CN113292052A - Hollow metal nitride/carbon microsphere composite material and preparation method and application thereof - Google Patents

Hollow metal nitride/carbon microsphere composite material and preparation method and application thereof Download PDF

Info

Publication number
CN113292052A
CN113292052A CN202110475031.2A CN202110475031A CN113292052A CN 113292052 A CN113292052 A CN 113292052A CN 202110475031 A CN202110475031 A CN 202110475031A CN 113292052 A CN113292052 A CN 113292052A
Authority
CN
China
Prior art keywords
composite material
carbon microsphere
stirring
microsphere composite
drying
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.)
Pending
Application number
CN202110475031.2A
Other languages
Chinese (zh)
Inventor
刘肖燕
王雪薇
杨梦华
吴金凤
李和兴
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.)
Shanghai Normal University
University of Shanghai for Science and Technology
Original Assignee
Shanghai Normal 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 Shanghai Normal University filed Critical Shanghai Normal University
Priority to CN202110475031.2A priority Critical patent/CN113292052A/en
Publication of CN113292052A publication Critical patent/CN113292052A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/0615—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium
    • C01B21/062—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium with chromium, molybdenum or tungsten
    • 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
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • 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
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • 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

Abstract

The invention relates to a hollow metal nitride/carbon microsphere composite material and a preparation method and application thereof, wherein organic molecules containing amino, metal carbonyl compounds and organic solvents are mixed and stirred; carrying out ultrasonic reaction under the protection of inert gas; washing and drying to obtain a precursor; stirring and melting the mixture and phenol, and then adding water and formaldehyde solution; continuously stirring and adding NaOH to adjust the pH value; adding ethanol and the silicon dioxide nano dispersion liquid, uniformly stirring, spray-drying, and collecting the obtained powder material; roasting in inert gas atmosphere, naturally cooling, etching with sodium hydroxide aqueous solution, washing, and drying to obtain the target product. Compared with the prior art, the method does not need explosive ammonia gas as a nitrogen source, and has the advantages of high production efficiency, high yield, easy industrialization and the like; tests show that the lithium-sulfur battery assembled by the material serving as a sulfur anode carrier and a diaphragm modification layer has high capacity cycling stability and wide application prospect.

Description

Hollow metal nitride/carbon microsphere composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of synthesis of nano materials, relates to modification of a lithium-sulfur battery diaphragm, and particularly relates to a hollow metal nitride/carbon microsphere composite material as well as a preparation method and application thereof.
Background
The lithium-sulfur battery is expected to become the next generation of energy storage and power secondary battery due to the characteristics of high capacity, low cost, environmental friendliness and the like. However, the practical application of lithium-sulfur batteries is still limited, and the following problems mainly exist: shuttling effects of lithium polysulfide intermediates, poor sulfur conductivity, volume expansion of sulfur during lithiation, and problems with lithium dendrites. Among them, the shuttle effect of lithium polysulfide is a major problem that hinders the development of positive electrodes of lithium sulfur batteries. Separators are an important component of lithium sulfur batteries. The commercial polyolefin separator had a large pore size and could not suppress Li2SnShuttling effects in lithium sulfur batteries.
Disclosure of Invention
If a barrier layer is constructed between the diaphragm and the anode, the rapid transmission of lithium ions is ensured, the migration of LiPSs is strongly limited, the shuttle effect can be well inhibited, and meanwhile, the barrier layer can be used as a second current collector to realize the capture and secondary conversion of lithium polysulfide and improve the utilization rate of active sulfur.
Metal nitride (MoN, Mo)2N or Mo3N2) Has an electronic structure similar to that of noble metals, and is an excellent electrocatalyst. Carbon-based materials are considered to be excellent sulfur host materials due to their advantages of low cost, good electrical conductivity, ease of processing, and the like. Therefore, the metal nitride and the carbon-based material are compounded for modifying the diaphragm, so that shuttling of the LiPSs can be effectively prevented, and the high efficiency is realizedAnd electrons and ions are transmitted, so that the battery capacity and the cycling stability of the lithium-sulfur battery are improved.
The invention aims to provide a hollow metal nitride/carbon microsphere composite material and a preparation method and application thereof aiming at the defects of lithium polysulfide shuttling, low utilization rate of active sulfur and the like in the conventional lithium-sulfur battery. The high-performance hollow metal nitride/carbon microsphere composite material is prepared by spray drying, the prepared material is applied to modification of the positive electrode and the diaphragm of the lithium-sulfur battery, a functional interlayer with adsorption and catalysis effects can be established between the sulfur positive electrode and the diaphragm, the shuttle effect is effectively inhibited, the in-situ reaction of lithium polysulfide is catalyzed, and the utilization rate of sulfur is improved.
The purpose of the invention can be realized by the following technical scheme:
the invention provides a preparation method of a hollow metal nitride/carbon microsphere composite material, which comprises the following steps:
s1: preparing a precursor:
s11: mixing and stirring an organic molecule containing amino, a metal carbonyl compound and an organic solvent;
s12: carrying out ultrasonic reaction under the protection of inert gas;
s13: washing and drying to obtain a precursor;
s2: spray drying:
s21: stirring and melting the obtained precursor and phenol, and then adding water and formaldehyde solution;
s22: continuously stirring and adding NaOH to adjust the pH value;
s23: adding ethanol and the silicon dioxide nano dispersion liquid, uniformly stirring, spray-drying, and collecting the obtained powder material;
s3: and roasting the obtained powder material in an inert gas atmosphere, naturally cooling, collecting the material, etching the material by using a sodium hydroxide aqueous solution, and then washing and drying to obtain the hollow metal nitride/carbon microsphere composite material.
Preferably, in step S1, the organic molecule containing an amino group includes urea, melamine, ethanolamine, ethylenediamine or isopropylamine.
Preferably, in step S1, the metal carbonyl compound includes at least one of iron carbonyl, molybdenum carbonyl, cobalt carbonyl, nickel carbonyl, and tungsten carbonyl.
Preferably, in step S1, the organic solvent includes at least one of methanol, ethanol, chloroform, n-butane, cyclohexane, n-hexadecane, benzene, and toluene.
Preferably, in step S1, the ratio of the amount of the amino group-containing organic molecule, the amount of the metal carbonyl compound and the amount of the organic solvent used is 0.1 to 30g:0.01 to 300g:10 to 500 mL.
Preferably, in step S1, the temperature of the ultrasonic reaction is 30 to 90 ℃, and the reaction time is 0.5 to 10 hours.
Preferably, in the step S1, the drying time is 6-24 hours, and the temperature is 60-120 ℃.
Preferably, in step S2, the ratio of the usage amounts of the phenol, the deionized water, the formaldehyde, the ethanol, the nano-dispersion of the silicon dioxide and the organic molecule containing amino groups is 1-25 g: 1-100 mL: 2-100 mL: 1-50 g: 0.1-30 g.
Preferably, in step S2, the mass fraction of the silica nano dispersion is 10-30 wt% SiO2EtOH, the size of the silicon dioxide in the silicon dioxide nano dispersion liquid is 3-50 nm.
Preferably, in step S2, the temperature of the molten mixture is 40 ℃.
Preferably, in step S2, NaOH is added to adjust the pH value to 4-12, and the stirring time is 0.2-6 h.
Preferably, in step S2, the temperature of spray drying is room temperature to 800 ℃.
Preferably, in step S3, the obtained powder material is roasted at a high temperature in an argon atmosphere, and the heating rate is 1-10 ℃ for min-1The roasting temperature is 400-1000 ℃, and the roasting time is 1-10 h.
Preferably, in step S3, the concentration of the aqueous solution of sodium hydroxide is 5mol L-1。
The invention provides a hollow metal nitride/carbon microsphere composite material obtained by the preparation method in a second aspect.
The third aspect of the invention provides application of the hollow metal nitride/carbon microsphere composite material, which is used for modifying the positive electrode and the diaphragm of the lithium-sulfur battery, and a functional interlayer with adsorption and catalysis effects is established between the positive electrode and the diaphragm of the sulfur battery.
Compared with the prior art, the hollow metal nitride/carbon microsphere composite material is prepared by a spray drying method by taking amino-containing organic molecules as nitrogen sources and metal carbonyl compounds as metal sources. In the traditional method for preparing the metal compound, ammonia gas is mostly used as a nitrogen source in a reaction at high temperature, and certain dangerousness is realized. Compared with the traditional method, the method avoids the use of ammonia gas, has higher safety, and has the advantages of high reaction speed, high yield, easy industrialization and the like. The superfine metal nitride nano particles in the prepared hollow metal nitride/carbon microsphere composite material are uniformly dispersed in the hollow carbon microsphere and used as a positive host and a diaphragm modification layer of the lithium-sulfur battery, the material can chemically anchor lithium polysulfide and can catalyze the rapid conversion of the lithium polysulfide, the shuttle effect can be efficiently inhibited, the effects of improving the capacity and the cycle stability of the lithium-sulfur battery are remarkable, and the material has great application potential.
Drawings
FIG. 1 is a scanning electron microscope image of a hollow molybdenum nitride/carbon microsphere composite material in example 2 of the present invention;
FIGS. 2(a) and 2(b) are transmission electron micrographs of hollow molybdenum nitride/carbon microsphere composite material of example 2 of the present invention at different magnifications (500nm and 10 nm);
FIG. 3 is an X-ray diffraction pattern of the hollow molybdenum nitride/carbon microsphere composite material of examples 1,2 and 3 of the present invention;
FIG. 4 shows the scanning rate of 0.1mV s for the hollow molybdenum nitride/carbon microsphere composite material of examples 1,2 and 3 according to the present invention-1Cyclic Voltammetry (CV) profile of (a);
FIG. 5 is a charge-discharge curve diagram of the hollow molybdenum nitride/carbon microsphere composite material of examples 1,2 and 3 of the present invention at a current density of 0.2C;
FIG. 6 is a graph showing the capacity cycling curve of the hollow molybdenum nitride/carbon microsphere composite material of examples 1,2 and 3 according to the present invention at a current density of 0.2C.
Detailed Description
A preparation method of a hollow metal nitride/carbon microsphere composite material comprises the following steps:
s1: preparing a precursor:
s11: mixing and stirring an organic molecule containing amino, a metal carbonyl compound and an organic solvent;
s12: carrying out ultrasonic reaction under the protection of inert gas;
s13: washing and drying to obtain a precursor;
s2: spray drying:
s21: stirring and melting the obtained precursor and phenol, and then adding water and formaldehyde solution;
s22: continuously stirring and adding NaOH to adjust the pH value;
s23: adding ethanol and the silicon dioxide nano dispersion liquid, uniformly stirring, spray-drying, and collecting the obtained powder material;
s3: and roasting the obtained powder material in an inert gas atmosphere, naturally cooling, collecting the material, etching the material by using a sodium hydroxide aqueous solution, and then washing and drying to obtain the hollow metal nitride/carbon microsphere composite material.
Preferably, in step S1, the organic molecule containing an amino group includes urea, melamine, ethanolamine, ethylenediamine or isopropylamine.
Preferably, in step S1, the metal carbonyl compound includes at least one of iron carbonyl, molybdenum carbonyl, cobalt carbonyl, nickel carbonyl, and tungsten carbonyl.
Preferably, in step S1, the organic solvent includes at least one of methanol, ethanol, chloroform, n-butane, cyclohexane, n-hexadecane, benzene, and toluene.
Preferably, in step S1, the ratio of the amount of the amino group-containing organic molecule, the amount of the metal carbonyl compound and the amount of the organic solvent used is 0.1 to 30g:0.01 to 300g:10 to 500 mL.
Preferably, in step S1, the temperature of the ultrasonic reaction is 30 to 90 ℃, and the reaction time is 0.5 to 10 hours.
Preferably, in the step S1, the drying time is 6-24 hours, and the temperature is 60-120 ℃.
Preferably, in step S2, the ratio of the usage amounts of the phenol, the deionized water, the formaldehyde, the ethanol, the nano-dispersion of the silicon dioxide and the organic molecule containing amino groups is 1-25 g: 1-100 mL: 2-100 mL: 1-50 g: 0.1-30 g.
Preferably, in step S2, the mass fraction of the silica nano dispersion is 10-30 wt% SiO2EtOH, the size of the silicon dioxide in the silicon dioxide nano dispersion liquid is 3-50 nm.
Preferably, in step S2, the temperature of the molten mixture is 40 ℃.
Preferably, in step S2, NaOH is added to adjust the pH value to 4-12, and the stirring time is 0.2-6 h.
Preferably, in step S2, the temperature of spray drying is room temperature to 800 ℃.
Preferably, in step S3, the obtained powder material is roasted at a high temperature in an argon atmosphere, and the heating rate is 1-10 ℃ for min-1The roasting temperature is 400-1000 ℃, and the roasting time is 1-10 h.
Preferably, in step S3, the concentration of the aqueous solution of sodium hydroxide is 5mol L-1。
The hollow metal nitride/carbon microsphere composite material obtained by the preparation method.
The hollow metal nitride/carbon microsphere composite material is applied to modification of a positive electrode and a diaphragm of a lithium-sulfur battery, and a functional interlayer with adsorption and catalysis effects is established between the positive electrode and the diaphragm.
The invention is described in detail below with reference to the figures and specific embodiments.
In the invention, the spray dryer for preparing the hollow metal nitride/carbon microsphere composite material is YC-015 type spray drying produced by Shanghai Yachen instrument equipment company Limited; performing transmission electron microscope characterization on the composite material by using a Japanese JEM-2100 projection electron microscope; the composite material is subjected to XRD characterization by using a BRUKER D8ADVANCE X-ray diffractometer; the electrochemical workstation used for electrochemical testing in the lithium sulfur battery test is MPG-2 type Bio-logic, and the blue electricity testing device is CT2001A type LANHE blue electricity battery testing system.
In the invention, the prepared hollow metal nitride/carbon microsphere composite material is applied to the lithium-sulfur battery test, 80mg of the hollow metal nitride/carbon microsphere composite material and high-purity sulfur are ground and mixed according to a certain proportion, and the hollow metal nitride/carbon microsphere composite material loaded with 68 wt% of sulfur is obtained by adopting a traditional melting diffusion method. Then, 40mg of the composite material, super P and PVDF are mixed in a proper amount of NMP according to the mass ratio of 8:1:1, stirred into slurry, coated on a carbon-coated aluminum foil, dried in vacuum at 60 ℃ for 12 hours, and cut into a circular pole piece with the diameter of 12 mm. And then mixing 80mg of the hollow metal nitride/carbon microsphere composite material and PVDF in a proper amount of NMP according to the mass ratio of 9:1, stirring into slurry, coating the slurry on a PP diaphragm, drying in vacuum at 60 ℃ for 12h, and cutting into a circular diaphragm with the diameter of 18 mm.
In the test of the hollow metal nitride/carbon microsphere composite material in the lithium-sulfur battery, the hollow metal nitride/carbon microsphere composite material loaded with sulfur is used as a positive electrode, the hollow metal nitride/carbon microsphere composite material is coated with a diaphragm, and a lithium sheet is used as a negative electrode to assemble the battery. Then, CV and constant current charge and discharge tests were performed on the assembled battery.
Example 1
Adding 5g of melamine, 2g of molybdenum carbonyl and 40mL of n-hexadecane into a flask and stirring; then carrying out ultrasonic reaction for 4 hours at the temperature of 80 ℃ under argon; washing with n-pentane for 4-5 times, and drying at 105 ℃ for 12h to obtain a precursor; the precursor and 2.5g of phenol are stirred and melted at 40 ℃. 20mL of water and 20mL of formaldehyde solution are added, 1M sodium hydroxide solution is added to adjust the pH to 9, stirring is continued for 1h, and then 35mL of ethanol and 15g of 20 wt% SiO2EtOH silicon dioxide dispersion with size of 10nm, stirring for 15min, and spray drying at 200 deg.C to obtain material; roasting the obtained material at high temperature in argon atmosphere, wherein the heating rate is 10 ℃ for min-1Roasting at 500 ℃ for 5h and at 900 ℃ for 2h, naturally cooling to obtain a material, etching the material for 3-4 times by using a 5M sodium hydroxide solution, washing for 3-4 times by using deionized water, and finally blowing at 80 DEG CDrying for 12h to obtain the hollow molybdenum nitride/carbon microsphere composite material.
Example 2
Adding 5g of melamine, 3g of molybdenum carbonyl and 40mL of n-hexadecane into a flask and stirring; then carrying out ultrasonic reaction for 4 hours at the temperature of 80 ℃ under argon; washing with n-pentane for 4-5 times, and drying at 105 ℃ for 12h to obtain a precursor; the precursor and 2.5g of phenol are stirred and melted at 40 ℃. 20mL of water and 20mL of formaldehyde solution are added, 1M sodium hydroxide solution is added to adjust the pH to 9, stirring is continued for 1h, and then 35mL of ethanol and 15g of 20 wt% SiO2EtOH silicon dioxide dispersion with size of 10nm, stirring for 15min, and spray drying at 200 deg.C to obtain material; roasting the obtained material at high temperature in argon atmosphere, wherein the heating rate is 10 ℃ for min-1And roasting at 500 ℃ for 5h and at 900 ℃ for 2h, naturally cooling to obtain a material, etching the material for 3-4 times by using a 5M sodium hydroxide solution, washing for 3-4 times by using deionized water, and finally drying by blowing at 80 ℃ for 12h to obtain the hollow molybdenum nitride/carbon microsphere composite material.
Example 2 scanning electron microscope images of the hollow molybdenum nitride/carbon microsphere composite material prepared in the embodiment show that the porous carbon spherical structure of the prepared material can be seen from the images (as shown in attached figure 1).
Example 2A diagram of a hollow molybdenum nitride/carbon microsphere composite transmission mirror prepared in example 2 shows that the prepared material has a spherical structure, and a molybdenum nitride catalyst is distributed on the surface of the sphere, and the particle size is 2-10nm (as shown in the attached FIGS. 2(a) and 2 (b))
Example 3
Adding 5g of melamine, 4g of molybdenum carbonyl and 40mL of n-hexadecane into a flask and stirring; then carrying out ultrasonic reaction for 4 hours at the temperature of 80 ℃ under argon; washing with n-pentane for 4-5 times, and drying at 105 ℃ for 12h to obtain a precursor; the precursor and 2.5g of phenol are stirred and melted at 40 ℃. 20mL of water and 20mL of formaldehyde solution were added, 1M sodium hydroxide solution was added to adjust the pH to 9, stirring was continued for 1 hour, and 35mL of ethanol and 15g of 20 wt% SiO2EtOH silicon dioxide dispersion with size of 10nm, stirring for 15min, and spray drying at 200 deg.C to obtain material; subjecting the obtained material to argonRoasting at high temperature in the atmosphere, wherein the heating rate is 10 ℃ for min-1And roasting at 500 ℃ for 5h and at 900 ℃ for 2h, naturally cooling to obtain a material, etching the material for 3-4 times by using a 5M sodium hydroxide solution, washing for 3-4 times by using deionized water, and finally drying by blowing at 80 ℃ for 12h to obtain the hollow molybdenum nitride/carbon microsphere composite material.
The X-ray diffraction patterns of the hollow molybdenum nitride/carbon microsphere composite materials prepared in examples 1,2 and 3 show that a distinct graphitization characteristic peak (about 23 degrees) and a distinct molybdenum nitride characteristic peak (JCPDS No.25-1366) can be clearly observed, which indicates that the synthesized material is a hollow molybdenum nitride/carbon microsphere composite material (as shown in FIG. 3).
Comparing the Cyclic Voltammetry (CV) graphs of the hollow molybdenum nitride/carbon microsphere composites prepared in examples 1,2 and 3, it can be seen that the battery assembled by the hollow molybdenum nitride/carbon microsphere composite prepared from 3g of molybdenum carbonyl has a larger peak current density and a smaller polarization voltage, indicating that the battery promotes faster sulfur redox reaction and faster kinetics during the cycling process (as shown in fig. 4).
As can be seen from comparison of the charge-discharge curves of the hollow molybdenum nitride/carbon microsphere composites prepared in examples 1,2 and 3, the platforms of the batteries assembled by three different variables correspond to the peak value of the cyclic voltammetry Curve (CV), and the batteries assembled by the hollow molybdenum nitride/carbon microsphere composites prepared by 3g of molybdenum carbonyl have a longer capacity platform, which indicates that the utilization rate of sulfur is high and the batteries have smaller redox platform gaps (as shown in fig. 5).
Comparison of capacity cycling curves of the hollow molybdenum nitride/carbon microsphere composite materials prepared in examples 1,2 and 3 shows that a battery assembled by the hollow molybdenum nitride/carbon microsphere composite material prepared from 3g of molybdenum carbonyl has higher initial capacity at a current density of 0.2C and higher discharge capacity after 100 cycles (as shown in figure 6).
Example 4
Adding 5g of melamine, 3g of molybdenum carbonyl and 50mL of n-hexadecane into a flask and stirring; then carrying out ultrasonic reaction for 4 hours at the temperature of 80 ℃ under argon; washing with n-pentane for 4-5 times, and drying at 105 ℃ for 12h to obtain a precursor; the precursor is converted into precursorThe mixture was melted with 2.5g of phenol at 40 ℃ with stirring. 20mL of water and 20mL of formaldehyde solution were added, 1M sodium hydroxide solution was added to adjust the pH to 9, stirring was continued for 1 hour, and 35mL of ethanol and 15g of 20 wt% SiO2EtOH silicon dioxide dispersion with size of 10nm, stirring for 15min, and spray drying at 200 deg.C to obtain material; roasting the obtained material at high temperature in argon atmosphere, wherein the heating rate is 10 ℃ for min-1And roasting at 500 ℃ for 5h and at 900 ℃ for 2h, naturally cooling to obtain a material, etching the material for 3-4 times by using a 5M sodium hydroxide solution, washing for 3-4 times by using deionized water, and finally drying by blowing at 80 ℃ for 12h to obtain the hollow molybdenum nitride/carbon microsphere composite material.
Example 5
Adding 5g of melamine, 3g of molybdenum carbonyl and 40mL of n-hexadecane into a flask and stirring; then carrying out ultrasonic reaction for 4 hours at the temperature of 60 ℃ under argon; washing with n-pentane for 4-5 times, and drying at 105 ℃ for 12h to obtain a precursor; the precursor and 2.5g of phenol are stirred and melted at 40 ℃. 20mL of water and 20mL of formaldehyde solution were added, 1M sodium hydroxide solution was added to adjust the pH to 9, stirring was continued for 1 hour, and 35mL of ethanol and 15g of 20 wt% SiO2EtOH silicon dioxide dispersion with size of 10nm, stirring for 15min, and spray drying at 200 deg.C to obtain material; roasting the obtained material at high temperature in argon atmosphere, wherein the heating rate is 10 ℃ for min-1And roasting at 500 ℃ for 5h and at 900 ℃ for 2h, naturally cooling to obtain a material, etching the material for 3-4 times by using a 5M sodium hydroxide solution, washing for 3-4 times by using deionized water, and finally drying by blowing at 80 ℃ for 12h to obtain the hollow molybdenum nitride/carbon microsphere composite material.
Example 6
Adding 5g of melamine, 3g of molybdenum carbonyl and 40mL of n-hexadecane into a flask and stirring; then carrying out ultrasonic reaction for 2h at the temperature of 80 ℃ under argon; washing with n-pentane for 4-5 times, and drying at 105 ℃ for 12h to obtain a precursor; the precursor and 2.5g of phenol are stirred and melted at 40 ℃. 20mL of water and 20mL of formaldehyde solution were added, 1M sodium hydroxide solution was added to adjust the pH to 9, stirring was continued for 1 hour, and 35mL of ethanol and 15g of 20 wt% SiO2EtOH silicon dioxide dispersions, whichStirring for 15min with a size of 10nm, and spray drying at 200 deg.C to obtain material; roasting the obtained material at high temperature in argon atmosphere, wherein the heating rate is 10 ℃ for min-1And roasting at 500 ℃ for 5h and at 900 ℃ for 2h, naturally cooling to obtain a material, etching the material for 3-4 times by using a 5M sodium hydroxide solution, washing for 3-4 times by using deionized water, and finally drying by blowing at 80 ℃ for 12h to obtain the hollow molybdenum nitride/carbon microsphere composite material.
Example 7
Adding 5g of melamine, 3g of molybdenum carbonyl and 40mL of n-hexadecane into a flask and stirring; then carrying out ultrasonic reaction for 4 hours at the temperature of 80 ℃ under argon; washing with n-pentane for 4-5 times, and drying at 105 ℃ for 6 hours to obtain a precursor; the precursor and 2.5g of phenol are stirred and melted at 40 ℃. 20mL of water and 20mL of formaldehyde solution were added, 1M sodium hydroxide solution was added to adjust the pH to 9, stirring was continued for 1 hour, and 35mL of ethanol and 15g of 20 wt% SiO2EtOH silicon dioxide dispersion with size of 10nm, stirring for 15min, and spray drying at 200 deg.C to obtain material; roasting the obtained material at high temperature in argon atmosphere, wherein the heating rate is 10 ℃ for min-1And roasting at 500 ℃ for 5h and at 900 ℃ for 2h, naturally cooling to obtain a material, etching the material for 3-4 times by using a 5M sodium hydroxide solution, washing for 3-4 times by using deionized water, and finally drying by blowing at 80 ℃ for 12h to obtain the hollow molybdenum nitride/carbon microsphere composite material.
Example 8
Adding 5g of melamine, 3g of molybdenum carbonyl and 40mL of n-hexadecane into a flask and stirring; then carrying out ultrasonic reaction for 4 hours at the temperature of 80 ℃ under argon; washing with n-pentane for 4-5 times, and drying at 105 ℃ for 12h to obtain a precursor; the precursor and 5g of phenol are stirred and melted at 40 ℃. 20mL of water and 20mL of formaldehyde solution were added, 1M sodium hydroxide solution was added to adjust the pH to 9, stirring was continued for 1 hour, and 35mL of ethanol and 15g of 20 wt% SiO2EtOH silicon dioxide dispersion with size of 10nm, stirring for 15min, and spray drying at 200 deg.C to obtain material; roasting the obtained material at high temperature in argon atmosphere, wherein the heating rate is 10 ℃ for min-1Roasting at 500 deg.C for 5 hr, roasting at 900 deg.C for 2 hr, naturally cooling to obtain material, and further using 5M hydrogenAnd etching the sodium oxide solution for 3-4 times, washing the obtained product for 3-4 times by using deionized water, and finally carrying out blast drying at 80 ℃ for 12 hours to obtain the hollow molybdenum nitride/carbon microsphere composite material.
Example 9
Adding 5g of melamine, 3g of molybdenum carbonyl and 40mL of n-hexadecane into a flask and stirring; then carrying out ultrasonic reaction for 4 hours at the temperature of 80 ℃ under argon; washing with n-pentane for 4-5 times, and drying at 105 ℃ for 12h to obtain a precursor; the precursor and 2.5g of phenol are stirred and melted at 40 ℃. 40mL of water and 20mL of formaldehyde solution were added, 1M sodium hydroxide solution was added to adjust the pH to 9, stirring was continued for 1 hour, and 35mL of ethanol and 15g of 20 wt% SiO2EtOH silicon dioxide dispersion with size of 10nm, stirring for 15min, and spray drying at 200 deg.C to obtain material; roasting the obtained material at high temperature in argon atmosphere, wherein the heating rate is 10 ℃ for min-1And roasting at 500 ℃ for 5h and at 900 ℃ for 2h, naturally cooling to obtain a material, etching the material for 3-4 times by using a 5M sodium hydroxide solution, washing for 3-4 times by using deionized water, and finally drying by blowing at 80 ℃ for 12h to obtain the hollow molybdenum nitride/carbon microsphere composite material.
Example 10
Adding 5g of melamine, 3g of molybdenum carbonyl and 40mL of n-hexadecane into a flask and stirring; then carrying out ultrasonic reaction for 4 hours at the temperature of 80 ℃ under argon; washing with n-pentane for 4-5 times, and drying at 105 ℃ for 12h to obtain a precursor; the precursor and 2.5g of phenol are stirred and melted at 40 ℃. 20mL of water and 40mL of formaldehyde solution were added, 1M sodium hydroxide solution was added to adjust the pH to 9, stirring was continued for 1 hour, and 35mL of ethanol and 15g of 20 wt% SiO2EtOH silicon dioxide dispersion with size of 10nm, stirring for 15min, and spray drying at 200 deg.C to obtain material; roasting the obtained material at high temperature in argon atmosphere, wherein the heating rate is 10 ℃ for min-1And roasting at 500 ℃ for 5h and at 900 ℃ for 2h, naturally cooling to obtain a material, etching the material for 3-4 times by using a 5M sodium hydroxide solution, washing for 3-4 times by using deionized water, and finally drying by blowing at 80 ℃ for 12h to obtain the hollow molybdenum nitride/carbon microsphere composite material.
Example 11
Will 5Adding melamine, molybdenum carbonyl and 40mL of n-hexadecane into a flask and stirring; then carrying out ultrasonic reaction for 4 hours at the temperature of 80 ℃ under argon; washing with n-pentane for 4-5 times, and drying at 105 ℃ for 12h to obtain a precursor; the precursor and 2.5g of phenol are stirred and melted at 40 ℃. 20mL of water and 20mL of formaldehyde solution were added, 1M sodium hydroxide solution was added to adjust the pH to 7, stirring was continued for 1 hour, and 35mL of ethanol and 15g of 20 wt% SiO2EtOH silicon dioxide dispersion with size of 10nm, stirring for 15min, and spray drying at 200 deg.C to obtain material; roasting the obtained material at high temperature in argon atmosphere, wherein the heating rate is 10 ℃ for min-1And roasting at 500 ℃ for 5h and at 900 ℃ for 2h, naturally cooling to obtain a material, etching the material for 3-4 times by using a 5M sodium hydroxide solution, washing for 3-4 times by using deionized water, and finally drying by blowing at 80 ℃ for 12h to obtain the hollow molybdenum nitride/carbon microsphere composite material.
Example 12
Adding 5g of melamine, 3g of molybdenum carbonyl and 40mL of n-hexadecane into a flask and stirring; then carrying out ultrasonic reaction for 4 hours at the temperature of 60 ℃ under argon; washing with n-pentane for 4-5 times, and drying at 105 ℃ for 12h to obtain a precursor; the precursor and 2.5g of phenol are stirred and melted at 40 ℃. 20mL of water and 20mL of formaldehyde solution were added, 1M sodium hydroxide solution was added to adjust the pH to 9, stirring was continued for 4 hours, and 35mL of ethanol and 15g of 20 wt% SiO2EtOH silicon dioxide dispersion with size of 10nm, stirring for 15min, and spray drying at 200 deg.C to obtain material; roasting the obtained material at high temperature in argon atmosphere, wherein the heating rate is 10 ℃ for min-1And roasting at 500 ℃ for 5h and at 900 ℃ for 2h, naturally cooling to obtain a material, etching the material for 3-4 times by using a 5M sodium hydroxide solution, washing for 3-4 times by using deionized water, and finally drying by blowing at 80 ℃ for 12h to obtain the hollow molybdenum nitride/carbon microsphere composite material.
Example 13
Adding 5g of melamine, 3g of molybdenum carbonyl and 40mL of n-hexadecane into a flask and stirring; then carrying out ultrasonic reaction for 4 hours at 40 ℃ under argon; washing with n-pentane for 4-5 times, and drying at 105 ℃ for 12h to obtain a precursor; stirring the precursor and 2.5g of phenol at 40 DEG CAnd (4) melting. 20mL of water and 20mL of formaldehyde solution were added, 1M sodium hydroxide solution was added to adjust the pH to 9, and the mixture was stirred for 1 hour, 50mL of ethanol and 15g of 20 wt% SiO2EtOH silicon dioxide dispersion with size of 10nm, stirring for 15min, and spray drying at 200 deg.C to obtain material; roasting the obtained material at high temperature in argon atmosphere, wherein the heating rate is 10 ℃ for min-1And roasting at 500 ℃ for 5h and at 900 ℃ for 2h, naturally cooling to obtain a material, etching the material for 3-4 times by using a 5M sodium hydroxide solution, washing for 3-4 times by using deionized water, and finally drying by blowing at 80 ℃ for 12h to obtain the hollow molybdenum nitride/carbon microsphere composite material.
Example 14
Adding 5g of melamine, 3g of molybdenum carbonyl and 40mL of n-hexadecane into a flask and stirring; then carrying out ultrasonic reaction for 4 hours at 40 ℃ under argon; washing with n-pentane for 4-5 times, and drying at 105 ℃ for 12h to obtain a precursor; the precursor and 2.5g of phenol are stirred and melted at 40 ℃. 20mL of water and 20mL of formaldehyde solution were added, 1M sodium hydroxide solution was added to adjust the pH to 9, the mixture was stirred for 1 hour, and 35mL of ethanol and 30g of 20 wt% SiO2EtOH silicon dioxide dispersion with size of 10nm, stirring for 15min, and spray drying at 200 deg.C to obtain material; roasting the obtained material at high temperature in argon atmosphere, wherein the heating rate is 10 ℃ for min-1And roasting at 500 ℃ for 5h and at 900 ℃ for 2h, naturally cooling to obtain a material, etching the material for 3-4 times by using a 5M sodium hydroxide solution, washing for 3-4 times by using deionized water, and finally drying by blowing at 80 ℃ for 12h to obtain the hollow molybdenum nitride/carbon microsphere composite material.
Example 15
Adding 5g of melamine, 3g of molybdenum carbonyl and 40mL of n-hexadecane into a flask and stirring; then carrying out ultrasonic reaction for 4 hours at 40 ℃ under argon; washing with n-pentane for 4-5 times, and drying at 105 ℃ for 12h to obtain a precursor; the precursor and 2.5g of phenol are stirred and melted at 40 ℃. 20mL of water and 20mL of formaldehyde solution were added, 1M sodium hydroxide solution was added to adjust the pH to 9, stirring was continued for 1 hour, and 35mL of ethanol and 15g of 20 wt% SiO2EtOH in the form of a silica dispersion of size 50nm, stirred for 15min and stripped at 200 ℃Spray drying under the part to obtain a material; roasting the obtained material at high temperature in argon atmosphere, wherein the heating rate is 10 ℃ for min-1And roasting at 500 ℃ for 5h and at 900 ℃ for 2h, naturally cooling to obtain a material, etching the material for 3-4 times by using a 5M sodium hydroxide solution, washing for 3-4 times by using deionized water, and finally drying by blowing at 80 ℃ for 12h to obtain the hollow molybdenum nitride/carbon microsphere composite material.
Example 16
Adding 5g of melamine, 3g of molybdenum carbonyl and 40mL of n-hexadecane into a flask and stirring; then carrying out ultrasonic reaction for 4 hours at 40 ℃ under argon; washing with n-pentane for 4-5 times, and drying at 105 ℃ for 12h to obtain a precursor; the precursor and 2.5g of phenol are stirred and melted at 40 ℃. 20mL of water and 20mL of formaldehyde solution were added, 1M sodium hydroxide solution was added to adjust the pH to 9, stirring was continued for 1 hour, and 35mL of ethanol and 15g of 20 wt% SiO2EtOH silicon dioxide dispersion with size of 10nm, stirring for 15min, and spray drying at 200 deg.C to obtain material; roasting the obtained material at high temperature in an argon atmosphere, wherein the heating rate is 5 ℃ for min-1And roasting at 500 ℃ for 5h and at 900 ℃ for 2h, naturally cooling to obtain a material, etching the material for 3-4 times by using a 5M sodium hydroxide solution, washing for 3-4 times by using deionized water, and finally drying by blowing at 80 ℃ for 12h to obtain the hollow molybdenum nitride/carbon microsphere composite material.
Example 17
Adding 5g of melamine, 3g of molybdenum carbonyl and 40mL of n-hexadecane into a flask and stirring; then carrying out ultrasonic reaction for 4 hours at 40 ℃ under argon; washing with n-pentane for 4-5 times, and drying at 105 ℃ for 12h to obtain a precursor; the precursor and 2.5g of phenol are stirred and melted at 40 ℃. 20mL of water and 20mL of formaldehyde solution were added, 1M sodium hydroxide solution was added to adjust the pH to 9, stirring was continued for 1 hour, and 35mL of ethanol and 15g of 20 wt% SiO2EtOH silicon dioxide dispersion with size of 10nm, stirring for 15min, and spray drying at 200 deg.C to obtain material; roasting the obtained material at high temperature in argon atmosphere, wherein the heating rate is 10 ℃ for min-1Roasting at 200 ℃ for 5h and at 900 ℃ for 2h, naturally cooling to obtain a material, etching the material for 3-4 times by using a 5M sodium hydroxide solution, and thenWashing with deionized water for 3-4 times, and finally drying by blowing air at 80 ℃ for 12 hours to obtain the hollow molybdenum nitride/carbon microsphere composite material.
Example 18
Adding 5g of melamine, 3g of molybdenum carbonyl and 40mL of n-hexadecane into a flask and stirring; then carrying out ultrasonic reaction for 4 hours at 40 ℃ under argon; washing with n-pentane for 4-5 times, and drying at 105 ℃ for 12h to obtain a precursor; the precursor and 2.5g of phenol are stirred and melted at 40 ℃. 20mL of water and 20mL of formaldehyde solution were added, 1M sodium hydroxide solution was added to adjust the pH to 9, stirring was continued for 1 hour, and 35mL of ethanol and 15g of 20 wt% SiO2EtOH silicon dioxide dispersion with size of 10nm, stirring for 15min, and spray drying at 200 deg.C to obtain material; roasting the obtained material at high temperature in argon atmosphere, wherein the heating rate is 10 ℃ for min-1And roasting at 500 ℃ for 5h, roasting at 900 ℃ for 1-10 h, naturally cooling to obtain a material, etching the material for 3-4 times by using a 5M sodium hydroxide solution, washing for 3-4 times by using deionized water, and finally drying by blowing at 80 ℃ for 12h to obtain the hollow molybdenum nitride/carbon microsphere composite material.
Example 19
Adding 5g of different organic molecules containing amino groups (melamine, urea, ethanolamine, ethylenediamine and isopropanol), 3g of molybdenum carbonyl and 40mL of n-hexadecane into a flask and stirring; then carrying out ultrasonic reaction for 4 hours at 40 ℃ under argon; washing with n-pentane for 4-5 times, and drying at 105 ℃ for 12h to obtain a precursor; the precursor and 2.5g of phenol are stirred and melted at 40 ℃. 20mL of water and 20mL of formaldehyde solution were added, 1M sodium hydroxide solution was added to adjust the pH to 9, stirring was continued for 1 hour, and 35mL of ethanol and 15g of 20 wt% SiO2EtOH silicon dioxide dispersion with size of 10nm, stirring for 15min, and spray drying at 200 deg.C to obtain material; roasting the obtained material at high temperature in argon atmosphere, wherein the heating rate is 10 ℃ for min-1And roasting at 500 ℃ for 5h and at 900 ℃ for 2h, naturally cooling to obtain a material, etching the material for 3-4 times by using a 5M sodium hydroxide solution, washing for 3-4 times by using deionized water, and finally drying by blowing at 80 ℃ for 12h to obtain the hollow molybdenum nitride/carbon microsphere composite material.
Example 20
Adding 5g of melamine, 3g of tungsten carbonyl and 40mL of n-hexadecane into a flask and stirring; then carrying out ultrasonic reaction for 4 hours at 40 ℃ under argon; washing with n-pentane for 4-5 times, and drying at 105 ℃ for 12h to obtain a precursor; the precursor and 2.5g of phenol are stirred and melted at 40 ℃. 20mL of water and 20mL of formaldehyde solution were added, 1M sodium hydroxide solution was added to adjust the pH to 9, stirring was continued for 1 hour, and 35mL of ethanol and 15g of 20 wt% SiO2EtOH silicon dioxide dispersion with size of 10nm, stirring for 15min, and spray drying at 200 deg.C to obtain material; roasting the obtained material at high temperature in argon atmosphere, wherein the heating rate is 10 ℃ for min-1And roasting at 500 ℃ for 5h and at 900 ℃ for 2h, naturally cooling to obtain a material, etching the material for 3-4 times by using a 5M sodium hydroxide solution, washing for 3-4 times by using deionized water, and finally drying by blowing at 80 ℃ for 12h to obtain the hollow tungsten nitride/carbon microsphere composite material.
Example 21
Adding 5g of melamine, 3g of molybdenum carbonyl and 40mL of methanol into a flask and stirring; then carrying out ultrasonic reaction for 4 hours at 40 ℃ under argon; washing with n-pentane for 4-5 times, and drying at 105 ℃ for 12h to obtain a precursor; the precursor and 2.5g of phenol are stirred and melted at 40 ℃. 20mL of water and 20mL of formaldehyde solution were added, 1M sodium hydroxide solution was added to adjust the pH to 9, stirring was continued for 1 hour, and 35mL of ethanol and 15g of 20 wt% SiO2EtOH silicon dioxide dispersion with size of 10nm, stirring for 15min, and spray drying at 200 deg.C to obtain material; roasting the obtained material at high temperature in argon atmosphere, wherein the heating rate is 10 ℃ for min-1And roasting at 500 ℃ for 5h and at 900 ℃ for 2h, naturally cooling to obtain a material, etching the material for 3-4 times by using a 5M sodium hydroxide solution, washing for 3-4 times by using deionized water, and finally drying by blowing at 80 ℃ for 12h to obtain the hollow molybdenum nitride/carbon microsphere composite material.
In summary, the hollow metal nitride/carbon microsphere composite material of the present invention is prepared by a spray drying method using an amino group-containing organic molecule as a nitrogen source and a metal carbonyl compound as a metal source. In the traditional method for preparing the metal compound, ammonia gas is mostly used as a nitrogen source in a reaction at high temperature, and certain dangerousness is realized. Compared with the traditional method, the method avoids the use of ammonia gas, has higher safety, and has the advantages of high reaction speed, high yield, easy industrialization and the like. The superfine metal nitride nano particles in the prepared hollow metal nitride/carbon microsphere composite material are uniformly dispersed in the hollow carbon microsphere and used as a positive host and a diaphragm modification layer of the lithium-sulfur battery, the material can chemically anchor lithium polysulfide and can catalyze the rapid conversion of the lithium polysulfide, the shuttle effect can be efficiently inhibited, the effects of improving the capacity and the cycle stability of the lithium-sulfur battery are remarkable, and the material has great application potential.
The embodiments described above are intended to facilitate the understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (10)

1. The preparation method of the hollow metal nitride/carbon microsphere composite material is characterized by comprising the following steps of:
s1: preparing a precursor:
s11: mixing and stirring an organic molecule containing amino, a metal carbonyl compound and an organic solvent;
s12: carrying out ultrasonic reaction under the protection of inert gas;
s13: washing and drying to obtain a precursor;
s2: spray drying:
s21: stirring and melting the obtained precursor and phenol, and then adding water and formaldehyde solution;
s22: continuously stirring and adding NaOH to adjust the pH value;
s23: adding ethanol and the silicon dioxide nano dispersion liquid, uniformly stirring, spray-drying, and collecting the obtained powder material;
s3: and roasting the obtained powder material in an inert gas atmosphere, naturally cooling, collecting the material, etching the material by using a sodium hydroxide aqueous solution, and then washing and drying to obtain the hollow metal nitride/carbon microsphere composite material.
2. The method for preparing a hollow metal nitride/carbon microsphere composite material according to claim 1, wherein the step S1 comprises any one or more of the following conditions:
(i) the organic molecules containing amino groups comprise urea, melamine, ethanolamine, ethylenediamine or isopropylamine;
(ii) the metal carbonyl compound comprises at least one of carbonyl iron, carbonyl molybdenum, carbonyl cobalt, carbonyl nickel and carbonyl tungsten;
(iii) the organic solvent includes at least one of methanol, ethanol, chloroform, n-butane, cyclohexane, n-hexadecane, benzene, and toluene.
3. The method for preparing a hollow metal nitride/carbon microsphere composite material according to claim 1 or 2, wherein in step S1, the ratio of the amount of the organic molecule containing an amino group, the amount of the metal carbonyl compound and the amount of the organic solvent is 0.1 to 30g:0.01 to 300g:10 to 500 mL.
4. The method for preparing a hollow metal nitride/carbon microsphere composite material according to claim 1, wherein the step S1 comprises any one or more of the following conditions:
(i) the temperature of the ultrasonic reaction is 30-90 ℃, and the reaction time is 0.5-10 h;
(ii) the drying time is 6-24 h, and the temperature is 60-120 ℃.
5. The method for preparing a hollow metal nitride/carbon microsphere composite material according to claim 1, wherein in step S2, the ratio of the usage amount of phenol, deionized water, formaldehyde, ethanol, silica nano dispersion liquid and amino-containing organic molecules is 1-25 g: 1-100 mL: 2-100 mL: 1-50 g: 0.1-30 g.
6. The method for preparing a hollow metal nitride/carbon microsphere composite material according to claim 1 or 5, wherein in step S2, the mass fraction of the silicon dioxide nano dispersion liquid is 10-30 wt% SiO2EtOH, the size of the silicon dioxide in the silicon dioxide nano dispersion liquid is 3-50 nm.
7. The method for preparing a hollow metal nitride/carbon microsphere composite material according to claim 1, wherein the step S2 comprises any one or more of the following conditions:
(i) the temperature for stirring and melting is 40 ℃;
(ii) adding NaOH to adjust the pH value to 4-12, and stirring for 0.2-6 h;
(iii) the temperature of spray drying is room temperature-800 ℃.
8. The method for preparing a hollow metal nitride/carbon microsphere composite material according to claim 1, wherein the step S3 comprises any one or more of the following conditions:
(1) roasting the obtained powder material at high temperature in an argon atmosphere, wherein the heating rate is 1-10 ℃ for min-1The roasting temperature is 400-1000 ℃, and the roasting time is 1-10 h;
(ii) the concentration of the aqueous sodium hydroxide solution was 5mol L-1。
9. The hollow metal nitride/carbon microsphere composite material obtained by the preparation method of any one of claims 1 to 8.
10. The use of the hollow metal nitride/carbon microsphere composite material according to claim 9, wherein the composite material is used for modification of a positive electrode and a diaphragm of a lithium-sulfur battery, and a functional interlayer with adsorption and catalysis effects is established between the positive electrode and the diaphragm.
CN202110475031.2A 2021-04-29 2021-04-29 Hollow metal nitride/carbon microsphere composite material and preparation method and application thereof Pending CN113292052A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110475031.2A CN113292052A (en) 2021-04-29 2021-04-29 Hollow metal nitride/carbon microsphere composite material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110475031.2A CN113292052A (en) 2021-04-29 2021-04-29 Hollow metal nitride/carbon microsphere composite material and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN113292052A true CN113292052A (en) 2021-08-24

Family

ID=77320510

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110475031.2A Pending CN113292052A (en) 2021-04-29 2021-04-29 Hollow metal nitride/carbon microsphere composite material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN113292052A (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5352269A (en) * 1989-11-09 1994-10-04 Mccandlish Larry E Spray conversion process for the production of nanophase composite powders
CN105161311A (en) * 2015-08-11 2015-12-16 上海应用技术学院 Method for preparing titanium nitride/carbon composite materials
JP6271665B1 (en) * 2016-09-20 2018-01-31 國家中山科學研究院 Method for producing spherical aluminum nitride powder
CN109904453A (en) * 2019-01-14 2019-06-18 浙江大学 A kind of porous titanium nitride microballoon and preparation method thereof and the application in lithium-sulfur cell
CN110265225A (en) * 2019-05-23 2019-09-20 天津大学 The method for preparing N doping three-dimensional porous carbosphere load molybdenum carbide/molybdenum nitride and iron nano-particle composite material
CN112652758A (en) * 2020-12-14 2021-04-13 云帆(镇江)新能源材料有限公司 Silicon oxide/carbon microsphere composite negative electrode material for lithium ion battery and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5352269A (en) * 1989-11-09 1994-10-04 Mccandlish Larry E Spray conversion process for the production of nanophase composite powders
CN105161311A (en) * 2015-08-11 2015-12-16 上海应用技术学院 Method for preparing titanium nitride/carbon composite materials
JP6271665B1 (en) * 2016-09-20 2018-01-31 國家中山科學研究院 Method for producing spherical aluminum nitride powder
CN109904453A (en) * 2019-01-14 2019-06-18 浙江大学 A kind of porous titanium nitride microballoon and preparation method thereof and the application in lithium-sulfur cell
CN110265225A (en) * 2019-05-23 2019-09-20 天津大学 The method for preparing N doping three-dimensional porous carbosphere load molybdenum carbide/molybdenum nitride and iron nano-particle composite material
CN112652758A (en) * 2020-12-14 2021-04-13 云帆(镇江)新能源材料有限公司 Silicon oxide/carbon microsphere composite negative electrode material for lithium ion battery and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JIANLI WANG 等: "Facile preparation of porous TiN-C microspheres as an efficient sulfur host for high performance lithium-sulfur battery", 《MATERIALS TODAY ENERGY》 *

Similar Documents

Publication Publication Date Title
CN111362254B (en) Preparation method and application of nitrogen-doped carbon nanotube-loaded phosphorus-doped cobaltosic oxide composite material
CN109244427B (en) Preparation method of carbon-coated zinc sulfide loaded graphene as potassium ion battery cathode
CN102324511B (en) Preparation method for lithium ion battery composite cathode material
CN111180714B (en) Carbon/molybdenum dioxide/silicon/carbon composite material, battery cathode comprising same and lithium ion battery
CN107464938B (en) Molybdenum carbide/carbon composite material with core-shell structure, preparation method thereof and application thereof in lithium air battery
CN112599743B (en) Carbon-coated nickel cobaltate multi-dimensional assembled microsphere negative electrode material and preparation method thereof
CN112349899A (en) Silicon-based composite negative electrode material, preparation method thereof and lithium ion battery
CN111313000A (en) Lithium-sulfur battery positive electrode material and preparation method and application thereof
CN107732192B (en) Silicon-carbon composite material for lithium ion battery cathode and preparation method thereof
CN113871607A (en) Halide-doped carbon/sulfur positive electrode material and preparation method and application thereof
CN109786769B (en) Carbon-supported noble metal oxide bifunctional catalyst and preparation method and application thereof
CN114497475A (en) Zinc-containing nitrogen-doped porous carbon-coated zinc-based negative electrode material for lithium ion battery
CN113264519A (en) Modified carbon nanotube and preparation method thereof, negative electrode material, negative electrode plate and lithium ion battery
CN116799210A (en) Composite lithium supplementing material and preparation method thereof, lithium supplementing coating and preparation method thereof, and lithium battery
CN111974430A (en) Preparation method of monoatomic copper catalyst and application of monoatomic copper catalyst in positive electrode of lithium-sulfur battery
CN111192997A (en) Diaphragm for activated carbon-loaded tin oxide lithium-sulfur battery and preparation method and application thereof
CN107394219B (en) VC/graphene composite material, preparation method thereof and application thereof in lithium-air battery
CN110586104A (en) Titanium dioxide, copper oxide and cobalt titanate composite nanofiber and preparation method thereof
Chen et al. Porous SiOCN with ultrafine CoSe2 nanoparticle modified separators for promoting polysulfides capture and redox kinetics in lithium-sulfur batteries
CN113292052A (en) Hollow metal nitride/carbon microsphere composite material and preparation method and application thereof
CN112510179B (en) Battery negative electrode material and preparation method and application thereof
CN115084488A (en) Copper sulfide-doped carbon-based composite material, preparation method thereof and sodium ion battery
CN111509229A (en) Nitrogen-doped porous carbon-coated V2O3The positive electrode material of the lithium-sulfur battery and the preparation method thereof
Zhang et al. Co-W bimetallic carbides as sulfur host for high-performance lithium–sulfur batteries
CN111490235A (en) Micron-particle high-capacity lithium ion battery cathode material based on conversion reaction and preparation method and application thereof

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
RJ01 Rejection of invention patent application after publication

Application publication date: 20210824

RJ01 Rejection of invention patent application after publication