CN110931724B - Nickel-tin alloy based composite material with nanosphere structure and preparation method thereof - Google Patents

Nickel-tin alloy based composite material with nanosphere structure and preparation method thereof Download PDF

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CN110931724B
CN110931724B CN201910987624.XA CN201910987624A CN110931724B CN 110931724 B CN110931724 B CN 110931724B CN 201910987624 A CN201910987624 A CN 201910987624A CN 110931724 B CN110931724 B CN 110931724B
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nickel
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tin alloy
tin
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CN110931724A (en
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王建明
何志顺
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Zhejiang University ZJU
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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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • 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
    • H01M4/582—Halogenides
    • 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 discloses a nickel-tin alloy-based composite material with a nano-sphere structure and a preparation method thereof. The preparation method comprises the steps of firstly preparing the nickel-tin binary glycerate nanosphere material, and then carrying out one-step heat treatment by taking the nickel-tin binary glycerate nanosphere material as a precursor to prepare the nickel-tin alloy based nanosphere structure composite material. The method has the advantages of novel thought, simple and convenient operation, short synthesis period and low cost, and the nickel-tin alloy-based nanosphere structure composite material prepared by the method has great application potential in the energy storage fields of lithium batteries, sodium batteries and the like.

Description

Nickel-tin alloy based composite material with nanosphere structure and preparation method thereof
Technical Field
The invention belongs to the field of inorganic nano composite materials, and particularly relates to a nickel-tin alloy-based nano sphere structure composite material and a preparation method thereof.
Background
Organic-inorganic coordination hybrid is a crystalline porous material with a network structure formed by connecting an inorganic metal center (metal ion or metal cluster) and a bridging Organic substance through coordination. Because the materials have the characteristics of porosity, large specific surface area, rich and various structures, multiple metal sites and the like, the materials are widely applied to multiple fields, such as catalysis, sensors, optics, molecular magnets, anti-cancer drugs and the like. Although metal coordination hybrids have been studied in energy-related fields and applications, studies using them as templates/precursors for energy conversion and storage devices have been rarely reported. Particularly, in the organic-inorganic coordination heterozygote taking tin as a metal source, because tin ions are easy to hydrolyze in water to generate precipitates, reports about the preparation of the tin-based organic-inorganic coordination heterozygote are rare; in addition, binary and even multi-metal coordination hybrids have less literature reports on the controlled preparation of binary and even multi-metal coordination hybrids due to their possible diversity and complexity of reaction products, difficult control of reaction conditions, and the like. By changing the types and the proportions of metal ions, organic ligands and additives and adjusting the reaction temperature and the reaction time, the morphology obtained by preparation can be effectively changed, and the controllable preparation of micro-nano can be realized in size; the prepared organic-inorganic coordination heterozygote material with special morphology is subjected to one-step high-temperature heat treatment in inert gas, the inorganic metal center can be converted into a metal simple substance or a compound thereof, and the organic ligand can be carbonized, so that the metal/metal oxide composite material coated by the carbon layer is obtained. Because of the regular network arrangement of inorganic metal centers and organic ligands in the organic-inorganic coordination heterozygote material, the metal/metal compound after heat treatment is uniformly coated by a carbon layer at a low-size layer (several nanometers), and the large-range agglomeration among nano metal/metal compound particles can be effectively avoided; in addition, part of inorganic metals (such as nickel, cobalt and the like) have certain catalytic performance in the high-temperature heat treatment process, and amorphous carbon can be effectively converted into a graphene material, so that the thermal stability and the mechanical stability of the carbon material are improved; in addition, when binary or even multi-element metal coordination heterozygote is used as a template/precursor, more abundant multi-component materials can be obtained in the composite material obtained after heat treatment, and the comprehensive performance of the composite material can be further improved through the synergistic effect among different components in subsequent performance tests. Therefore, the composite material obtained by heat treatment with the organic-inorganic coordination hybrid material as the template/precursor can not only realize effective and uniform compounding between the metal/metal compound and the carbon material in one step, but also basically keep the morphology of the template/precursor, thereby realizing the design of special morphology and the controllable preparation of a micro-nano structure, and in addition, when the binary or even multi-element organic-inorganic coordination hybrid material is adopted as the template/precursor, the controllable preparation of even more abundant multi-component composite material can be realized.
At present, most of methods for preparing tin-based compound/carbon composite materials are two-step methods, namely, tin-based compound nano particles are prepared firstly and then are compounded with organic matters or carbon materials through a normal-temperature or high-temperature method, so that the tin-based compound/carbon composite materials or precursors thereof are formed.
The tin-based compound/carbon nano composite material is prepared by preparing a binary (nickel and tin) organic-inorganic coordination heterozygote material and performing one-step heat treatment by taking the binary (nickel and tin) organic-inorganic coordination heterozygote material as a precursor, wherein the tin-based compound is uniformly coated by a carbon layer; in addition, due to the existence of nickel, in the high-temperature heat treatment process, on one hand, the amorphous carbon material is effectively catalyzed, the graphitization degree of the carbon material is improved, and on the other hand, the rare Ni is formed with tin3Sn4Alloy, and further formed to have Ni as a main body3Sn4A composite material of the base. Therefore, the method is simple and convenient to operate and can be used for quickly preparing the tin-based compound/carbon nano composite material.
Disclosure of Invention
Aiming at the defects, the invention provides the nickel-tin alloy-based nanosphere structure composite material coated by the carbon layer, which is simple to operate, low in cost and has a certain graphitization degree, and the preparation method thereof. The method is a method for preparing the nickel-tin alloy-based composite material with the nanosphere structure by taking nickel salt, tin salt, glycerol and polyvinylpyrrolidone (PVP) as raw materials, and particularly is a method for preparing the nickel-tin alloy-based composite material with the nanosphere structure, which has the advantages of novel scheme, simple and convenient operation, short synthesis period and low cost.
The technical scheme adopted by the invention is as follows: the composite material is a nanosphere with the particle size of 300-500 nm, the nanosphere is formed by self-assembling a part of graphene-based carbon matrix and nickel-tin alloy-based nanoparticles embedded in the carbon matrix, the particle size of the nickel-tin alloy-based nanoparticles is 10-60 nm, the part of graphene-based carbon matrix has 3-6 graphene layers at the interface of the nanoparticles and carbon, and the nickel-tin alloy-based nanoparticles are uniformly dispersed in the part of graphene-based carbon matrix.
A second object of the present invention is to provide a method for preparing the above nickel-tin alloy-based nanosphere structure composite material, comprising the steps of:
weighing nickel salt, tin salt and polyvinyl pyrrolidone (PVP);
dispersing all reaction raw materials weighed in the step (1) in a mixed solvent of glycerol and isopropanol, and fully dissolving and dispersing under an ultrasonic condition to form a light green reaction clear liquid;
transferring the light green reaction clear liquid obtained in the step (2) to a stainless steel reaction kettle with a Teflon lining, carrying out solvothermal reaction in an oven, and after the reaction is finished, carrying out centrifugal separation to obtain a precipitate which is a nickel-tin diglyceride material;
step four, using the nickel-tin diglyceride obtained in step 3 as a precursor, performing heat treatment in a tube furnace protected by argon atmosphere, and obtaining Ni after heat treatment3Sn4A carbon-based nanosphere structure composite material.
In the presence of Ni3Sn4In the preparation method of the base/carbon nanosphere structure composite material, nickel salt, tin salt and glycerol are used as raw materials, polyvinylpyrrolidone (PVP) is used as a dispersing agent, a glycerol-isopropanol mixed solvent is used as a reaction solvent, and a precursor of the material is prepared by a solvothermal method: nickel tin diglyceride, then the precursor is processed by one-step heat treatment in inert atmosphere, finally Ni is obtained3Sn4A carbon-based nanosphere structure composite material. The preparation process can be divided into the following stages:
1. ni solvothermal condition2+And Sn2+Self-assembly with glycerol anion:
under solvothermal high-temperature high-pressure conditions, Ni2+And Sn2+Self-assembling with glycerol negative ions by means of coordination to form a space periodically arranged organic-inorganic coordination hybrid material. During the self-assembly process, due to Ni2+And Sn2+All have abundant empty d orbitals (3d or 4d), Ni2+And Sn2+Can be coordinated with glycerol negative ions, thereby realizing the preparation of the nickel-tin binary organic-inorganic coordination heterozygote material. Interestingly, the morphology of the obtained organic-inorganic coordination heterozygote can be regulated and controlled by selecting and proportioning the reaction solvent. When the mixed solvent of glycerol and isopropanol is selected, the nano-spherical organic-inorganic coordination hybrid material can be obtained.
2. One-step heat treatment conversion to obtain Ni3Sn4Base/carbon nanosphere structure composite material:
the obtained nickel-tin binary organic-inorganic coordination heterozygote material is subjected to heat treatment in inert atmosphere to realize Ni3Sn4And (3) preparing the composite material with the base/carbon nanosphere structure in one step. During the heat treatment, since the heat treatment is performed under the protection of an inert atmosphere, the organic ligand is remained in the form of carbon layer due to the excessive carbon content, and the metal ion (Ni)2+,Sn2+) Under the reduction action of the carbon material, the nickel-tin alloy (Ni) can be converted into a nickel-tin alloy with stable properties3Sn4) A predominantly tin-based compound. And because the metal ions and the organic ligands are arranged in a regular network, the carbon layer converted by the organic ligands can be effectively coated around the metal compound nanoparticles to prevent further agglomeration among the nanoparticles. In addition, due to the existence of nickel, in the high-temperature heat treatment process of the inert atmosphere, on one hand, the amorphous carbon material can be effectively catalyzed, the graphitization degree of the carbon material is improved, and on the other hand, the rare Ni is formed with tin3Sn4Alloy, and further realizing mainly Ni3Sn4Preparation of carbon-based composite materials. By optimizing the heat treatment conditions, the spherical shape of the precursor can be maintained, so that Ni is obtained3Sn4A carbon-based nanosphere structure composite material.
In the preparation method of the nickel-tin alloy-based nanosphere structure composite material, the nickel salt in the step (1) is one of nickel nitrate, nickel chloride, nickel sulfate and nickel acetate, and the tin salt is one of stannous dichloride and stannous sulfate.
Preferably, the molar ratio of the nickel salt to the tin salt is: the ratio of the nickel salt to the tin salt is 2: 1-1: 2, and the ratio of PVP to total transition metal salt is as follows: PVP: total salt 1 g: 0.9mmol, total transition metal salt is the sum of nickel and tin salts.
Preferably, the volume ratio of the glycerol to the isopropanol in the mixed solvent is as follows: glycerol isopropanol-1: 5.
Preferably, the PVP: 1-1.5 g of mixed solvent: 48 mL.
Preferably, the solvothermal reaction temperature in the step (3) is 150-200 ℃, and the reaction time is 4-8 h.
Preferably, the heat treatment conditions in step (4) are: under the protection of argon atmosphere, firstly heating to 250 ℃ at a heating rate of 1-5 ℃/min, carrying out heat treatment at the heat treatment temperature (250 ℃) for 1-2 hours, then heating to 450 ℃ at the same heating rate (1-5 ℃/min), and carrying out heat treatment at the heat treatment temperature (450 ℃) for 2-4 hours.
The structure, morphology and properties of the nickel-tin alloy-based nanosphere structure composite material and the precursor thereof obtained by the method are characterized by means of infrared spectroscopy (IR), X-ray powder diffractometer (XRD), Raman spectroscopy (Raman), Scanning Electron Microscope (SEM), Transmission Electron Microscope (TEM) and the like, and the characteristics show that: the material is nanospheres with the particle size of 300-500 nm, and the nanospheres are prepared from carbon matrixes of partial graphene and Ni embedded in the carbon matrixes3Sn4Self-assembly of base nanoparticles, said Ni3Sn4The particle size of the base nanoparticle is 10-60 nm, the part of the graphene-based carbon matrix has 3-6 graphene layers at the interface of the nanoparticle and the carbon, and the Ni3Sn4The base nanoparticles are uniformly dispersed in said partially graphitized carbon matrix.
The invention has the beneficial effects that:
(1) the invention uses organic-inorganic coordination heterozygote material as precursor and self-sacrifice template, prepares nickel-tin binary organic-inorganic coordination heterozygote material with spherical shape by optimizing reaction conditions, and obtains nickel-tin alloy-based nanosphere structure composite material by one-step heat treatment in inert atmosphere. Compared with the traditional two-step method, the preparation method is novel, the operation is simple and convenient, the synthesis period is short, the cost is low, and the micro-morphology of the prepared material is particularly novel.
(2) The prepared nickel-tin alloy-based composite material with the nanosphere structure has the advantages that the particle size of metal compound nanoparticles is 10-60 nm, and the main component of the metal compound nanoparticles is rare Ni3Sn4The alloy, and they are dispersed evenly in carbon matrix nanospheres with a certain degree of graphitization, while a novel 3-6 graphene layers can be seen at the interface where these nanoparticles are in contact with carbon.
According to the invention, under the process condition, the nickel-tin alloy-based composite material with the nanosphere structure can be simply, conveniently and rapidly prepared, and the prepared material does not need to be subjected to subsequent treatment. Therefore, the invention provides a method for rapidly preparing a nickel-tin alloy-based composite material with a nanosphere structure. The nickel-tin alloy-based composite material with the nanosphere structure prepared by the invention has great application potential in the energy storage fields of lithium batteries, sodium batteries and the like.
Drawings
FIG. 1 (a) is an X-ray powder diffraction (XRD) pattern of nickel tin diglyceride and stannyl glycerate prepared by the present invention, and FIG. 1 (b) is an infrared spectrum of nickel tin diglyceride and stannyl glycerate prepared by the present invention;
FIG. 2 (a) shows Ni prepared by the present invention3Sn4The X-ray powder diffraction (XRD) patterns of the Sn @ C composite material based on the nano-sphere structure composite material and the contrast are shown in (b) of figure 2, wherein Ni prepared by the method is shown in the invention3Sn4Raman (Raman) spectra of the base nanosphere structure composite and the control Sn @ C composite;
FIG. 3 shows the nickel tin diglyceride (a) and Ni prepared by the present invention3Sn4Scanning Electron Microscope (SEM) images of the base nanosphere structure composite material (b);
FIG. 4 (a) to FIG. 4 (c) are Ni prepared by the present invention3Sn4Transmission Electron Microscope (TEM) pictures of the composite material with the base nanosphere structure at different magnifications, and (d) of FIG. 4 is the corresponding element scan (Mappi) of the composite materialng) pictures;
FIG. 5 shows Ni prepared by the present invention3Sn4The electrochemical lithium storage large current cycle performance result when the composite material with the base nano-sphere structure and the Sn @ C composite material which is compared are used as the cathode material of the lithium ion battery.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
Ni prepared from nickel nitrate, stannous chloride, polyvinylpyrrolidone (PVP) and glycerol as raw materials3Sn4The steps of the composite material with the base nanometer ball structure are as follows:
(1) 0.45mmol of nickel nitrate, 0.45mmol of stannous chloride and 1g of polyvinylpyrrolidone (PVP) are respectively weighed.
(2) And adding the weighed reaction raw materials into a small beaker, adding 8mL of glycerol and 40mL of isopropanol, and performing ultrasonic treatment for 60min to disperse and dissolve the substances in the mixed solvent to form a light green reaction clear solution.
(3) The light green reaction clear liquid is transferred into a stainless steel reaction kettle with a Teflon lining and reacts for 6 hours in a high-temperature oven at 180 ℃.
(4) After the reaction is finished, the reaction kettle is naturally cooled to room temperature, and the obtained light green powder is washed by absolute ethyl alcohol for a plurality of times and is dried at 70 ℃ overnight.
(5) And (2) carrying out heat treatment on the obtained light green powder in a tube furnace under the argon atmosphere, wherein the heat treatment conditions are as follows: the temperature is raised to 250 ℃ at the heating rate of 2 ℃/min, and after the heat treatment is carried out for 1h at the heat treatment temperature (250 ℃), the temperature is raised to 450 ℃ at the same heating rate (2 ℃/min), and the heat treatment is carried out for 2h at the heat treatment temperature (450 ℃). The black powder obtained after the heat treatment is Ni3Sn4A composite material with a base nanosphere structure.
It can be seen in fig. 1 (a) that both the nickel tin diglyceride prepared by example 1 and the comparative tin glycerate produced distinct diffraction peaks at the low angle (<10 °) position, indicating the nature of the better crystalline and organic-inorganic coordination hybrids; by comparison, it can be seen that the vibrational peaks of M-O bond and O-M-O bond in (b) of FIG. 1 are both clearly present, indicating the formation of organic-inorganic coordination hybrids.
Example 2
Ni prepared from nickel chloride, stannous chloride, polyvinylpyrrolidone (PVP) and glycerol3Sn4The steps of the base nanostructure composite material are as follows:
(1) 0.45mmol of nickel chloride, 0.45mmol of stannous chloride and 1g of polyvinylpyrrolidone (PVP) are weighed respectively.
(2) And adding the weighed reaction raw materials into a small beaker, adding 8mL of glycerol and 40mL of isopropanol, and performing ultrasonic treatment for 60min to disperse and dissolve the substances in the mixed solvent to form a light green reaction clear solution.
(3) The light green reaction clear liquid is transferred into a stainless steel reaction kettle with a Teflon lining and reacts for 8 hours in a high-temperature oven at the temperature of 200 ℃.
(4) After the reaction is finished, the reaction kettle is naturally cooled to room temperature, and the obtained light green powder is washed by absolute ethyl alcohol for a plurality of times and is dried at 70 ℃ overnight.
(5) And (2) carrying out heat treatment on the obtained light green powder in a tube furnace under the argon atmosphere, wherein the heat treatment conditions are as follows: the temperature is raised to 250 ℃ at the heating rate of 1 ℃/min, and after the heat treatment is carried out for 1h at the heat treatment temperature (250 ℃), the temperature is raised to 450 ℃ at the same heating rate (1 ℃/min), and the heat treatment is carried out for 2h at the heat treatment temperature (450 ℃). The black powder obtained after the heat treatment is Ni3Sn4A composite material with a base nanosphere structure.
Ni prepared by example 2 can be found in (a) of FIG. 23Sn4The main component of the composite material with the base nanometer ball structure is Ni3Sn4The main component of the compared Sn @ C composite material is Sn simple substance, and in addition, the two composite materials both contain a small amount of SnO and SnO2These components may be due to partial oxidation of the material upon exposure to air; raman spectroscopy (FIG. 2 (b)) shows that Ni is compared to Sn @ C composite3Sn4The composite material with the base nano-sphere structure presents higher performanceThe degree of graphitization indicates that the presence of nickel can catalyze the conversion of a portion of the amorphous carbon to graphitized carbon during heat treatment.
Example 3
Ni prepared from nickel sulfate, stannous chloride, polyvinylpyrrolidone (PVP) and glycerol3Sn4The steps of the base nanostructure composite material are as follows:
(1) 0.45mmol of nickel sulfate, 0.45mmol of stannous chloride and 1g of polyvinylpyrrolidone (PVP) are weighed respectively.
