with sulvanite structure and application thereof
CN103165881A (en) * 2011-12-12 2013-06-19 张健 Lithium iron phosphate doped nanometer anode material and preparation method thereof
CN108249392A (en) * 2016-11-30 2018-07-06 连展科技电子（昆山）有限公司 Mushroom granule, heat conduction material and method for producing mushroom granule
CN108394937A (en) * 2018-03-26 2018-08-14 宁夏大学 Vulcanize the preparation method of ferromanganese solid solution and its application as lithium ion battery negative material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102031565A (en) * 2010-10-15 2011-04-27 中国科学院安徽光学精密机械研究所 Polycrystal material with sulvanite structure and application thereof
CN103165881A (en) * 2011-12-12 2013-06-19 张健 Lithium iron phosphate doped nanometer anode material and preparation method thereof
CN108249392A (en) * 2016-11-30 2018-07-06 连展科技电子（昆山）有限公司 Mushroom granule, heat conduction material and method for producing mushroom granule
CN108394937A (en) * 2018-03-26 2018-08-14 宁夏大学 Vulcanize the preparation method of ferromanganese solid solution and its application as lithium ion battery negative material

Also Published As

Publication number Publication date
CN114715858A (en) 2022-07-08

Similar Documents

Publication Publication Date Title
CN111293300B (en) Zinc-cobalt sulfide/carbon nano anode material and preparation method thereof
CN110474044A (en) A kind of high-performance water system Zinc ion battery positive electrode and the preparation method and application thereof
Chu et al. MOF-derived hollow NiCo 2 O 4 nanowires as stable Li-ion battery anodes
CN107452951B (en) XS2@YSe2The preparation method of the anode material of lithium-ion battery of core-shell structure
Gu et al. Thin-carbon-layer-enveloped cobalt–iron oxide nanocages as a high-efficiency sulfur container for Li–S batteries
CN110289416B (en) Preparation method of bismuth-molybdenum bimetallic sulfide as negative electrode material of sodium-ion battery
Zheng et al. Constructing a novel heterostructure of NiSe 2/CoSe 2 nanoparticles with boosted sodium storage properties for sodium-ion batteries
CN108232142B (en) Zinc sulfide/graphene composite material, and preparation method and application thereof
CN105355919A (en) Preparation method of copper, cobalt and sulfur micropowder
CN108394937B (en) Preparation method of manganese iron sulfide solid solution and application of manganese iron sulfide solid solution as negative electrode material of lithium ion battery
CN112436145A (en) Preparation method and application of MOF-74 derived carbon-coated cobalt-nickel bimetallic sulfide for sodium ion battery negative electrode
CN111403731B (en) 3d orbital alloy sulfide material and preparation method and application thereof
CN110265652B (en) Preparation method of nano flaky Sb/C composite material for lithium ion/sodium ion battery cathode
CN108598409B (en) Lithium ion battery cathode material FeS/Fe/C and preparation method thereof
CN109742361B (en) Preparation method and application of composite sodium-ion battery negative electrode material
CN111592045A (en) Potassium manganate potassium ion battery anode material
He et al. A novel coordination polymer based on a new multidentate ligand: synthesis, structure and properties
CN109279663B (en) Borate sodium-ion battery negative electrode material and preparation and application thereof
CN114937764A (en) Cobalt disulfide composite material protected by double carbon layers and preparation method and application thereof
CN117855436A (en) Sodium vanadium fluorophosphate-based positive electrode material and preparation method and application thereof
CN114715858B (en) Preparation method of copper vanadium selenide solid solution, negative electrode material and sodium ion battery
CN116903048A (en) In-situ induced and constructed vacancy-rich bimetallic sulfide lithium ion battery anode material and preparation method thereof
CN109473634A (en) Solid phase heat together synthesizes two selenizing molybdenums/N doping carbon-point method
CN107017406B (en) FeS2Nanocrystalline and synthetic method and application thereof
CN106784750A (en) A kind of TiO/C negative materials and its preparation method and application

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant