CN114956038A - Molybdenum carbide modified hollow nitrogen-doped carbon particles and preparation method and application thereof - Google Patents

Molybdenum carbide modified hollow nitrogen-doped carbon particles and preparation method and application thereof Download PDF

Info

Publication number
CN114956038A
CN114956038A CN202210567459.4A CN202210567459A CN114956038A CN 114956038 A CN114956038 A CN 114956038A CN 202210567459 A CN202210567459 A CN 202210567459A CN 114956038 A CN114956038 A CN 114956038A
Authority
CN
China
Prior art keywords
doped carbon
molybdenum carbide
carbon particles
modified hollow
hollow nitrogen
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.)
Granted
Application number
CN202210567459.4A
Other languages
Chinese (zh)
Other versions
CN114956038B (en
Inventor
黄建林
牟机熔
欧历棋
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.)
South China University of Technology SCUT
Original Assignee
South China University of Technology SCUT
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 South China University of Technology SCUT filed Critical South China University of Technology SCUT
Priority to CN202210567459.4A priority Critical patent/CN114956038B/en
Publication of CN114956038A publication Critical patent/CN114956038A/en
Application granted granted Critical
Publication of CN114956038B publication Critical patent/CN114956038B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/205—Preparation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • C01B32/914—Carbides of single elements
    • C01B32/949—Tungsten or molybdenum carbides
    • 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
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
    • 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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • 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
    • 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)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses molybdenum carbide modified hollow nitrogen-doped carbon particles and a preparation method and application thereof. The preparation method of the molybdenum carbide modified hollow nitrogen-doped carbon particles comprises the following steps: 1) preparing carboxylated polystyrene microspheres; 2) preparing a carboxylated polystyrene microsphere co-modified by ZIF-8 and phosphomolybdic acid; 3) and (3) putting the carboxylated polystyrene microspheres co-modified by ZIF-8 and phosphomolybdic acid in a protective atmosphere, and calcining to obtain the molybdenum carbide modified hollow nitrogen-doped carbon particles. The molybdenum carbide modified hollow nitrogen-doped carbon particles can improve the sulfur load and polysulfide adsorption, are favorable for promoting the conversion between sulfur and polysulfide, have simple preparation method and low production cost, and are combined with sublimed sulfur to prepare the cathode material to be assembled into the sodium-sulfur battery, so that the sodium-sulfur battery has excellent cycle stability and rate capability and is suitable for large-scale application.

Description

Molybdenum carbide modified hollow nitrogen-doped carbon particles and preparation method and application thereof
Technical Field
The invention relates to the technical field of room-temperature sodium-sulfur batteries, in particular to molybdenum carbide modified hollow nitrogen-doped carbon particles and a preparation method and application thereof.
Background
In recent years, with the rapid development of electric vehicles and large-scale energy storage systems, development of a novel battery having both high energy density and low cost has become a research hotspot. The room temperature sodium-sulfur battery has the advantages of high energy density, rich raw material reserves, environmental protection and the like, and becomes one of promising candidates of next-generation energy storage devices. However, due to the influence of factors such as the insulation of sulfur and discharge products, the "shuttle effect" of polysulfide, and volume expansion, room temperature sodium-sulfur batteries have a series of problems such as poor cycle performance, poor rate performance, and low coulombic efficiency, which limits the large-scale commercial application of room temperature sodium-sulfur batteries.
Therefore, an efficient catalyst is developed to be used as a sulfur anode carrier, so that the anchoring of sodium polysulfide and the rapid conversion of the sodium polysulfide are realized, and the catalyst has very important significance for solving the shuttle effect of the room-temperature sodium-sulfur battery and improving the performance of the battery.
Disclosure of Invention
The invention aims to provide molybdenum carbide modified hollow nitrogen-doped carbon particles and a preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
a preparation method of molybdenum carbide modified hollow nitrogen-doped carbon particles comprises the following steps:
1) dispersing styrene, methyl methacrylate, acrylic acid, a pH regulator and an initiator in water, and reacting to obtain carboxylated polystyrene microspheres;
2) dispersing carboxylated polystyrene microspheres, zinc salt, phosphomolybdic acid and 2-methylimidazole in methanol for reaction to obtain ZIF-8 and phosphomolybdic acid co-modified carboxylated polystyrene microspheres;
3) and (3) putting the carboxylated polystyrene microspheres co-modified by ZIF-8 and phosphomolybdic acid in a protective atmosphere, and calcining to obtain the molybdenum carbide modified hollow nitrogen-doped carbon particles.
Preferably, the molar ratio of the styrene, the methyl methacrylate and the acrylic acid in the step 1) is 1: 0.03-0.07.
Preferably, the pH regulator in step 1) is at least one of ammonium bicarbonate and sodium bicarbonate.
Preferably, the addition amount of the pH regulator in the step 1) is 0.02-0.03% of the mass of the styrene.
Preferably, the initiator in the step 1) is at least one of ammonium persulfate, potassium persulfate and sodium persulfate.
Preferably, the addition amount of the initiator in the step 1) is 0.025-0.035% of the mass of the styrene.
Preferably, the reaction in the step 1) is carried out at 70-90 ℃, and the reaction time is 10-15 h.
Preferably, the molar ratio of the zinc salt, phosphomolybdic acid and 2-methylimidazole in the step 2) is 1: 0.8-2.4: 6-10.
Preferably, the zinc salt in step 2) is at least one of zinc nitrate, zinc sulfate and zinc chloride.
Preferably, the reaction in step 2) is carried out at room temperature, and the reaction time is 15-20 h.
Preferably, the protective atmosphere in step 3) is one of a nitrogen atmosphere and an argon atmosphere.
Preferably, the calcination in step 3) is specifically performed by: heating to 800-1000 ℃ at the heating rate of 3-5 ℃/min, and then preserving the heat for 1-3 h.
Hollow nitrogen-doped carbon particles modified by molybdenum carbide are prepared by the preparation method.
The room-temperature sodium-sulfur battery cathode material comprises the molybdenum carbide modified hollow nitrogen-doped carbon particles and sublimed sulfur.
Preferably, the mass ratio of the molybdenum carbide modified hollow nitrogen-doped carbon particles to the sublimed sulfur is 1: 1.2-2.0.
The preparation method of the room-temperature sodium-sulfur battery positive electrode material comprises the following steps: dispersing the molybdenum carbide modified hollow nitrogen-doped carbon particles and sublimed sulfur in a volatile organic solvent, grinding until the volatile organic solvent is completely volatilized, heating to 150-160 ℃, keeping the temperature for 6-12 h, naturally cooling to room temperature, placing in a protective atmosphere, and treating at 200-300 ℃ for 10-30 min to obtain the room-temperature sodium-sulfur battery cathode material.
Preferably, the volatile organic solvent is carbon disulfide.
Preferably, the protective atmosphere is one of a nitrogen atmosphere and an argon atmosphere.
The room-temperature sodium-sulfur battery comprises the positive electrode material.
The invention has the beneficial effects that: the molybdenum carbide modified hollow nitrogen-doped carbon particles can improve the sulfur load and polysulfide adsorption, are favorable for promoting the conversion between sulfur and polysulfide, have simple preparation method and low production cost, and are combined with sublimed sulfur to prepare the cathode material to be assembled into the sodium-sulfur battery, so that the sodium-sulfur battery has excellent cycle stability and rate capability and is suitable for large-scale application.
Specifically, the method comprises the following steps:
1) molybdenum carbide (alpha-MoC) in molybdenum carbide-modified hollow nitrogen-doped carbon particles of the present invention 1-x ) The conductive graphite has high conductivity, and is beneficial to improving the conductivity and the graphitization degree of particles;
2) the hollow structure of the molybdenum carbide modified hollow nitrogen-doped carbon particles can realize high sulfur load, and can provide enough buffer space to adapt to volume expansion of sulfur;
3) the hollow nitrogen-doped carbon shell in the molybdenum carbide-modified hollow nitrogen-doped carbon particle can provide a site for adsorption of polysulfide;
4) the polar molybdenum carbide (alpha-MoC) embedded in the molybdenum carbide modified hollow nitrogen-doped carbon particles of the invention 1-x ) The nanoparticles can provide abundant chemisorption sites for polysulfides, and can show high electrochemical catalytic activity for the redox process of sodium polysulfide, so that the room-temperature sodium-sulfur battery can show excellent electrochemical performance;
5) the preparation method of the molybdenum carbide modified hollow nitrogen-doped carbon particles is simple, low in production cost and suitable for large-scale popularization and application.
Drawings
FIG. 1 is a TEM and SEM images of MoC @ HNC-15 in example 1.
FIG. 2 is a nitrogen adsorption-desorption curve for MoC @ HNC-15 in example 1.
Fig. 3 is a schematic view of a process for preparing the positive electrode material of the room-temperature sodium-sulfur battery in example 1.
Fig. 4 is a TGA profile of the room temperature sodium-sulfur battery positive electrode material of example 1.
Fig. 5 is a graph of electrochemical performance test results for the CR2032 coin cell of example 1.
FIG. 6 is an SEM photograph of MoC @ HNC-10 in example 2.
Fig. 7 is a graph of electrochemical performance test results for the CR2032 coin cell of example 2.
Fig. 8 is an SEM image of HNC in comparative example 1.
Fig. 9 is a graph showing the results of electrochemical performance tests on CR2032 coin cells of comparative example 1.
Fig. 10 is a graph of the electrochemical performance test results for the CR2032 coin cell of comparative example 2.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
a preparation method of hollow nitrogen-doped carbon particles modified by molybdenum carbide comprises the following steps:
1) adding 21mL of styrene, 1.1mL of methyl methacrylate, 0.92mL of acrylic acid and 0.49g of ammonium bicarbonate into 100mL of ultrapure water, stirring and heating to 70 ℃, adding 0.53g of ammonium persulfate, heating to 80 ℃, stirring and reacting for 12 hours, centrifugally washing a product by using deionized water, and freeze-drying to obtain a carboxylated polystyrene microsphere (marked as PS);
2) adding 0.3g of carboxylated polystyrene microspheres and 3.284g of 2-methylimidazole into 100mL of methanol, ultrasonically dispersing for 30min, dissolving 1.487g of zinc nitrate and 0.0506g of phosphomolybdic acid (PMA) by using 100mL of methanol under stirring, dropwise adding, reacting at room temperature for 16h, centrifuging, and collecting a solid product to obtain carboxylated polystyrene microspheres (recorded as PS/PMA @ ZIF-8-15) co-modified by ZIF-8 and phosphomolybdic acid;
3) and (2) putting the carboxylated polystyrene microspheres co-modified by ZIF-8 and phosphomolybdic acid into a tubular furnace, introducing argon for protection, heating to 900 ℃ at the heating rate of 5 ℃/min, preserving the heat for 2h, and cooling to room temperature to obtain the molybdenum carbide modified hollow nitrogen-doped carbon particles (marked as MoC @ HNC-15).
And (3) performance testing:
the Transmission Electron Microscope (TEM) and Scanning Electron Microscope (SEM) images of MoC @ HNC-15 in this example are shown in FIG. 1(a, b and c are TEM images, and d and e are SEM images), and the nitrogen adsorption-desorption curve is shown in FIG. 2.
As can be seen from fig. 1: the MoC @ HNC-15 in the embodiment is in a honeycomb shape, and can be known as a hollow structure from an illustration, so that the sulfur loading is facilitated.
As can be seen from fig. 2: micropores and mesopores coexist in the MoC @ HNC-15 in the embodiment, and a space can be provided for accommodating sulfur.
The preparation method of the room-temperature sodium-sulfur battery positive electrode material comprises the following steps:
dispersing MoC @ HNC-15 and sublimed sulfur in a mass ratio of 1:1.22 in 15mL of carbon disulfide, grinding the mixture in a fume hood until the carbon disulfide is completely volatilized, transferring the mixture to a hydrothermal reaction kettle, heating the hydrothermal reaction kettle to 155 ℃, preserving the heat for 12 hours, naturally cooling the mixture to room temperature, transferring the mixture to a tubular furnace, introducing argon for protection, and treating the mixture at 200 ℃ for 25 minutes to obtain the room-temperature sodium-sulfur battery cathode material (the preparation flow diagram is shown in figure 3).
And (3) performance testing:
the thermal weight loss (TGA) curve of the room temperature sodium-sulfur battery positive electrode material in this example is shown in fig. 4.
As can be seen from fig. 4: the sulfur content in the positive electrode material of the room-temperature sodium-sulfur battery in this example was 52 wt%.
A room-temperature sodium-sulfur battery is prepared by the following steps:
the positive electrode material of the room-temperature sodium-sulfur battery is made into a positive electrode plate, metal sodium is made into a negative electrode plate, ethylene carbonate-diethyl carbonate solution of sodium perchlorate with the concentration of 1.0mol/L (the volume ratio of ethylene carbonate to diethyl carbonate is 1:1) is used as electrolyte, and a CR2032 button battery is assembled in a glove box filled with argon.
And (3) performance testing:
fig. 5 shows the results of the electrochemical performance test of the CR2032 coin cell in this example.
As can be seen from fig. 5: the rate performance of the CR2032 button cell in the embodiment is excellent, and the specific discharge capacity is up to 351.8mAh/g even when the discharge rate is 10C.
Example 2:
a preparation method of hollow nitrogen-doped carbon particles modified by molybdenum carbide comprises the following steps:
1) adding 21mL of styrene, 1.1mL of methyl methacrylate, 0.92mL of acrylic acid and 0.49g of ammonium bicarbonate into 100mL of ultrapure water, stirring and heating to 70 ℃, adding 0.53g of ammonium persulfate, heating to 80 ℃, stirring and reacting for 12 hours, centrifugally washing a product by using deionized water, and freeze-drying to obtain a carboxylated polystyrene microsphere (marked as PS);
2) adding 0.3g of carboxylated polystyrene microspheres and 3.284g of 2-methylimidazole into 100mL of methanol, ultrasonically dispersing for 30min, dissolving 1.487g of zinc nitrate and 0.076g of phosphomolybdic acid by using 100mL of methanol under stirring, dropwise adding, reacting at room temperature for 16h, centrifuging, and collecting a solid product to obtain ZIF-8 and phosphomolybdic acid co-modified carboxylated polystyrene microspheres (marked as PS/PMA @ ZIF-8-10);
3) and (2) putting the carboxylated polystyrene microspheres co-modified by ZIF-8 and phosphomolybdic acid into a tubular furnace, introducing argon for protection, heating to 900 ℃ at the heating rate of 5 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain the molybdenum carbide modified hollow nitrogen-doped carbon particles (marked as MoC @ HNC-10).
A room temperature sodium-sulfur battery cathode material and assembled CR2032 coin cells (i.e., room temperature sodium-sulfur batteries) were prepared according to the method of example 1.
And (3) performance testing:
1) SEM images of MoC @ HNC-10 in this example are shown in FIG. 6(a, b, and c represent different magnifications).
As can be seen from fig. 6: the MoC @ HNC-10 in this example is a hollow spherical structure.
2) Fig. 7 shows the results of the electrochemical performance test of the CR2032 coin cell in this example.
As can be seen from fig. 7: the rate performance of the CR2032 coin cell in the embodiment is excellent, and the specific discharge capacity is up to 300.6mAh/g even when the discharge rate is 10C.
Example 3:
a preparation method of hollow nitrogen-doped carbon particles modified by molybdenum carbide comprises the following steps:
1) adding 21mL of styrene, 1.1mL of methyl methacrylate, 0.92mL of acrylic acid and 0.49g of ammonium bicarbonate into 100mL of ultrapure water, stirring and heating to 70 ℃, adding 0.53g of ammonium persulfate, heating to 80 ℃, stirring and reacting for 12 hours, centrifugally washing a product by using deionized water, and freeze-drying to obtain a carboxylated polystyrene microsphere (marked as PS);
2) adding 0.3g of carboxylated polystyrene microspheres and 3.284g of 2-methylimidazole into 100mL of methanol, ultrasonically dispersing for 30min, dissolving 0.681g of zinc chloride and 0.0506g of phosphomolybdic acid by using 100mL of methanol under stirring, dropwise adding, reacting for 16h at room temperature, centrifuging, and collecting a solid product to obtain the ZIF-8 and phosphomolybdic acid co-modified carboxylated polystyrene microspheres (recorded as PS/PMA @ ZIF-8-15);
3) and (2) putting the carboxylated polystyrene microspheres co-modified by ZIF-8 and phosphomolybdic acid into a tubular furnace, introducing argon for protection, heating to 900 ℃ at the heating rate of 5 ℃/min, preserving the heat for 2h, and cooling to room temperature to obtain the molybdenum carbide modified hollow nitrogen-doped carbon particles (marked as MoC @ HNC-15).
A room temperature sodium-sulfur battery cathode material and assembled CR2032 coin cells (i.e., room temperature sodium-sulfur batteries) were prepared according to the method of example 1.
Through the test (the test method is the same as that of the embodiment 1), the MoC @ HNC-15 in the embodiment is in a hollow spherical structure, and the performance of the CR2032 coin cell in the embodiment is similar to that of the CR2032 coin cell in the embodiment 1.
Example 4:
a preparation method of hollow nitrogen-doped carbon particles modified by molybdenum carbide comprises the following steps:
1) adding 21mL of styrene, 1.1mL of methyl methacrylate, 0.92mL of acrylic acid and 0.49g of ammonium bicarbonate into 100mL of ultrapure water, stirring and heating to 70 ℃, adding 0.53g of ammonium persulfate, heating to 80 ℃, stirring and reacting for 12 hours, centrifugally washing a product by using deionized water, and freeze-drying to obtain a carboxylated polystyrene microsphere (marked as PS);
2) adding 0.3g of carboxylated polystyrene microspheres and 3.284g of 2-methylimidazole into 100mL of methanol, ultrasonically dispersing for 30min, dissolving 0.681g of zinc chloride and 0.076g of phosphomolybdic acid by using 100mL of methanol under stirring, dropwise adding, reacting at room temperature for 16h, centrifuging, and collecting a solid product to obtain the ZIF-8 and phosphomolybdic acid co-modified carboxylated polystyrene microspheres (recorded as PS/PMA @ ZIF-8-10);
3) and (2) putting the carboxylated polystyrene microspheres co-modified by ZIF-8 and phosphomolybdic acid into a tubular furnace, introducing argon for protection, heating to 900 ℃ at the heating rate of 5 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain the molybdenum carbide modified hollow nitrogen-doped carbon particles (marked as MoC @ HNC-10).
A room temperature sodium-sulfur battery cathode material and assembled CR2032 coin cells (i.e., room temperature sodium-sulfur batteries) were prepared according to the method of example 1.
Through the test (the test method is the same as that of the embodiment 1), the MoC @ HNC-10 in the embodiment is in a hollow spherical structure, and the performance of the CR2032 coin cell in the embodiment is similar to that of the CR2032 coin cell in the embodiment 2.
Example 5:
a preparation method of hollow nitrogen-doped carbon particles modified by molybdenum carbide comprises the following steps:
1) adding 21mL of styrene, 1.1mL of methyl methacrylate, 0.92mL of acrylic acid and 0.49g of ammonium bicarbonate into 100mL of ultrapure water, stirring and heating to 70 ℃, adding 0.53g of ammonium persulfate, heating to 80 ℃, stirring and reacting for 12 hours, centrifugally washing a product by using deionized water, and freeze-drying to obtain a carboxylated polystyrene microsphere (marked as PS);
2) adding 0.3g of carboxylated polystyrene microspheres and 3.284g of 2-methylimidazole into 100mL of methanol, ultrasonically dispersing for 30min, stirring and dissolving 1.438g of zinc sulfate and 0.0506g of phosphomolybdic acid by using 100mL of methanol, dropwise adding, reacting for 16h at room temperature, centrifuging, and collecting a solid product to obtain ZIF-8 and phosphomolybdic acid co-modified carboxylated polystyrene microspheres (recorded as PS/PMA @ ZIF-8-15);
3) and (2) putting the carboxylated polystyrene microspheres co-modified by ZIF-8 and phosphomolybdic acid into a tubular furnace, introducing argon for protection, heating to 900 ℃ at the heating rate of 5 ℃/min, preserving the heat for 2h, and cooling to room temperature to obtain the molybdenum carbide modified hollow nitrogen-doped carbon particles (marked as MoC @ HNC-15).
A room temperature sodium-sulfur battery cathode material and assembled CR2032 coin cells (i.e., room temperature sodium-sulfur batteries) were prepared according to the method of example 1.
Through the test (the test method is the same as that of the embodiment 1), the MoC @ HNC-15 in the embodiment is in a hollow spherical structure, and the performance of the CR2032 coin cell in the embodiment is similar to that of the CR2032 coin cell in the embodiment 1.
Example 6:
a preparation method of hollow nitrogen-doped carbon particles modified by molybdenum carbide comprises the following steps:
1) adding 21mL of styrene, 1.1mL of methyl methacrylate, 0.92mL of acrylic acid and 0.49g of ammonium bicarbonate into 100mL of ultrapure water, stirring and heating to 70 ℃, adding 0.53g of ammonium persulfate, heating to 80 ℃, stirring and reacting for 12 hours, centrifugally washing a product by using deionized water, and freeze-drying to obtain a carboxylated polystyrene microsphere (marked as PS);
2) adding 0.3g of carboxylated polystyrene microsphere and 3.284g of 2-methylimidazole into 100mL of methanol, ultrasonically dispersing for 30min, stirring and dissolving 1.438g of zinc sulfate and 0.076g of phosphomolybdic acid by using 100mL of methanol, dropwise adding, reacting at room temperature for 16h, centrifuging, and collecting a solid product to obtain a ZIF-8 and phosphomolybdic acid co-modified carboxylated polystyrene microsphere (marked as PS/PMA @ ZIF-8-10);
3) and (2) putting the carboxylated polystyrene microspheres co-modified by ZIF-8 and phosphomolybdic acid into a tubular furnace, introducing argon for protection, heating to 900 ℃ at the heating rate of 5 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain the molybdenum carbide modified hollow nitrogen-doped carbon particles (marked as MoC @ HNC-10).
A room temperature sodium-sulfur battery cathode material and assembled CR2032 coin cells (i.e., room temperature sodium-sulfur batteries) were prepared according to the method of example 1.
Through the test (the test method is the same as that of the embodiment 1), the MoC @ HNC-10 in the embodiment is in a hollow spherical structure, and the performance of the CR2032 coin cell in the embodiment is similar to that of the CR2032 coin cell in the embodiment 2.
Comparative example 1:
a nitrogen-doped hollow carbon particle, the preparation method of which comprises the following steps:
1) adding 21mL of styrene, 1.1mL of methyl methacrylate, 0.92mL of acrylic acid and 0.49g of ammonium bicarbonate into 100mL of ultrapure water, stirring and heating to 70 ℃, adding 0.53g of ammonium persulfate, heating to 80 ℃, stirring and reacting for 12 hours, centrifugally washing a product by using deionized water, and freeze-drying to obtain a carboxylated polystyrene microsphere (marked as PS);
2) adding 0.3g of carboxylated polystyrene microsphere and 3.284g of 2-methylimidazole into 100mL of methanol, ultrasonically dispersing for 30min, dissolving 1.487g of zinc nitrate in 100mL of methanol by stirring, dropwise adding, reacting at room temperature for 16h, centrifuging, and collecting a solid product to obtain a ZIF-8 modified carboxylated polystyrene microsphere (marked as PS @ ZIF-8);
3) and (3) placing the ZIF-8 modified carboxylated polystyrene microspheres in a tube furnace, introducing argon for protection, heating to 900 ℃ at the heating rate of 5 ℃/min, preserving heat for 2 hours, and cooling to room temperature to obtain the nitrogen-doped hollow carbon particles (marked as HNC).
A room temperature sodium-sulfur battery cathode material and assembled CR2032 coin cells (i.e., room temperature sodium-sulfur batteries) were prepared according to the method of example 1.
And (3) performance testing:
1) SEM images of HNC in this comparative example are shown in fig. 8(a, b and c represent different magnifications).
As can be seen from fig. 8: the HNC in this comparative example is raspberry-like in structure.
2) The results of the electrochemical performance test of the CR2032 coin cell of this comparative example are shown in fig. 9.
As can be seen from fig. 9: the CR2032 button cell in the comparative example has poor rate performance, and the specific discharge capacity is only 139.5mAh/g when the discharge rate is 10C.
Comparative example 2:
a preparation method of nitrogen-doped carbon particles modified by molybdenum carbide comprises the following steps:
1) adding 3.284g of 2-methylimidazole into 100mL of methanol, ultrasonically dispersing for 30min, stirring and dissolving 1.438g of zinc nitrate and 0.0506g of phosphomolybdic acid by using 100mL of methanol, dropwise adding, reacting at room temperature for 16h, centrifuging, and collecting a solid product to obtain ZIF-8 (marked as PMA ZIF-8-15) modified by phosphomolybdic acid;
2) and (3) putting the ZIF-8 modified by phosphomolybdic acid into a tubular furnace, introducing argon for protection, heating to 900 ℃ at the heating rate of 5 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain the nitrogen-doped carbon particles (recorded as MoC @ NC-15) modified by molybdenum carbide.
A room temperature sodium-sulfur battery cathode material and assembled CR2032 coin cells (i.e., room temperature sodium-sulfur batteries) were prepared according to the method of example 1.
And (3) performance testing:
the results of the electrochemical performance test of the CR2032 coin cell of this comparative example are shown in fig. 10.
As can be seen from fig. 10: the CR2032 button cell in the comparative example has poor rate performance, and the specific discharge capacity is only 251.8mAh/g when the discharge rate is 10C.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A preparation method of molybdenum carbide modified hollow nitrogen-doped carbon particles is characterized by comprising the following steps:
1) dispersing styrene, methyl methacrylate, acrylic acid, a pH regulator and an initiator in water, and reacting to obtain carboxylated polystyrene microspheres;
2) dispersing carboxylated polystyrene microspheres, zinc salt, phosphomolybdic acid and 2-methylimidazole in methanol for reaction to obtain ZIF-8 and phosphomolybdic acid co-modified carboxylated polystyrene microspheres;
3) and (3) putting the carboxylated polystyrene microspheres co-modified by ZIF-8 and phosphomolybdic acid in a protective atmosphere, and calcining to obtain the molybdenum carbide modified hollow nitrogen-doped carbon particles.
2. The method of claim 1, wherein the molybdenum carbide-modified hollow nitrogen-doped carbon particle comprises: the molar ratio of the styrene to the methyl methacrylate to the acrylic acid in the step 1) is 1: 0.03-0.07.
3. The method of producing molybdenum carbide-modified hollow nitrogen-doped carbon particles according to claim 1 or 2, wherein: the reaction in the step 1) is carried out at 70-90 ℃ for 10-15 h.
4. The method of claim 1, wherein the molybdenum carbide-modified hollow nitrogen-doped carbon particle comprises: the molar ratio of the zinc salt, the phosphomolybdic acid and the 2-methylimidazole in the step 2) is 1: 0.8-2.4: 6-10.
5. The method of producing molybdenum carbide-modified hollow nitrogen-doped carbon particles according to claim 1 or 4, wherein: the reaction in the step 2) is carried out at room temperature, and the reaction time is 15-20 h.
6. The method of producing molybdenum carbide-modified hollow nitrogen-doped carbon particles according to any one of claims 1, 2 and 4, wherein: the specific operation of the calcination in the step 3) is as follows: heating to 800-1000 ℃ at the heating rate of 3-5 ℃/min, and then preserving the heat for 1-3 h.
7. A molybdenum carbide-modified hollow nitrogen-doped carbon particle characterized by being produced by the production method according to any one of claims 1 to 6.
8. A room temperature sodium-sulfur battery positive electrode material, characterized by comprising the molybdenum carbide-modified hollow nitrogen-doped carbon particles of claim 7 and sublimed sulfur.
9. The positive electrode material for a room temperature sodium-sulfur battery according to claim 8, characterized in that: the mass ratio of the molybdenum carbide modified hollow nitrogen-doped carbon particles to the sublimed sulfur is 1: 1.2-2.0.
10. A room temperature sodium-sulfur battery, characterized in that the composition of the positive electrode comprises the positive electrode material for room temperature sodium-sulfur batteries according to claim 8 or 9.
