CN111883753B - MoS with hierarchical shell-core structure2Negative active material of-C composite porous microsphere - Google Patents

MoS with hierarchical shell-core structure2Negative active material of-C composite porous microsphere Download PDF

Info

Publication number
CN111883753B
CN111883753B CN202010685833.1A CN202010685833A CN111883753B CN 111883753 B CN111883753 B CN 111883753B CN 202010685833 A CN202010685833 A CN 202010685833A CN 111883753 B CN111883753 B CN 111883753B
Authority
CN
China
Prior art keywords
porous
mos
solution
microspheres
active material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010685833.1A
Other languages
Chinese (zh)
Other versions
CN111883753A (en
Inventor
罗玲静
鞠清华
徐光文
樊梦林
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 Dingying Information Technology Co.,Ltd.
Original Assignee
Shanghai Dingying Information Technology Co ltd
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 Dingying Information Technology Co ltd filed Critical Shanghai Dingying Information Technology Co ltd
Priority to CN202010685833.1A priority Critical patent/CN111883753B/en
Publication of CN111883753A publication Critical patent/CN111883753A/en
Application granted granted Critical
Publication of CN111883753B publication Critical patent/CN111883753B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
    • 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
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to the technical field of sodium ion batteries and discloses a MoS with a hierarchical shell-core structure2Negative active material of-C composite porous microsphere, porous MoS2The hollow sphere is made of layered nano MoS2The porous MoS is formed by stacking, has larger specific surface area, has unique hollow structure and hollow structure, provides a diffusion channel for the extraction and the embedding of sodium ions, and is porous2Forming a coating layer of porous phenolic resin microspheres outside the hollow spheres, performing ion exchange on ammonium alginate and calcium ions for crosslinking, forming a three-dimensional mesh-structured alginic acid gel layer outside the coating layer, and carbonizing at high temperature to make the porous MoS2The hollow ball grows in the porous structure with rich carbon layer uniformly, and buffers MoS2Stress generated by volume change relieves the volume expansion phenomenon and inhibits the layered nano MoS2Porous MoS of porous carbon layer having excellent conductivity2And a three-dimensional conductive network is formed outside the hollow spheres, so that the transmission and diffusion of electrons are promoted.

Description

MoS with hierarchical shell-core structure2Negative active material of-C composite porous microsphere
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a cathode active material of MoS2-C composite porous microspheres with a hierarchical shell-core structure.
Background
At present, lithium ion batteries are continuously applied to electric vehicles and energy storage systems, the supply and demand problems of metal lithium resources are increasingly remarkable, and sodium resources are rich in reserves, wide in distribution and low in cost, so that in recent years, sodium ion batteries become research hotspots, and in order to obtain sodium ion batteries with high energy density and long cycle life, a sodium ion battery cathode active material with high specific capacity and low cost needs to be developed.
The active materials of the cathode of the current sodium ion battery mainly comprise active carbon cathode materials, such as graphene, carbon nano tubes and the like; transition metal oxides, e.g. SnO2、Mn2O3Etc.; transition metal sulfides such as CoS, MoS2Etc., wherein the layer of MoS2The layers have weak van der Waals force and larger interlayer spacing, are beneficial to the intercalation and deintercalation of sodium ions in the charging and discharging processes, have higher theoretical specific capacity and MoS2Cheap and easily available, low cost, and is a sodium ion battery cathode active material with wide application prospect, but MoS2Volume expansion occurs during electrochemical cycling, resulting in layered MoS2The accumulation is generated, and the cycle new and reversible specific capacity of the negative electrode material are seriously influenced.
The invention aims to overcome the defects in the prior art and provides a negative active material of MoS2-C composite porous microspheres with a hierarchical shell-core structure.
Technical scheme (I)
In order to achieve the purpose, the invention provides the following technical scheme: MoS with hierarchical shell-core structure2The negative active material of the-C composite porous microsphere comprises the following raw materials and components: phenolic resin nano-porous MoS2The mass ratio of the microspheres to the ammonium alginate to the calcium carbonate is 100:6-12: 2-5.
Preferably, said hierarchical putamen structure MoS2The preparation process of the negative active material of the-C composite porous microsphere is as follows:
(1) adding deionized water into a reaction bottle, uniformly stirring until no bubbles are generated by adding potassium permanganate and citric acid in a mass ratio of 1:1-1.5 into the reaction bottle, pouring the solution into a hydrothermal reaction kettle, heating to 150 ℃ and 170 ℃, and reacting for 6-12h to obtain porous MnCO3And (3) microspheres.
(2) Adding deionized water and porous MnCO into a reaction bottle3Adding sodium molybdate into the microspheres after ultrasonic treatment, carrying out ultrasonic treatment, adding L-cysteine, continuing ultrasonic treatment, pouring the solution into a hydrothermal reaction kettleHeating to 240 ℃ for reaction for 20-30h, placing the solid mixed product into a dilute hydrochloric acid solution with the mass fraction of 2-4%, uniformly stirring for 12-24h, removing the by-product manganese sulfide, and obtaining the porous MoS2The hollow ball.
(3) Adding ammonia water solution with pH of 10-12 into a reaction bottle, adding cetyl trimethyl ammonium bromide and lauryl sodium sulfate as composite active agents, and adding porous MoS2Subjecting the hollow spheres to ultrasonic treatment, stirring at a constant speed for 4-10h, recording as solution A, adding phenol, formaldehyde aqueous solution and sodium hydroxide into deionized water, stirring at a constant speed at room temperature for reaction for 30-50min, recording as solution B, slowly dropwise adding the solution B into the solution A, stirring at a constant speed at 60-80 ℃ for reaction for 36-72h to obtain porous phenolic resin microspheres coated with porous MoS2The hollow ball.
(4) Adding deionized water and calcium carbonate into a reaction bottle, performing ultrasonic treatment, adding ammonium alginate, stirring at constant speed for 3-5h, and adding porous phenolic resin microspheres to coat porous MoS2The hollow sphere is continuously subjected to ultrasonic treatment, the solution is slowly dripped into a calcium chloride solution with the mass fraction of 2-3%, the calcium chloride solution is uniformly stirred for 20-30h and crosslinked to form a sol, the sol product is vacuum-dried to remove the solvent, the solid mixed product is placed in an atmosphere furnace for calcination, the calcined product is placed in a dilute nitric acid solution for standing for 20-30h to remove calcium ions, deionized water is used for washing the calcined product until the calcined product is neutral, and MoS with a hierarchical shell-core structure is obtained2-C composite porous microspheres as a negative active material of the sodium-ion battery.
Preferably, the porous MnCO in the step (2)3The mass ratio of the microspheres to the sodium molybdate to the L-cysteine is 5-10:10: 38-42.
Preferably, the cetyl trimethyl ammonium bromide, the sodium dodecyl sulfate and the porous MoS in the step (3)2The mass ratio of the hollow spheres, the phenol, the formaldehyde and the sodium hydroxide is 30-40:17-22:30-50:10:7-8: 1.5-2.5.
Preferably, the atmosphere furnace in the step (4) is nitrogen, the heating rate is 5-10 ℃/min, the calcining temperature is 600-700 ℃, and the calcining time is 2-4 h.
The invention has the following beneficial effects:
compared with the prior art, the invention has the following beneficial technical effects:
with porous MnCO3The microspheres are used as templates, and the layered nano MoS is obtained by an ion exchange method2Stack-formed porous MoS2The hollow sphere has larger specific surface area, has unique hollow structure and hollow structure, provides a diffusion channel for the extraction and the embedding of sodium ions, promotes the transmission of the sodium ions, uses cetyl trimethyl ammonium bromide and sodium dodecyl sulfate as composite active agents, and is applied to porous MoS2Forming a coating layer of porous phenolic resin microspheres outside the hollow spheres, then performing ion exchange on ammonium alginate and calcium ions for crosslinking, forming a three-dimensional network-structured alginic acid gel layer outside the porous phenolic resin coating layer, and further performing high-temperature treatment to ensure that the porous phenolic resin and the alginic acid gel are in a porous MoS2A porous carbon layer of a graded shell-core structure and a porous MoS are formed outside the hollow ball2The hollow ball uniformly grows in the porous structure with rich carbon layer, thereby effectively buffering MoS2Stress generated by volume change in the electrochemical circulation process relieves the volume expansion phenomenon and inhibits the layered nano MoS2And grading the porous carbon layer of the shell-core structure in the porous MoS2The three-dimensional conductive network is formed on the outer side of the hollow sphere, so that the conductive performance is excellent, the transmission and diffusion of electrons are promoted, and the cycle stability and the reversible specific capacity of the negative electrode material are enhanced under the synergistic effect.
