CN113690438B - Selenide-containing composite material and preparation method and application thereof - Google Patents

Selenide-containing composite material and preparation method and application thereof Download PDF

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CN113690438B
CN113690438B CN202110818453.5A CN202110818453A CN113690438B CN 113690438 B CN113690438 B CN 113690438B CN 202110818453 A CN202110818453 A CN 202110818453A CN 113690438 B CN113690438 B CN 113690438B
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selenide
composite material
selenium
powder
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CN113690438A (en
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黄永鑫
张蒙蒙
陈人杰
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Beijing Institute of Technology BIT
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    • 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
    • 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
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention belongs to the technical field of preparation of a sodium ion battery cathode material, and particularly relates to a selenide-containing composite material and a preparation method and application thereof. The preparation method comprises three steps of metal oxide microspheres, selenium-containing solution and selenide-containing composite material. Transition metal hydroxide is prepared by a coprecipitation method, bimetallic components (tin and transition metal) are effectively introduced, a metal oxide microsphere structure is obtained after calcination, selenium powder obtains selenium ions through a reducing agent, the metal oxide microsphere structure is taken as a template, the selenium ions and oxygen in the metal oxide microsphere structure are exchanged, so that selenide containing the bimetallic components with high purity, good crystal form and complete and controllable structure is obtained, and the controllable structure of the selenide containing composite material is realized by controlling the structure of the metal oxide microsphere; the selenide-containing composite material is of an eggshell structure, and the specific surface area and active sites of the material can be increased by the structure, so that the sodium storage capacity of the selenide-containing composite material is improved.

Description

Selenide-containing composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of preparation of cathode materials of sodium-ion batteries, and particularly relates to a selenide-containing composite material and a preparation method and application thereof.
Background
With the rapid development of industry, people exploit a large amount of fossil fuels, which causes serious energy crisis, and the traditional energy sources such as coal, petroleum and the like cause great pollution to the environment. In the face of energy crisis and the increasing deterioration of the environment, the nation is actively developing energy structure transformation. Green energy sources such as wind energy, tidal energy and solar energy have the characteristics of discontinuity and instability, and the phenomena of abandoning wind and water exist in a large quantity in the using process, so that the energy storage device is required to be utilized to realize the high-efficiency storage and utilization of the energy.
A secondary battery has been widely developed as an energy storage device, and a lithium battery has been widely used from a smart phone, a notebook computer to a new energy automobile. However, the shortage and uneven distribution of lithium resources face the dilemma of resource scarcity, and research on sodium ion batteries is being carried out. With the continuous and deep research, researchers find that sodium ion batteries have the advantages of abundant resource reserves, wide distribution, low cost, no development bottleneck, environmental friendliness, compatibility with the existing production equipment of lithium ion batteries, better power characteristics, wide temperature range adaptability, safety, no over-discharge problem and the like, and more researchers are engaged in the research of sodium ion battery cathode materials.
At present, the negative electrode material of the sodium ion battery is mainly a carbonaceous material, has low specific capacity (generally-300 mAh/g) and high electrode potential (0.3V vs Na) + /Na) is a key issue limiting its widespread use. Therefore, the study of the scholars is focused on the conversion reaction type sodium ion battery negative electrode material. Since the interaction force of the metal-selenium bond in the metal selenide is smaller than that of the metal oxide and the sulfide, and the metal selenide has a wider sodium ion migration channel, the metal selenide is considered to be an ideal negative electrode material of a high-specific energy sodium ion battery. The practicability of the metal selenide negative electrode is realized, and the problems of low ionic/electronic conductivity, serious volume expansion and poor electrochemical reversibility of the material need to be mainly solved. In general, the selenide is difficult to simultaneously consider high specific energy and high structural stability, and the multi-metal doping can effectively form a synergistic effect and synchronously optimize the electrochemical performance of the selenide cathode. In the prior art, the selenide is mostly produced by adopting a one-step hydrothermal synthesis method of a tin source and a selenium source, and the size and the structure of the selenide synthesized by the method are difficult to control.
Disclosure of Invention
Therefore, the invention aims to overcome the defect that the selenide material obtained by a one-step hydrothermal method is difficult to control in structure, so that the high-performance multi-metal selenide composite structure is difficult to prepare, and provides a selenide-containing composite material, and a preparation method and application thereof.
Therefore, the invention provides the following technical scheme.
The invention provides a preparation method of a selenide-containing composite material, which comprises the following steps,
(1) Mixing sulfate or nitrate of transition metal, a carbon source and sodium stannate, placing at 0-3 ℃, adjusting the pH to 8-10 to obtain a metal hydroxide microsphere precursor, and performing first calcination to obtain metal oxide microspheres;
(2) Mixing selenium powder with a reducing agent to obtain a selenium-containing solution;
(3) Mixing the metal oxide microspheres with a carbon source to form a mixed solution; and (3) adding the selenium-containing solution obtained in the step (2) into the mixed solution, and performing hydrothermal reaction and secondary calcination to obtain the selenide-containing composite material.