CN202210567459.4A 2022-05-24 2022-05-24 Molybdenum carbide modified hollow nitrogen-doped carbon particles and preparation method and application thereof Active CN114956038B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210567459.4A CN114956038B (en) 2022-05-24 2022-05-24 Molybdenum carbide modified hollow nitrogen-doped carbon particles and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210567459.4A CN114956038B (en) 2022-05-24 2022-05-24 Molybdenum carbide modified hollow nitrogen-doped carbon particles and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN114956038A true CN114956038A (en) 2022-08-30
CN114956038B CN114956038B (en) 2023-10-03

Family

ID=82984848

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210567459.4A Active CN114956038B (en) 2022-05-24 2022-05-24 Molybdenum carbide modified hollow nitrogen-doped carbon particles and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114956038B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111617645A (en) * 2020-05-20 2020-09-04 大连理工大学 Preparation method of low-resistance high-selectivity mixed matrix membrane based on hollow MOFs (metal-organic frameworks) material
CN114438620A (en) * 2022-01-06 2022-05-06 苏州科技大学 Hierarchical porous molybdenum carbide nanofiber and preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111617645A (en) * 2020-05-20 2020-09-04 大连理工大学 Preparation method of low-resistance high-selectivity mixed matrix membrane based on hollow MOFs (metal-organic frameworks) material
CN114438620A (en) * 2022-01-06 2022-05-06 苏州科技大学 Hierarchical porous molybdenum carbide nanofiber and preparation method and application thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
HEE JUNG LEE ET. AL.: ""Well-dispersed hollow porous carbon spheres synthesized by direct pyrolysis of core–shell type metal–organic frameworks and their sorption properties"", 《CHEMICAL COMMUNICATIONS》 *
JIAO LI ET. AL.: ""PMO12@ZIF-8/ZnO-derived hierarchical porous molybdenum carbide as efficient electrocatalysts for hydrogen evolution"", 《NEW JOURNAL OF CHEMISTRY》 *
XUEFENG ZHOU ET. AL.: ""A High-Efficiency Mo2C Electrocatalyst Promoting the Polysulfide Redox Kinetics for Na–S Batteries"", 《ADVANCED MATERIALS》 *

Also Published As

Publication number Publication date
CN114956038B (en) 2023-10-03

Similar Documents

Publication Publication Date Title
CN111362254A (en) Preparation method and application of nitrogen-doped carbon nanotube-loaded phosphorus-doped cobaltosic oxide composite material
CN113675402A (en) Metal-nitrogen doped porous carbon material and preparation method and application thereof
CN113097464B (en) ZnS-SnS @3DC composite material and preparation method and application thereof
CN106299344B (en) A kind of sodium-ion battery nickel titanate negative electrode material and preparation method thereof
CN111312999A (en) Preparation method of graphene-coated nickel-iron bimetallic sulfide sodium-ion battery negative electrode material
CN110790248B (en) Iron-doped cobalt phosphide microsphere electrode material with flower-shaped structure and preparation method and application thereof
CN114933293A (en) Preparation of sodium vanadium fluorophosphate and application thereof in sodium-ion battery
CN108539158B (en) rGO/WS2Preparation method of composite material and application of composite material in positive electrode material of lithium-sulfur battery
CN112694079B (en) Heteropolyacid etching capsule-shaped hollow porous carbon shell, preparation method and application thereof in lithium-sulfur battery
CN110611068B (en) Preparation method of novel lithium-sulfur battery diaphragm material
CN112670494A (en) Vanadate electrode material and preparation method and application thereof
CN111554874A (en) FeS2-xSexSolid solution cathode material and preparation method thereof
CN114956038B (en) Molybdenum carbide modified hollow nitrogen-doped carbon particles and preparation method and application thereof
CN110429250A (en) A kind of height ratio capacity positive electrode of sodium-sulfur cell material and preparation method thereof
CN113735180B (en) Method for preparing sodium ion battery anode material by using LDH-based precursor to obtain cobalt iron sulfide
CN114751395A (en) Nitrogen-doped porous carbon sphere/S composite material, preparation method thereof and application thereof in lithium-sulfur battery
CN115084509A (en) Preparation method and application of selenium indium sulfide/carbon cathode material for potassium ion battery
CN111446439B (en) S@MxSnSy@ C composite positive electrode active material, preparation method thereof and application of active material in lithium-sulfur battery
CN110723727B (en) Pine-branch-shaped samarium oxide graphene sulfur gel structural material, and preparation method and application thereof
CN113130879A (en) Preparation method of high-adsorption catalytic performance cathode material of lithium-sulfur battery
CN117673331B (en) Positive electrode material coating material and preparation method thereof, modified positive electrode material and preparation method thereof, and sodium ion battery
CN111740109B (en) Preparation method of boron and phosphorus doped graphitized carbon-nitrogen compound cathode material activated by KOH
CN114597366B (en) Ultrahigh-activity composite material, preparation method thereof and application thereof in magnesium-sulfur battery
CN115557534B (en) Preparation method of water-based zinc ion battery composite positive electrode material
CN110970612B (en) Preparation of transition metal oxide positive electrode material and application of transition metal oxide positive electrode material in sodium ion battery

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