Drawings
FIG. 1 is a porous MoS2Scanning electron microscope pictures of the field emission of the hollow sphere;
FIG. 2 shows porous MoS coated with porous phenolic resin microspheres2Scanning electron microscope pictures of the field emission of the hollow sphere;
FIG. 3 is a MoS of hierarchical putamen structure2-C composite porous microspheres transmission scanning electron microscopy pictures.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: grading shellCore structured MoS2The negative active material of the-C composite porous microsphere comprises the following raw materials and components: phenolic resin nano-porous MoS2The mass ratio of the microspheres to the ammonium alginate to the calcium carbonate is 100:6-12: 2-5.
MoS of hierarchical shell-core structure2The preparation process of the negative active material of the-C composite porous microsphere is as follows:
(1) adding deionized water into a reaction bottle, uniformly stirring until no bubbles are generated by adding potassium permanganate and citric acid in a mass ratio of 1:1-1.5 into the reaction bottle, pouring the solution into a hydrothermal reaction kettle, heating to 150 ℃ and 170 ℃, and reacting for 6-12h to obtain porous MnCO3And (3) microspheres.
(2) Adding deionized water and porous MnCO into a reaction bottle3Adding sodium molybdate into microspheres after ultrasonic treatment, performing ultrasonic treatment, adding L-cysteine at a mass ratio of 5-10:10:38-42, continuing ultrasonic treatment, pouring the solution into a hydrothermal reaction kettle, heating to 200-2The hollow ball.
(3) Adding ammonia water solution with pH of 10-12 into a reaction bottle, adding cetyl trimethyl ammonium bromide and lauryl sodium sulfate as composite active agents, and adding porous MoS2Hollow ball, ultrasonic treated, uniformly stirred for 4-10 hr, recorded as solution A, and deionized water added with phenol, formaldehyde water solution and sodium hydroxide, wherein cetyl trimethyl ammonium bromide, sodium dodecyl sulfate and porous MoS2The mass ratio of the hollow spheres, the phenol, the formaldehyde and the sodium hydroxide is 30-40:17-22:30-50:10:7-8:1.5-2.5, the mixture is stirred at a constant speed at room temperature for 30-50min to react, the solution B is recorded as a solution B, the solution B is slowly dripped into the solution A, the mixture is stirred at a constant speed at 60-80 ℃ for 36-72h to obtain the porous MoS coated with the porous phenolic resin microspheres2The hollow ball.
(4) Adding deionized water and calcium carbonate into a reaction bottle, performing ultrasonic treatment, adding ammonium alginate, stirring at constant speed for 3-5h, and adding porous phenolic resin microspheres to coat porous MoS2Hollow ball, go onCarrying out ultrasonic treatment, slowly dripping the solution into a calcium chloride solution with the mass fraction of 2-3%, uniformly stirring for 20-30h, crosslinking to form a sol, vacuum drying the sol product to remove the solvent, placing the solid mixed product in an atmosphere furnace in nitrogen atmosphere, heating at the rate of 5-10 ℃/min to 600-700 ℃, carrying out heat preservation and calcination for 2-4h, placing the calcined product in a dilute nitric acid solution, standing for 20-30h to remove calcium ions, washing the calcined product with deionized water until the calcined product is neutral, and obtaining MoS with a graded shell-core structure2-C composite porous microspheres as a negative active material of the sodium-ion battery.
Example 1
(1) Adding deionized water into a reaction bottle, uniformly stirring until no bubbles are generated by adding potassium permanganate and citric acid in a mass ratio of 1:1, pouring the solution into a hydrothermal reaction kettle, heating to 150 ℃, and reacting for 6 hours to obtain porous MnCO3And (3) microspheres.
(2) Adding deionized water and porous MnCO into a reaction bottle3Carrying out ultrasonic treatment on microspheres, adding sodium molybdate, carrying out ultrasonic treatment, adding L-cysteine with the mass ratio of 5:10:38, continuing ultrasonic treatment, pouring the solution into a hydrothermal reaction kettle, heating to 200 ℃, reacting for 20 hours, placing the solid mixed product into a dilute hydrochloric acid solution with the mass fraction of 2%, stirring at a constant speed for 12 hours, removing the by-product manganese sulfide, and obtaining the porous MoS2The hollow ball.
(3) Adding an ammonia water solution with the pH value of 10 into a reaction bottle, adding hexadecyl trimethyl ammonium bromide and lauryl sodium sulfate as composite active agents, and then adding porous MoS2Hollow ball, ultrasonic treated, uniformly stirred for 4 hr, recorded as solution A, and deionized water added with phenol, formaldehyde water solution and sodium hydroxide, wherein cetyl trimethyl ammonium bromide, sodium dodecyl sulfate and porous MoS2The mass ratio of the hollow spheres to the phenol to the formaldehyde to the sodium hydroxide is 30:17:30:10:7:1.5, the mixture is stirred at a constant speed at room temperature for 30min to react, the solution B is recorded as a solution B, the solution B is slowly dripped into the solution A, and the mixture is stirred at a constant speed at 60 ℃ to react for 36h, so that porous MoS coated with the porous phenolic resin microspheres is obtained2The hollow ball.
(4) To the reaction flaskAdding deionized water and calcium carbonate, performing ultrasonic treatment, adding ammonium alginate, stirring at constant speed for 3 hr, adding porous phenolic resin microspheres to coat porous MoS2The mass ratio of the hollow spheres to the ammonium alginate and the calcium carbonate is 100:6:2, the solution is continuously subjected to ultrasonic treatment, the solution is slowly dripped into a calcium chloride solution with the mass fraction of 2%, the solution is stirred at a constant speed for 20 hours and is crosslinked to form a sol, the sol product is dried in vacuum to remove the solvent, the solid mixed product is placed in an atmosphere furnace in the nitrogen atmosphere, the heating rate is 5 ℃/min, the temperature is raised to 600 ℃, the heat preservation and calcination are carried out for 2 hours, the calcined product is placed in a dilute nitric acid solution and is kept stand for 20 hours to remove calcium ions, deionized water is used for washing the calcined product until the calcined product is neutral, and the MoS with the graded shell-core structure is obtained2-C composite porous microspheres as the negative active material 1 of the sodium-ion battery.
Example 2
(1) Adding deionized water into a reaction bottle, uniformly stirring until no bubbles are generated by adding potassium permanganate and citric acid in a mass ratio of 1:1.2 into the reaction bottle, pouring the solution into a hydrothermal reaction kettle, heating to 170 ℃, and reacting for 12 hours to obtain porous MnCO3And (3) microspheres.
(2) Adding deionized water and porous MnCO into a reaction bottle3Carrying out ultrasonic treatment on microspheres, adding sodium molybdate, carrying out ultrasonic treatment, adding L-cysteine with the mass ratio of 6:10:39, continuing ultrasonic treatment, pouring the solution into a hydrothermal reaction kettle, heating to 240 ℃, reacting for 20 hours, placing the solid mixed product into a dilute hydrochloric acid solution with the mass fraction of 4%, stirring at a constant speed for 18 hours, removing the by-product manganese sulfide, and obtaining the porous MoS2The hollow ball.
(3) Adding an ammonia water solution with the pH value of 12 into a reaction bottle, adding hexadecyl trimethyl ammonium bromide and lauryl sodium sulfate as composite active agents, and then adding porous MoS2Hollow spheres are ultrasonically treated and then uniformly stirred for 5 hours, recorded as solution A, and phenol, formaldehyde aqueous solution and sodium hydroxide are added into deionized water, wherein hexadecyl trimethyl ammonium bromide, lauryl sodium sulfate and porous MoS2The mass ratio of the hollow spheres to the phenol to the formaldehyde to the sodium hydroxide is 34:19:38:10:7.6:1.8, and the mixture is stirred at a constant speed at room temperature to reactTaking the solution B as the solution B after 50min, slowly dropwise adding the solution B into the solution A, and reacting at 80 ℃ under uniform stirring for 48h to obtain porous MoS coated with porous phenolic resin microspheres2The hollow ball.
(4) Adding deionized water and calcium carbonate into a reaction bottle, performing ultrasonic treatment, adding ammonium alginate, stirring at constant speed for 5h, and adding porous phenolic resin microspheres to coat porous MoS2The mass ratio of the hollow spheres to the ammonium alginate and the calcium carbonate is 100:8:3, the solution is continuously subjected to ultrasonic treatment, the solution is slowly dripped into a calcium chloride solution with the mass fraction of 2%, the solution is uniformly stirred for 30 hours and is crosslinked to form a sol, the sol product is dried in vacuum to remove the solvent, the solid mixed product is placed in an atmosphere furnace in the nitrogen atmosphere, the heating rate is 8 ℃/min, the temperature is increased to 700 ℃, the heat preservation and calcination are carried out for 2 hours, the calcined product is placed in a dilute nitric acid solution and is kept still for 25 hours to remove calcium ions, deionized water is used for washing the calcined product until the calcined product is neutral, and the MoS with the graded shell-core structure is obtained2-C composite porous microspheres as the negative active material 2 of the sodium ion battery.
Example 3
(1) Adding deionized water into a reaction bottle, uniformly stirring until no bubbles are generated by adding potassium permanganate and citric acid in a mass ratio of 1:1.2 into the reaction bottle, pouring the solution into a hydrothermal reaction kettle, heating to 160 ℃, and reacting for 8 hours to obtain porous MnCO3And (3) microspheres.
(2) Adding deionized water and porous MnCO into a reaction bottle3Carrying out ultrasonic treatment on microspheres, adding sodium molybdate, carrying out ultrasonic treatment, adding L-cysteine with the mass ratio of 8:10:40, continuing ultrasonic treatment, pouring the solution into a hydrothermal reaction kettle, heating to 220 ℃, reacting for 25h, placing the solid mixed product into a dilute hydrochloric acid solution with the mass fraction of 3%, stirring at a constant speed for 18h, removing the by-product manganese sulfide, and obtaining the porous MoS2The hollow ball.
(3) Adding an ammonia water solution with the pH value of 11 into a reaction bottle, adding hexadecyl trimethyl ammonium bromide and lauryl sodium sulfate as composite active agents, and then adding porous MoS2Hollow spheres are subjected to ultrasonic treatment and then stirred at a constant speed for 6 hours, recorded as solution A, and phenol and formaldehyde are added into deionized waterAqueous solution and sodium hydroxide, wherein cetyl trimethyl ammonium bromide, sodium dodecyl sulfate, porous MoS2The mass ratio of the hollow spheres to the phenol to the formaldehyde to the sodium hydroxide is 35:20:44:10:7.6:2.2, the mixture is stirred at a constant speed at room temperature for 50min to react, the solution B is recorded as a solution B, the solution B is slowly dripped into the solution A, and the reaction is carried out at a constant speed at 70 ℃ for 60h to obtain porous MoS coated with the porous phenolic resin microspheres2The hollow ball.
(4) Adding deionized water and calcium carbonate into a reaction bottle, performing ultrasonic treatment, adding ammonium alginate, stirring at constant speed for 4h, and adding porous phenolic resin microspheres to coat porous MoS2The method comprises the following steps of continuously carrying out ultrasonic treatment on hollow spheres, ammonium alginate and calcium carbonate in a mass ratio of 100:10:4, slowly dropwise adding the solution into a calcium chloride solution with the mass fraction of 2.5%, uniformly stirring for 25 hours, crosslinking to form a sol, drying the sol product in vacuum to remove a solvent, placing a solid mixed product in an atmosphere furnace in a nitrogen atmosphere, heating to 650 ℃ at a heating rate of 8 ℃/min, carrying out heat preservation calcination for 3 hours, placing the calcined product in a dilute nitric acid solution, standing for 25 hours to remove calcium ions, washing the calcined product with deionized water until the calcined product is neutral, and obtaining MoS with a hierarchical shell-core structure2-C composite porous microspheres as the negative active material 3 of the sodium ion battery.
Example 4
(1) Adding deionized water into a reaction bottle, uniformly stirring until no bubbles are generated by adding potassium permanganate and citric acid in a mass ratio of 1:1.5 into the reaction bottle, pouring the solution into a hydrothermal reaction kettle, heating to 170 ℃, and reacting for 12 hours to obtain porous MnCO3And (3) microspheres.
(2) Adding deionized water and porous MnCO into a reaction bottle3Carrying out ultrasonic treatment on microspheres, adding sodium molybdate, carrying out ultrasonic treatment, adding L-cysteine with the mass ratio of 10:10:42, continuing ultrasonic treatment, pouring the solution into a hydrothermal reaction kettle, heating to 240 ℃, reacting for 30 hours, placing the solid mixed product into a dilute hydrochloric acid solution with the mass fraction of 4%, stirring at a constant speed for 24 hours, removing the by-product manganese sulfide, and obtaining the porous MoS2The hollow ball.
(3) Adding an ammonia solution with pH of 12 into a reaction flaskAdding cetyl trimethyl ammonium bromide and sodium dodecyl sulfate as composite activator, and adding porous MoS2Hollow spheres are ultrasonically treated and then uniformly stirred for 10 hours, recorded as solution A, and phenol, formaldehyde aqueous solution and sodium hydroxide are added into deionized water, wherein hexadecyl trimethyl ammonium bromide, lauryl sodium sulfate and porous MoS2The mass ratio of the hollow spheres to the phenol to the formaldehyde to the sodium hydroxide is 40:22:50:10:8:2.5, the mixture is stirred at a constant speed at room temperature for 50min to react, the solution B is recorded as a solution B, the solution B is slowly dripped into the solution A, and the mixture is stirred at a constant speed at 80 ℃ for 72h to react, so that porous MoS coated with the porous phenolic resin microspheres is obtained2The hollow ball.
(4) Adding deionized water and calcium carbonate into a reaction bottle, performing ultrasonic treatment, adding ammonium alginate, stirring at constant speed for 5h, and adding porous phenolic resin microspheres to coat porous MoS2The mass ratio of the hollow spheres to the ammonium alginate and the calcium carbonate is 100:12:5, the solution is continuously subjected to ultrasonic treatment, the solution is slowly dripped into a calcium chloride solution with the mass fraction of 3%, the solution is uniformly stirred for 30 hours and is crosslinked to form a sol, the sol product is dried in vacuum to remove the solvent, the solid mixed product is placed in an atmosphere furnace in the nitrogen atmosphere, the heating rate is 10 ℃/min, the temperature is increased to 700 ℃, the heat preservation and calcination are carried out for 4 hours, the calcined product is placed in a dilute nitric acid solution and is kept still for 30 hours to remove calcium ions, deionized water is used for washing the calcined product until the calcined product is neutral, and the MoS with the graded shell-core structure is obtained2-C composite porous microspheres as the negative active material 4 of the sodium ion battery.
Comparative example 1
(1) Adding deionized water into a reaction bottle, uniformly stirring until no bubbles are generated by adding potassium permanganate and citric acid in a mass ratio of 1:0.8 into the reaction bottle, pouring the solution into a hydrothermal reaction kettle, heating to 150 ℃, and reacting for 12 hours to obtain porous MnCO3And (3) microspheres.
(2) Adding deionized water and porous MnCO into a reaction bottle3Carrying out ultrasonic treatment on microspheres, adding sodium molybdate, carrying out ultrasonic treatment, adding L-cysteine according to the mass ratio of 4:10:36, continuing ultrasonic treatment, pouring the solution into a hydrothermal reaction kettle, heating to 240 ℃, reacting for 30 hours, and mixing solids to obtain the productPlacing the mixture into a dilute hydrochloric acid solution with the mass fraction of 2%, uniformly stirring for 24 hours, removing the by-product manganese sulfide, and obtaining porous MoS2The hollow ball.
(3) Adding an ammonia water solution with the pH value of 12 into a reaction bottle, adding hexadecyl trimethyl ammonium bromide and lauryl sodium sulfate as composite active agents, and then adding porous MoS2Hollow spheres are ultrasonically treated and then uniformly stirred for 5 hours, recorded as solution A, and phenol, formaldehyde aqueous solution and sodium hydroxide are added into deionized water, wherein hexadecyl trimethyl ammonium bromide, lauryl sodium sulfate and porous MoS2The mass ratio of the hollow spheres to the phenol to the formaldehyde to the sodium hydroxide is 28:16:26:10:6.5:3, the mixture is stirred at a constant speed at room temperature for 50min to react, the solution B is recorded as a solution B, the solution B is slowly dripped into the solution A, and the mixture is stirred at a constant speed at 80 ℃ for 72h to react, so that porous MoS coated with the porous phenolic resin microspheres is obtained2The hollow ball.
(4) Adding deionized water and calcium carbonate into a reaction bottle, performing ultrasonic treatment, adding ammonium alginate, stirring at constant speed for 4h, and adding porous phenolic resin microspheres to coat porous MoS2The mass ratio of the hollow spheres to the ammonium alginate and the calcium carbonate is 100:15:1.5, the solution is continuously subjected to ultrasonic treatment, the solution is slowly dripped into a calcium chloride solution with the mass fraction of 3%, the solution is uniformly stirred for 30 hours and is crosslinked to form a sol, the sol product is dried in vacuum to remove the solvent, the solid mixed product is placed in an atmosphere furnace in the nitrogen atmosphere, the heating rate is 10 ℃/min, the temperature is raised to 650 ℃, the heat preservation and calcination are carried out for 3 hours, the calcined product is placed in a dilute nitric acid solution and is kept still for 30 hours to remove calcium ions, deionized water is used for washing the calcined product until the calcined product is neutral, and the MoS with the hierarchical shell-core structure is obtained2the-C composite porous microspheres are used as a sodium ion battery negative electrode comparison material 1.
The sodium ion battery negative electrode active materials and the comparative materials in the examples and the comparative examples are respectively placed in an N, methyl pyrrolidone solvent, conductive carbon black and polyvinylidene fluoride are added, slurry is coated on copper foil, drying and tabletting are carried out, the sodium ion battery negative electrode is formed, a sodium sheet is used as a positive electrode, and the electrolyte is 1 mol/L NaPF6The solution of + ethylene carbonate + diethyl carbonate is used as electrolyte, the diaphragm is glass fiber film, and the solution is mixed with argonThe air glove box is assembled into a CR2025 button cell, and the constant-current charge-discharge performance is tested in a LAND CT2001A battery test system.
Item Current Density (A/g) Reversible specific capacity (mA. h/g)
Example 1 0.5 428.6
Example 2 0.5 469.2
Example 3 0.5 440.5
Example 4 0.5 432.2
Comparative example 1 0.5 330.8

Claims (4)

1. MoS with hierarchical shell-core structure2-C composite porous microsphere negative electrode active material, characterized in that: obtained from the following components, phenolic resin nano-porous MoS2Microspheres, ammonium alginate and calcium carbonate in a mass ratio of 100:6-12: 2-5; MoS of the hierarchical putamen structure2The preparation process of the negative active material of the-C composite porous microsphere is as follows:
(1) adding deionized water, potassium permanganate and citric acid with the mass ratio of 1:1-1.5 into a reaction bottle, uniformly stirring at a constant speed until no bubbles are generated, pouring the solution into a hydrothermal reaction kettle, heating to 150 ℃ and 170 ℃, and reacting for 6-12h to obtain porous MnCO3Microspheres;
(2) adding deionized water and porous MnCO into a reaction bottle3Adding sodium molybdate into the microspheres after ultrasonic treatment, performing ultrasonic treatment, adding L-cysteine, continuing ultrasonic treatment, pouring the mixture into a hydrothermal reaction kettle, heating the mixture to the temperature of 200 ℃ and 240 ℃, reacting for 20-30h, placing the solid mixed product into a dilute hydrochloric acid solution with the mass fraction of 2-4%, stirring at a constant speed for 12-24h, removing the by-product manganese sulfide, and obtaining the porous MoS2Hollow spheres;
(3) adding ammonia water solution with pH of 10-12 into a reaction bottle, adding cetyl trimethyl ammonium bromide and lauryl sodium sulfate as composite active agents, and adding porous MoS2Subjecting the hollow spheres to ultrasonic treatment, stirring at a constant speed for 4-10h, recording as solution A, adding phenol, formaldehyde aqueous solution and sodium hydroxide into deionized water, stirring at a constant speed at room temperature for reaction for 30-50min, recording as solution B, slowly dropwise adding the solution B into the solution A, stirring at a constant speed at 60-80 ℃ for reaction for 36-72h to obtain porous phenolic resin microspheres coated with porous MoS2Hollow spheres;
(4) adding deionized water and calcium carbonate into a reaction bottle, performing ultrasonic treatment, adding ammonium alginate, stirring at constant speed for 3-5h, and adding porous phenolic resin microspheres to coat porous MoS2The hollow ball is continuously subjected to ultrasonic treatment, the solution is slowly dripped into a calcium chloride solution with the mass fraction of 2-3%, the calcium chloride solution is uniformly stirred for 20-30h and crosslinked to form a sol, the sol product is dried in vacuum to remove the solvent, the solid mixed product is placed in an atmosphere furnace for calcination, the calcined product is placed in a dilute nitric acid solution and is kept stand for 20-30h to remove calcium ions, and deionized water is used for removing the calcium ionsWashing the calcined product until the calcined product is neutral to obtain MoS with a hierarchical shell-core structure2-C composite porous microspheres as a negative active material of the sodium-ion battery.
2. MoS of hierarchical putamen structure according to claim 12-C composite porous microsphere negative active material characterized by: the porous MnCO in the step (2)3The mass ratio of the microspheres to the sodium molybdate to the L-cysteine is 5-10:10: 38-42.
3. MoS of a hierarchical putamen structure according to claim 22-C composite porous microsphere negative active material characterized by: cetyl trimethyl ammonium bromide, sodium dodecyl sulfate and porous MoS in the step (3)2The mass ratio of the hollow spheres, the phenol, the formaldehyde and the sodium hydroxide is 30-40:17-22:30-50:10:7-8: 1.5-2.5.
4. MoS of a hierarchical putamen structure according to claim 22-C composite porous microsphere negative active material characterized by: the atmosphere furnace in the step (4) is used for calcining nitrogen, the heating rate is 5-10 ℃/min, the calcining temperature is 600-700 ℃, and the calcining time is 2-4 h.
CN202010685833.1A 2020-07-16 2020-07-16 MoS with hierarchical shell-core structure2Negative active material of-C composite porous microsphere Active CN111883753B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010685833.1A CN111883753B (en) 2020-07-16 2020-07-16 MoS with hierarchical shell-core structure2Negative active material of-C composite porous microsphere

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010685833.1A CN111883753B (en) 2020-07-16 2020-07-16 MoS with hierarchical shell-core structure2Negative active material of-C composite porous microsphere

Publications (2)

Publication Number Publication Date
CN111883753A CN111883753A (en) 2020-11-03
CN111883753B true CN111883753B (en) 2021-11-09

Family

ID=73155745

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010685833.1A Active CN111883753B (en) 2020-07-16 2020-07-16 MoS with hierarchical shell-core structure2Negative active material of-C composite porous microsphere

Country Status (1)

Country Link
CN (1) CN111883753B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112331834B (en) * 2020-11-12 2021-07-16 郑州轻工业大学 Bulb-shaped O-MXn/C nano reactor and preparation method and application thereof
CN114512729B (en) * 2020-11-16 2023-07-14 比亚迪股份有限公司 Nanomaterial, negative electrode protection slurry, lithium negative electrode and lithium battery
CN112421041B (en) * 2020-11-17 2022-07-19 奇瑞商用车（安徽）有限公司 B-Mo-C carrier and preparation method and application thereof
CN113066956B (en) * 2021-03-17 2022-06-10 宁德新能源科技有限公司 Electrochemical device and electronic device
CN113517438B (en) * 2021-04-23 2022-07-29 山东科技大学 Internal confinement heterojunction yolk-shell electrode material and preparation method and application thereof
CN113725423A (en) * 2021-09-17 2021-11-30 陕西科技大学 MnCO3/MoS2Heterojunction composite material and preparation method and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104091936A (en) * 2014-07-17 2014-10-08 浙江大学 MoS2 nanotile and graphene composite nanomaterial and preparation method thereof
CN106299304A (en) * 2016-09-27 2017-01-04 华南理工大学 A kind of carbon cladding molybdenum sulfide composite and preparation method and application and a kind of sodium-ion battery
CN107681139A (en) * 2017-06-28 2018-02-09 四川大学 Nitrogenous carbon-clad metal sulfide receives the preparation method and applications of micro- composite
CN109956500A (en) * 2019-03-25 2019-07-02 天津大学 A kind of preparation method of the molybdenum disulfide material of the nano flower-like for lithium sode cell cathode
CN110867578A (en) * 2019-11-21 2020-03-06 江苏理工学院 Sodium ion battery and preparation method and application thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100120104A1 (en) * 2008-11-06 2010-05-13 John Stuart Reed Biological and chemical process utilizing chemoautotrophic microorganisms for the chemosythetic fixation of carbon dioxide and/or other inorganic carbon sources into organic compounds, and the generation of additional useful products
CN110676068B (en) * 2019-10-28 2021-12-03 江西高信前沿科技有限公司 Polydopamine-coated MoS2-porous carbon supercapacitor material and method for producing the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104091936A (en) * 2014-07-17 2014-10-08 浙江大学 MoS2 nanotile and graphene composite nanomaterial and preparation method thereof
CN106299304A (en) * 2016-09-27 2017-01-04 华南理工大学 A kind of carbon cladding molybdenum sulfide composite and preparation method and application and a kind of sodium-ion battery
CN107681139A (en) * 2017-06-28 2018-02-09 四川大学 Nitrogenous carbon-clad metal sulfide receives the preparation method and applications of micro- composite
CN109956500A (en) * 2019-03-25 2019-07-02 天津大学 A kind of preparation method of the molybdenum disulfide material of the nano flower-like for lithium sode cell cathode
CN110867578A (en) * 2019-11-21 2020-03-06 江苏理工学院 Sodium ion battery and preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
一种新型锂空气电池阴极材料的合成及性能研究;于心如;《中国硕士学位论文》;20191231;第37-38页 *
金属硫化物复合材料的制备及其作为锂-钠二次电池负极材料的性能研究;张耀辉;《中国博士学位论文》;20190831;第13页 *

Also Published As

Publication number Publication date
CN111883753A (en) 2020-11-03

Similar Documents

Publication Publication Date Title
CN111883753B (en) MoS with hierarchical shell-core structure2Negative active material of-C composite porous microsphere
CN103682327B (en) Based on the lithium ion battery and preparation method thereof of the hollow porous nickel oxide composite material of N doping carbon-coating parcel
CN108598394B (en) Carbon-coated titanium manganese phosphate sodium microspheres and preparation method and application thereof
CN105024044A (en) Preparation method of high-capacity silica-powder-doped lithium battery anode slurry
CN115020681B (en) Carbon-coated sodium ferric sulfate positive electrode material and preparation method thereof
CN110061215B (en) Composite structure for lithium ion battery cathode and preparation method thereof
CN114477130A (en) Method for preparing hard carbon negative electrode material for sodium ion battery by adopting porous material
CN114400309A (en) Sodium ion positive electrode material and preparation method and application thereof
CN114702022B (en) Preparation method and application of hard carbon anode material
CN109950480A (en) Preparation method of carbon-coated tin sulfide nanobelt of lithium ion battery negative electrode material
CN115676804B (en) Porous hard carbon anode material based on asphalt, and preparation method and application thereof
CN112151781A (en) Rapid composite coating modification method for lithium battery positive electrode material
CN110707323A (en) Anion layer-expanding carbon material and preparation method and application thereof
CN108682856B (en) Typha carbon-loaded vanadium sodium phosphate nano composite material and preparation method and application thereof
CN110790248A (en) Iron-doped cobalt phosphide microsphere electrode material with flower-like structure and preparation method and application thereof
CN108539158B (en) rGO/WS2Preparation method of composite material and application of composite material in positive electrode material of lithium-sulfur battery
CN112615057B (en) Preparation method of solid-state lithium ion battery and solid-state lithium ion battery
CN107910540B (en) Preparation method of carbon-silicon negative electrode material and lithium ion battery
CN108390025B (en) Graphene-coated carbon/sulfur composite material and preparation method thereof
CN111509228B (en) Porous carbon-coated reduced TiO2-nThe positive electrode material of the lithium-sulfur battery and the preparation method thereof
CN110098398B (en) Preparation method and application of honeycomb-like sulfur-doped carbon material
CN108417787B (en) Graphene-coated carbon nanofiber/sulfur composite material and preparation method thereof
CN110783542A (en) Paper towel derived carbon fiber loaded MoS 2Preparation method of micro-flower composite material and application of micro-flower composite material in lithium-sulfur battery
CN105185957A (en) Polyaniline modified spherical carbon-sulfur composite material and preparation method thereof
CN113078300B (en) Preparation method of core-shell type indium sulfide microsphere sulfur-loaded composite material and lithium-sulfur battery 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
CB03 Change of inventor or designer information
CB03 Change of inventor or designer information

Inventor after: Luo Lingjing

Inventor after: Ju Qinghua

Inventor after: Xu Guangwen

Inventor after: Fan Menglin

Inventor before: Fan Menglin

TA01 Transfer of patent application right
TA01 Transfer of patent application right

Effective date of registration: 20211021

Address after: 200000 room 210-527, No. 15, Lane 110, Guyuan Road, Hongkou District, Shanghai

Applicant after: Shanghai Dingying Information Technology Co.,Ltd.

Address before: 454850 No.41, row 2, Fanrong street, Xihan village, Huangzhuang Town, Wen County, Jiaozuo City, Henan Province

Applicant before: Fan Menglin

GR01 Patent grant
GR01 Patent grant