The transition metal in the step (1) is at least one of copper, ferrous iron and nickel; preferably, copper sulfate, nickel sulfate or ferrous nitrate;
the molar ratio of the sulfate or nitrate of the transition metal, the carbon source and the sodium stannate is 3.2: (4.1-5): (2.8-3.4).
The carbon source has a conductivity of more than 1 × 10 3 S/cm of single-layer redox graphene or carbon nanotubes.
In the step (1), the temperature of the first calcination is 300-350 ℃, and the time is 1.5-3 h.
In the step (2), the concentration of selenium in the selenium-containing solution is 25-35 g/L.
In the step (3), the molar ratio of selenium to carbon source in the metal oxide microspheres and the selenium-containing solution is (0.65-0.71): 2: (4.1-5).
The hydrothermal reaction comprises the specific steps of heating to 180-200 ℃ at a heating rate of 2-5 ℃/min and reacting for 2-10 h.
The second calcination comprises the specific steps of raising the temperature to 400-600 ℃ at the temperature raising rate of 2-5 ℃/min and reacting for 2-3 h.
And (2) stirring and reacting the selenium powder and a reducing agent for 5-10 min at the temperature of 70-80 ℃ to obtain a selenium-containing solution.
The invention also provides the selenide-containing composite material prepared by the preparation method.
In addition, the invention also provides the selenide-containing composite material prepared by the preparation method or the application of the selenide-containing composite material in the negative electrode material of the sodium-ion battery.
The technical scheme of the invention has the following advantages:
1. the preparation method of the selenide-containing composite material provided by the invention comprises three steps of metal oxide microspheres, selenium-containing solution and the selenide-containing composite material. The composite material prepared by the method is of an eggshell structure, the specific surface area and the active sites of the material can be increased by the structure, the sodium storage capacity of the selenide-containing composite material is further improved, meanwhile, a hollow structure can be formed inside the structure, a buffer space is provided for volume expansion, and the volume change can be adapted, so that the structural stability of the material is improved, and meanwhile, the method can control the structure of the selenide-containing composite material. The method overcomes the defects that the selenide material prepared by one-step hydrothermal method and solid phase selenization method in the prior art has uncontrollable structure, low selenide purity, easily damaged precursor composition and structure, complex preparation and the like. The transition metal hydroxide is prepared by a coprecipitation method, bimetallic components (tin and transition metal) are effectively introduced, a metal oxide microsphere structure is obtained after calcination, selenium powder obtains selenium ions through a reducing agent, the metal oxide microsphere structure is taken as a template, the selenium ions are exchanged with oxygen in the metal oxide microsphere structure, so that selenide containing the bimetallic components with high purity, good crystal form and complete and controllable structure is obtained, and the controllable structure of the selenide containing composite material is realized by controlling the structure of the metal oxide microsphere; the selenide and the carbon source are uniformly compounded, so that the graphene can be interpenetrated among active material particles to form a three-dimensional conductive network structure; the material can simultaneously give consideration to high specific capacity and long cycle stability.
The selenide-containing composite material is compounded with the carbon source, so that the fatigue stress generated by volume expansion is reduced, the structural integrity of the selenide-containing composite material is maintained, and the service life is prolonged. Meanwhile, the compound carbon source can improve the electronic conductivity of the material and make up for the problem of poor conductivity of the metal selenide.
2. According to the preparation method of the selenide-containing composite material, metal ions of Cu, ni and Fe are introduced, a metal-Sn-hydroxide microsphere precursor is generated through coprecipitation, an oxide spherical template is produced through calcination, and oxygen ions and selenium ions are exchanged through hydrothermal treatment, so that the selenide-containing composite material with an eggshell structure is finally generated.
By controlling the molar ratio of the raw materials in each step, the reaction can be fully carried out. By controlling the temperature of the first calcination, the temperature of the second calcination, and the temperature and time of the hydrothermal reaction, the morphology of the selenide-containing composite material can be ensured, and if the calcination temperature is too high, the hydrothermal reaction temperature is too high, or the hydrothermal reaction time is too long, the morphology of the selenide-containing composite material is easily damaged, and the eggshell structure is damaged, so that the cycle stability of the material and the specific capacity of the material are influenced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 shows Cu in example 1 of the present invention 2 SnSe 4 -XRD pattern of rGO composite;
FIG. 2 shows Cu in example 1 of the present invention 2 SnSe 4 -scanning electron micrographs of rGO composite;
FIG. 3 shows Cu in example 1 of the present invention 2 SnSe 4 -transmission electron microscopy images of rGO composite;
FIG. 4 shows Cu in example 1 of the present invention 2 SnSe 4 -a cycling stability diagram for rGO composite sodium ion battery negative electrode;
FIG. 5 shows Cu in example 1 of the present invention 2 SnSe 4 -a rate profile of rGO composite sodium ion battery negative electrode;
FIG. 6 shows Cu in example 1 of the present invention 2 SnSe 4 -capacity density test results of rGO composites with Cu 2 SnSe 4 -cycle performance test results for rGO composite sodium ion batteries;
FIG. 7 is a scanning electron micrograph of a comparative example 1 composite of the present invention;
FIG. 8 is a graph of the cycle stability of the negative electrode of the composite sodium ion battery of comparative example 1 of the present invention;
FIG. 9 is a scanning electron micrograph of a comparative example 2 composite of the present invention;
FIG. 10 is a graph of the cycling stability of the negative electrode of the composite sodium ion battery of comparative example 2 of the present invention;
FIG. 11 is a scanning electron micrograph of a comparative example 3 composite of the present invention;
fig. 12 is a graph of the cycling stability of the negative electrode of the composite sodium ion battery of comparative example 3 of the present invention.
Detailed Description
The following examples are provided to better understand the present invention, not to limit the best mode, and not to limit the content and protection scope of the present invention, and any product that is the same or similar to the present invention and is obtained by combining the present invention with other features of the prior art and the present invention falls within the protection scope of the present invention.
The examples do not indicate specific experimental procedures or conditions, and can be performed according to the procedures or conditions of the conventional experimental procedures described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
The graphene used in the following examples and comparative examples had a conductivity of 10 5 S/cm, conductivity of the carbon nanotube of 10 4 S/cm。
Example 1
The embodiment provides a preparation method of a selenide-containing composite material, which comprises the following steps of,
(1) Taking 3.2mmol NaSnO 3 Added to 60mL of deionized water to form NaSnO 3 An aqueous solution; 50mg of graphene oxide powderUltrasonically dispersing the graphene oxide into 95mL of deionized water, and carrying out ultrasonic treatment for 30min to form a graphene oxide aqueous solution; mixing 3.2mmol of CuSO 4 ·5H 2 Adding O into the graphene oxide aqueous solution, placing the graphene oxide aqueous solution into a cold bath kettle, stirring and cooling the graphene oxide aqueous solution to 0 ℃, adding 800mL of ammonia water into the solution, adjusting the pH value to 9, quickly stirring the solution until the color of the solution becomes dark blue, and then dropwise adding NaSnO into the solution 3 Adding the aqueous solution dropwise for 30min to obtain CuSn (OH) 6 Precipitating; cuSn (OH) 6 Centrifuging the precipitate at high speed, washing with water and ethanol until the filtrate is neutral, oven drying for 24 hr to obtain CuSn (OH) 6 A powder; then the powder is put into a tubular furnace at 350 ℃ to be calcined for 2h to obtain dark green CuSnO 3 And (3) powder. Wherein, the centrifugation time is 10 min/time, and the rotating speed is 8000rpm.
(2) 158mg of selenium powder is taken and added into 5mL of hydrazine hydrate, and the mixture is stirred and reacted for 5min at 70 ℃ to form Se-containing solution 2+ And cooling the solution to room temperature for later use.
(3) Adding 50mg of graphene oxide powder into deionized water to obtain 60mL of solution, performing ultrasonic dispersion for 30min, and adding 158mg of CuSnO 3 The powder is subjected to ultrasonic dispersion for 1 hour to form a mixed solution; adding Se into the mixture obtained in the step (2) 2+ Dropwise adding the solution into the mixed solution, heating to 200 ℃ at a heating rate of 2 ℃/min for hydrothermal reaction for 2 hours, centrifuging, washing with water, washing with alcohol, and drying the product after hydrothermal reaction to obtain Cu 2 SnSe 4 -rGO black powder, placing the powder in a tube furnace, heating the powder to 500 ℃ at a heating rate of 2 ℃/min under the argon atmosphere, reacting for 2h, removing redundant selenium, and obtaining Cu 2 SnSe 4 -rGO composite (rGO is reduced graphene oxide).
FIG. 1 shows Cu obtained in this example 2 SnSe 4 XRD pattern of-rGO composite, indicating Cu is obtained 2 SnSe 4 -rGO, where CSS is Cu 2 SnSe 4 For short. FIG. 2 is Cu 2 SnSe 4 Scanning electron micrographs of rGO composite, illustrating that the composite is spherical and structurally stable. FIG. 3 is Cu 2 SnSe 4 Transmission electron microscopy of rGO composite, from figure 3 it is observed that the composite is of eggshell structure.
The method for testing the electrochemical performance of the composite material in the embodiment specifically comprises the following steps:
(1) Weighing Cu 2 SnSe 4 -rGO composite material, acetylene black, sodium carboxymethylcellulose (CMC) in a mass ratio of 7 2 SnSe 4 Mixing the rGO composite material with acetylene black, grinding for 20min, adding CMC and ionized water, continuously grinding for 20min to obtain slurry, coating the slurry on a current collector copper foil, and drying for 24h at normal temperature to obtain a negative pole piece.
(2) Cutting the negative pole piece into pole pieces with the diameter of 16mm by using a 16mm cutter, selecting the pole pieces with uniform coating appearance, weighing the mass of the pole pieces by using a precision balance, and calculating Cu 2 SnSe 4 -mass of rGO composite; a glove box which brings the pole pieces into an argon atmosphere is used for assembling a half cell, and a negative pole shell, a sodium piece, a glass fiber diaphragm, dropwise added electrolyte and Cu are sequentially arranged 2 SnSe 4 -rGO composite, gaskets, spring plates, i.e. assembled batteries, compacted by a button cell sealer, of the type CR2032 button cell type with 1M NaClO electrolyte 4 EC (1) +5% FEC, where EC is ethylene carbonate, DEC is diethyl carbonate, and FEC is fluoroethane carbonate. The cell was taken out of the glove box and left to stand for 24 hours before measuring the electrochemical properties.
On a neowei battery charge-discharge tester, under the constant current charge-discharge conditions that the charge-discharge voltage interval is 0.01-3V and the current density is 100mA/g, the charge specific capacity, the cycle efficiency and the cycle stability of the button battery in 500 cycles are detected and analyzed. The coulombic efficiency of each cycle is more than 98 percent, the first cycle discharge specific capacity is removed, and the discharge specific capacity after 500 cycles is kept about 85 percent of the initial discharge capacity; under the condition that the electrochemical workstation condition is 0.01-3V, a multiplying power performance graph is respectively measured by current densities of 0.1, 0.2, 0.4, 0.8, 1.6 and 3.2A/g.
FIG. 4 is Cu 2 SnSe 4 -cycle stability diagram of rGO composite sodium ion battery negative electrode, wherein a, b, c, d and e are cycle stability curves of 1, 2, 10, 100 and 500 cycles respectively, and it can be seen from the diagram that the charging and discharging curves are basically stable after 10 cycles to 500 cycles, and the specific charging capacities of a, b, c, d and e are respectively shown as500. 550, 600, 605 and 550mAh g -1 And the better cycling stability is shown after 10 circles.
FIG. 5 is Cu 2 SnSe 4 Multiplying power curve diagram of negative electrode of sodium ion battery made of-rGO composite material, and current density is 0.1 Ag -1 Specific capacity is 830mA h g -1 (ii) a When the current density reaches 3.2 ag -1 When the specific capacity reaches 475mA h g -1 At this time, the efficiency is 57% under the low-rate current, which indicates that the obtained composite material has better rate performance.
FIG. 6 is Cu 2 SnSe 4 Results of the capacity density test (c and d) of rGO composites with Cu 2 SnSe 4 The cycle performance test results (a and b) of the rGO composite material sodium ion battery show that the conductivity of the composite material can be improved by adding a carbon source, the capacity density is as high as 600mAh/g, the expansion of the structure volume is inhibited, and the coulomb efficiency is close to 100% after 500 cycles of charge and discharge.
Example 2
The embodiment provides a preparation method of a selenide-containing composite material, which specifically comprises the following steps,
(1) Taking 2.8mmol NaSnO 3 Adding the mixture into 60mL of deionized water to form NaSnO 3 An aqueous solution; ultrasonically dispersing 55mg of graphene oxide powder into 95mL of deionized water, and carrying out ultrasonic treatment for 30min to form a graphene oxide aqueous solution; 3.2mmol of Fe (NO) 3 ) 2 Adding the mixture into a graphene oxide aqueous solution, putting the mixture into a cold bath kettle, stirring and cooling the mixture to 0 ℃, adding 700mL of ammonia water into the mixture, adjusting the pH value to 8, quickly stirring the mixture, and then dropwise adding NaSnO into the mixture 3 Adding the aqueous solution dropwise for 30min to obtain FeSn (OH) 6 Precipitating; feSn (OH) 6 Centrifuging the precipitate at high speed, washing with water and ethanol until the filtrate is neutral, oven drying for 24 hr to obtain FeSn (OH) 6 Powder; then placing the powder in a tubular furnace at 350 ℃ to calcine for 2h to obtain FeSnO 3 And (3) powder. Wherein the centrifugation time is 10 min/time, and the rotating speed is 8000rpm.
(2) 158mg of selenium powder is added into 5mL of hydrazine hydrate and stirred for reaction for 5min at 70 ℃ to form Se-containing solution 2+ Solution, cooling to roomWarm for standby.
(3) Adding 55mg of graphene oxide powder into deionized water to prepare 60mL of solution, ultrasonically dispersing for 30min, adding 158mg of FeSnO 3 Carrying out ultrasonic dispersion on the powder for 1 hour to form a mixed solution; adding Se into the solution obtained in step (2) 2+ Dropwise adding the solution into the mixed solution, heating to 200 ℃ at the heating rate of 2 ℃/min for hydrothermal reaction for 2h, centrifuging, washing with water, washing with alcohol, and drying the product after hydrothermal reaction to obtain Fe 2 SnSe 4 -rGO black powder, placing the rGO black powder in a tube furnace, heating to 500 ℃ at a heating rate of 3 ℃/min under the argon atmosphere, reacting for 2h, removing redundant selenium, and obtaining Fe 2 SnSe 4 -rGO composite.
Example 3
The embodiment provides a preparation method of a selenide-containing composite material, which specifically comprises the following steps,
(1) Taking 3.4mmol NaSnO 3 Adding the mixture into 60mL of deionized water to form NaSnO 3 An aqueous solution; ultrasonically dispersing 60mg of graphene oxide powder into 95mL of deionized water, and carrying out ultrasonic treatment for 30min to form a graphene oxide aqueous solution; adding 3.2mmol of NiSO 4 ·6H 2 Adding O into the graphene oxide aqueous solution, placing the graphene oxide aqueous solution into a cold bath kettle, stirring and cooling the graphene oxide aqueous solution to 0 ℃, adding 1000mL of ammonia water into the graphene oxide aqueous solution, adjusting the pH value to 10, quickly stirring the mixture, and then dropwise adding NaSnO into the mixture 3 Adding the aqueous solution dropwise for 30min to obtain NiSn (OH) 6 Precipitating; niSn (OH) 6 Centrifuging the precipitate at high speed, washing with water and ethanol until the filtrate is neutral, oven drying for 24 hr to obtain NiSn (OH) 6 Powder; then the powder is placed in a tubular furnace at 350 ℃ to be calcined for 2h to obtain NiSnO 3 And (3) powder. Wherein the centrifugation time is 10 min/time, and the rotating speed is 8000rpm.
(2) 158mg of selenium powder is added into 5mL of hydrazine hydrate and stirred for reaction for 5min at 70 ℃ to form Se-containing solution 2+ And cooling the solution to room temperature for later use.
(3) Adding 60mg of graphene oxide powder into deionized water to prepare 60mL of solution, ultrasonically dispersing for 30min, adding 158mg of NiSnO 3 The powder is further ultrasonically dispersed for 1h to form a mixed solution(ii) a Adding Se into the mixture obtained in the step (2) 2+ Dropwise adding the solution into the mixed solution, heating to 200 ℃ at a heating rate of 3 ℃/min for hydrothermal reaction for 2 hours, and centrifuging, washing with water, washing with alcohol and drying the hydrothermal product to obtain Ni 2 SnSe 4 -rGO black powder, placing the powder in a tubular furnace, heating the powder to 500 ℃ at a heating rate of 2 ℃/min under the argon atmosphere, reacting for 2h, removing redundant selenium, and obtaining Ni 2 SnSe 4 -rGO composite.
Example 4
The embodiment provides a preparation method of a selenide-containing composite material, which specifically comprises the following steps,
(1) Taking 4.8mmol of NaSnO 3 Added to 90mL of deionized water to form NaSnO 3 An aqueous solution; ultrasonically dispersing 75mg of multi-walled carbon nanotube powder into 95mL of deionized water for 30min to form a multi-walled carbon nanotube powder aqueous solution; mixing 4.8mmol of CuSO 4 ·5H 2 Adding O into the multi-wall carbon nanotube powder aqueous solution, placing the mixture into a cold bath kettle, stirring and cooling the mixture to 0 ℃, adding 800mL of ammonia water into the mixture, adjusting the pH value to 9, quickly stirring the mixture until the solution becomes dark blue, and then dropwise adding NaSnO into the mixture 3 Adding the aqueous solution dropwise for 45min to obtain CuSn (OH) 6 Precipitating; cuSn (OH) 6 Centrifuging the precipitate at high speed, washing with water and ethanol until the filtrate is neutral, oven drying for 24 hr to obtain CuSn (OH) 6 A powder; then placing the powder in a tubular furnace at 350 ℃ for calcining for 2h to obtain CuSnO 3 And (3) powder. Wherein the centrifugation time is 10 min/time, and the rotating speed is 8000rpm.
(2) 158mg of selenium powder is taken and added into 5mL of hydrazine hydrate, and the mixture is stirred and reacted for 5min at the temperature of 80 ℃ to form Se-containing solution 2+ And cooling the solution to room temperature for later use.
(3) Adding 50mg of multi-walled carbon nanotube powder into deionized water to prepare 60mL of solution, ultrasonically dispersing for 30min, adding 158mg of CuSnO 3 The powder is subjected to ultrasonic dispersion for 1 hour to form a mixed solution; adding Se into the mixture obtained in the step (2) 2+ Dropwise adding the solution into the mixed solution, heating to 200 ℃ at a heating rate of 2 ℃/min for hydrothermal reaction for 2h, and carrying out hydrothermal reaction on the productCentrifuging, washing with water, washing with alcohol, and drying to obtain Cu 2 SnSe 4 -MWCNTs black powder, placing the powder in a tube furnace, heating the powder to 400 ℃ at a heating rate of 2 ℃/min under an argon atmosphere, reacting for 3h, removing redundant selenium, and obtaining Cu 2 SnSe 4 -MWCNTs composites.
Example 5
The embodiment provides a preparation method of a selenide-containing composite material, which comprises the following steps of,
(1) Taking 4.2mmol NaSnO 3 Added to 90mL of deionized water to form NaSnO 3 An aqueous solution; ultrasonically dispersing 82.5mg of multi-walled carbon nanotube powder (MWCNTs) into 150mL of deionized water for 30min to form a multi-walled carbon nanotube powder aqueous solution; 4.8mmol of NiSO 4 ·6H 2 Adding O into the multi-wall carbon nanotube powder aqueous solution, placing the mixture into a cold bath kettle, stirring and cooling the mixture to 0 ℃, adding 1000mL of ammonia water into the mixture, adjusting the pH value to 10, quickly stirring the mixture, and then dropwise adding NaSnO into the mixture 3 Adding the aqueous solution dropwise for 45min to obtain NiSn (OH) 6 Precipitating; niSn (OH) 6 Centrifuging the precipitate at high speed, washing with water and ethanol until the filtrate is neutral, oven drying for 24 hr to obtain NiSn (OH) 6 A powder; then placing the powder in a tubular furnace at 350 ℃ for calcining for 2h to obtain CuSnO 3 And (3) powder. Wherein the centrifugation time is 10 min/time, and the rotating speed is 8000rpm.
(2) 158mg of selenium powder is added into 5mL of hydrazine hydrate and stirred for reaction for 5min at 80 ℃ to form Se-containing solution 2+ And cooling the solution to room temperature for later use.
(3) Adding 55mg of multi-walled carbon nanotube powder into deionized water to prepare 60mL of solution, performing ultrasonic dispersion for 30min, and adding 158mg of NiSnO 3 Carrying out ultrasonic dispersion on the powder for 1 hour to form a mixed solution; adding Se into the mixture obtained in the step (2) 2+ Dropwise adding the solution into the mixed solution, heating to 200 ℃ at a heating rate of 2 ℃/min for hydrothermal reaction for 2 hours, centrifuging, washing with water, washing with alcohol, and drying the hydrothermal product to obtain Ni 2 SnSe 4 -MWCNTs black powder, placing in a tube furnace, under argon atmosphere, ramping up at a rate of 4 ℃/minHeating to 400 ℃ for reaction for 3h, removing excessive selenium to obtain Ni 2 SnSe 4 -MWCNTs composites.
Example 6
The embodiment provides a preparation method of a selenide-containing composite material, which specifically comprises the following steps,
(1) Taking 5.1mmol NaSnO 3 Added to 90mL of deionized water to form NaSnO 3 An aqueous solution; ultrasonically dispersing 90mg of multi-walled carbon nanotube powder into 150mL of deionized water for 30min to form a multi-walled carbon nanotube powder aqueous solution; 4.8mmol of FeSO 4 ·5H 2 Adding O into the multi-wall carbon nanotube powder aqueous solution, placing the mixture into a cold bath kettle, stirring and cooling the mixture to 0 ℃, adding 700mL of ammonia water into the mixture, adjusting the pH value to 8, quickly stirring the mixture, and then dropwise adding NaSnO into the mixture 3 Adding the aqueous solution dropwise for 45min to obtain FeSn (OH) 6 Precipitating; feSn (OH) 6 Centrifuging the precipitate at high speed, washing with water and ethanol until the filtrate is neutral, oven drying for 24 hr to obtain FeSn (OH) 6 Powder; then placing the powder in a tubular furnace at 350 ℃ to calcine for 2h to obtain FeSnO 3 And (3) powder. Wherein, the centrifugation time is 10 min/time, and the rotating speed is 8000rpm.
(2) 158mg of selenium powder is taken and added into 5mL of hydrazine hydrate, and the mixture is stirred and reacted for 5min at the temperature of 80 ℃ to form Se-containing solution 2+ And cooling the solution to room temperature for later use.
(3) Adding 60mg of multi-walled carbon nanotube powder into 60mL of deionized water, ultrasonically dispersing for 30min, adding 158mg of FeSnO 3 Carrying out ultrasonic dispersion on the powder for 1 hour to form a mixed solution; adding Se into the mixture obtained in the step (2) 2+ Dropwise adding the solution into the mixed solution, heating to 200 ℃ at the heating rate of 2 ℃/min for hydrothermal reaction for 2h, centrifuging, washing with water, washing with alcohol, and drying the product after hydrothermal reaction to obtain Fe 2 SnSe 4 -MWCNTs black powder, placing the powder in a tube furnace, heating the powder to 400 ℃ at a heating rate of 2 ℃/min under an argon atmosphere, reacting for 3h, removing redundant selenium, and obtaining Fe 2 SnSe 4 -MWCNTs composites.
Comparative example 1
The comparative example provides a method for preparing a selenide-containing composite material, which comprises the following steps,
(1) Ultrasonically dispersing 100mg of graphene oxide powder into water to prepare 160mL of solution, and carrying out ultrasonic treatment for 50min to form a graphene oxide aqueous solution; taking 3.2mmol NaSnO 3 Added to the above solution.
(2) Adding 16mg selenium powder into 10mL hydrazine hydrate, stirring and reacting for 5min at 70 ℃ to form Se-containing powder 2+ And cooling the solution to room temperature for later use.
(3) Adding Se into the mixture obtained in the step (2) 2+ Dropwise adding the solution into the step (1), heating to 200 ℃ at the heating rate of 2 ℃/min for hydrothermal reaction for 4 hours, centrifuging, washing with water, washing with alcohol, and drying the product after hydrothermal reaction to obtain SnSe 4 -rGO black powder, placing the powder in a tube furnace, heating the powder to 500 ℃ at a heating rate of 2 ℃/min under the argon atmosphere, reacting for 2h, removing redundant selenium, and obtaining SnSe 4 -rGO composite.
FIG. 7 is an electron micrograph of the composite material obtained in this comparative example, from which it can be seen that the composite material of spherical structure cannot be obtained in this comparative example; FIG. 8 also shows that the composite material has unstable cycle performance and low specific capacity up to 400mAh g -1 。
Comparative example 2
The comparative example provides a method for preparing a selenide-containing composite, comprising the steps of,
(1) Taking 3.2mmol of NaSnO 3 Adding the mixture into 60mL of deionized water to form NaSnO 3 An aqueous solution; ultrasonically dispersing 50mg of graphene oxide powder into 95mL of deionized water for 30min to form a graphene oxide aqueous solution; mixing 3.2mmol of CuSO 4 ·5H 2 Adding O into the graphene oxide aqueous solution, placing the graphene oxide aqueous solution into a cold bath kettle, stirring and cooling the graphene oxide aqueous solution to 0 ℃, adding 1200mL of ammonia water into the graphene oxide aqueous solution, adjusting the pH value to 13, quickly stirring the mixture until the solution becomes dark blue, and then dropwise adding NaSnO into the mixture 3 Adding the aqueous solution dropwise for 30min to obtain CuSn (OH) 6 Precipitating; cuSn (OH) 6 Centrifuging the precipitate at high speed, washing with water and alcohol until the filtrate is neutral, oven drying for 24 hrTo obtain CuSn (OH) 6 A powder; then the powder is put into a tubular furnace at 350 ℃ to be calcined for 2h to obtain dark green CuSnO 3 And (3) powder. Wherein the centrifugation time is 10 min/time, and the rotating speed is 8000rpm.
(2) 158mg of selenium powder is added into 5mL of hydrazine hydrate and stirred for reaction for 5min at 70 ℃ to form Se-containing solution 2+ And cooling the solution to room temperature for later use.
(3) Adding 50mg of graphene oxide powder into 60mL of deionized water, performing ultrasonic dispersion for 30min, and adding 158mg of CuSnO 3 Carrying out ultrasonic dispersion on the powder for 1 hour to form a mixed solution; adding Se into the solution obtained in step (2) 2+ Dropwise adding the solution into the mixed solution, heating to 200 ℃ at the heating rate of 2 ℃/min for hydrothermal reaction for 2 hours, centrifuging, washing with water, washing with alcohol, and drying the product after hydrothermal reaction to obtain Cu 2 SnSe 4 -rGO black powder, placing the powder in a tube furnace, heating the powder to 500 ℃ at a heating rate of 2 ℃/min under the argon atmosphere, reacting for 2h, removing redundant selenium, and obtaining Cu 2 SnSe 4 -rGO composite.
FIG. 9 is an electron microscope image of the composite material obtained in the present comparative example, which shows that the composite material with a spherical structure cannot be obtained in the present comparative example, which indicates that the morphology of the product is not good and the morphology of the microspheres cannot be obtained when the alkalinity is too high; the structure is collapsed after further reaction of calcination, selenization, hydrothermal treatment and secondary calcination, so that the material with an eggshell structure cannot be obtained; as can also be seen in fig. 10, the cycle performance of the composite material is unstable and the specific capacity is low.
Comparative example 3
The comparative example provides a method for preparing a selenide-containing composite, comprising the steps of,
(1) Taking 3.2mmol of NaSnO 3 Adding the mixture into 60mL of deionized water to form NaSnO 3 An aqueous solution; ultrasonically dispersing 50mg of graphene oxide powder into 95mL of deionized water for 30min to form a graphene oxide aqueous solution; mixing 3.2mmol of CuSO 4 ·5H 2 Adding O into the graphene oxide aqueous solution, adding 800mL of ammonia water, adjusting the pH to 9, quickly stirring until the solution becomes dark blue, and then dropwise addingDropwise adding NaSnO 3 Adding the aqueous solution dropwise for 30min to obtain CuSn (OH) 6 Precipitating; cuSn (OH) 6 Centrifuging the precipitate at high speed, washing with water and ethanol until the filtrate is neutral, oven drying for 24 hr to obtain CuSn (OH) 6 Powder; then the powder is put into a tubular furnace at 350 ℃ to be calcined for 2h to obtain dark green CuSnO 3 And (3) powder. Wherein the centrifugation time is 10 min/time, and the rotating speed is 8000rpm. Wherein the reaction is carried out at room temperature.
(2) 158mg of selenium powder is taken and added into 5mL of hydrazine hydrate, and the mixture is stirred and reacted for 5min at 70 ℃ to form Se-containing solution 2+ And cooling the solution to room temperature for later use.
(3) Adding 50mg of graphene oxide powder into 60mL of deionized water, performing ultrasonic dispersion for 30min, and adding 158mg of CuSnO 3 Carrying out ultrasonic dispersion on the powder for 1 hour to form a mixed solution; adding Se into the solution obtained in step (2) 2+ Dropwise adding the solution into the mixed solution, heating to 200 ℃ at a heating rate of 2 ℃/min for hydrothermal reaction for 2 hours, centrifuging, washing with water, washing with alcohol, and drying the product after hydrothermal reaction to obtain Cu 2 SnSe 4 -rGO black powder, placing the rGO black powder in a tube furnace, heating the rGO black powder to 500 ℃ at a heating rate of 2 ℃/min under the argon atmosphere, reacting for 2h, removing redundant selenium, and obtaining Cu 2 SnSe 4 -rGO composite.
FIG. 11 is an electron micrograph of the composite material obtained in this comparative example, from which it can be seen that the composite material of spherical structure cannot be obtained in this comparative example; as can also be seen in fig. 12, the cycle performance of the composite material is unstable and the specific capacity is low.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.

Claims (10)

1. A preparation method of a selenide-containing composite material is characterized by comprising the following steps,
(1) Mixing sulfate or nitrate of transition metal, a carbon source and sodium stannate, placing at 0-3 ℃, adjusting the pH to 8-10 to obtain a metal hydroxide microsphere precursor, and performing first calcination to obtain metal oxide microspheres;
(2) Mixing selenium powder with a reducing agent to obtain a selenium-containing solution;
(3) Mixing the metal oxide microspheres with a carbon source to form a mixed solution; and (3) adding the selenium-containing solution obtained in the step (2) into the mixed solution, and performing hydrothermal reaction and secondary calcination to obtain the selenide-containing composite material.
2. The preparation method according to claim 1, wherein the transition metal in the step (1) is at least one of copper, ferrous iron and nickel;
the molar ratio of the sulfate or nitrate of the transition metal, the carbon source and the sodium stannate is 3.2: (4.1-5): (2.8-3.4).
3. The method according to claim 1 or 2, wherein the carbon source has a conductivity of > 1X 10 3 S/cm of single-layer redox graphene or carbon nanotubes.
4. The method according to claim 1 or 2, wherein in the step (1), the temperature of the first calcination is 300 to 350 ℃ and the time is 1.5 to 3 hours.
5. The method according to claim 1 or 2, wherein in the step (2), the concentration of selenium in the selenium-containing solution is 25 to 35g/L.
6. The method according to claim 1 or 2, wherein in the step (3), the molar ratio of the metal oxide microspheres to the selenium in the selenium-containing solution to the carbon source is (0.65-0.71): 2: (4.1-5).
7. The preparation method according to claim 1 or 2, wherein the hydrothermal reaction comprises heating to 180-200 ℃ at a heating rate of 2-5 ℃/min for 2-10 h.
8. The preparation method of claim 1 or 2, wherein the second calcination comprises raising the temperature to 400-600 ℃ at a rate of 2-5 ℃/min for 2-3 h.
9. The selenide-containing composite material prepared by the preparation method of any one of claims 1 to 8.
10. The selenide containing composite material prepared by the preparation method of any one of claims 1 to 8 or the selenide containing composite material of claim 9 in the negative electrode material of sodium ion battery.
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