(2) And adding the weighed reaction raw materials into a small beaker, adding 8mL of glycerol and 40mL of isopropanol, and performing ultrasonic treatment for 60min to disperse and dissolve the substances in the mixed solvent to form a light green reaction clear solution.
(3) The light green reaction clear liquid is transferred into a stainless steel reaction kettle with a Teflon lining and reacts for 6 hours in a high-temperature oven at 180 ℃.
(4) After the reaction is finished, the reaction kettle is naturally cooled to room temperature, and the obtained light green powder is washed by absolute ethyl alcohol for a plurality of times and is dried at 70 ℃ overnight.
(5) And (2) carrying out heat treatment on the obtained light green powder in a tube furnace under the argon atmosphere, wherein the heat treatment conditions are as follows: the temperature is raised to 250 ℃ at the heating rate of 2 ℃/min, and after the heat treatment is carried out for 1h at the heat treatment temperature (250 ℃), the temperature is raised to 450 ℃ at the same heating rate (2 ℃/min), and the heat treatment is carried out for 2h at the heat treatment temperature (450 ℃). The black powder obtained after the heat treatment is Ni3Sn4A composite material with a base nanosphere structure.
FIGS. 3 and 4 (a) - (d) are Ni or the nickel-tin diglyceride precursor prepared in example 33Sn4Scanning Electron Microscope (SEM) pictures and Transmission Electron Microscope (TEM) pictures of the composite material with the base nanometer spherical structure. It can be seen from fig. 3 that the sample substantially maintains the nano-spherical morphology of the precursor after heat treatment, the particle size is reduced, and in addition, after heat treatment at high temperature, the spherical surface appears obvious nanoparticles, which is shown in the later Transmission Electron Microscope (TEM) picture to be caused by the internal metal compound nanoparticles; it can be seen from (a) - (d) of fig. 4 that the nanosphere structure is composed ofPartially graphitized carbon matrix with Ni embedded therein3Sn4The nano particles are formed by self-assembly, wherein the particle size of the metal compound nano particles is 10-60 nm, novel 3-6 graphene layers can be seen at the contact interface of the nano particles and carbon, and two elements of Ni and Sn in an element scanning diagram are mainly distributed at the positions of the internal nano particles, which shows that the main component of the nano particles in the nano spheres is Ni3Sn4The C, O elements are distributed more evenly in the whole nanosphere area;
example 4
Ni prepared from nickel acetate, stannous chloride, polyvinylpyrrolidone (PVP) and glycerol as raw materials3Sn4The steps of the composite material with the base nanometer ball structure are as follows:
(1) 0.9mmol of nickel acetate, 0.45mmol of stannous chloride and 1.5g of polyvinylpyrrolidone (PVP) are respectively weighed.
(2) And adding the weighed reaction raw materials into a small beaker, adding 8mL of glycerol and 40mL of isopropanol, and performing ultrasonic treatment for 60min to disperse and dissolve the substances in the mixed solvent to form a light green reaction clear solution.
(3) The light green reaction clear liquid is transferred into a stainless steel reaction kettle with a Teflon lining and reacts for 6 hours in a high-temperature oven at the temperature of 150 ℃.
(4) After the reaction is finished, the reaction kettle is naturally cooled to room temperature, and the obtained light green powder is washed by absolute ethyl alcohol for a plurality of times and is dried at 70 ℃ overnight.
(5) And (2) carrying out heat treatment on the obtained light green powder in a tube furnace under the argon atmosphere, wherein the heat treatment conditions are as follows: the temperature is raised to 250 ℃ at the heating rate of 2 ℃/min, and after the heat treatment is carried out for 1h at the heat treatment temperature (250 ℃), the temperature is raised to 450 ℃ at the same heating rate (2 ℃/min), and the heat treatment is carried out for 2h at the heat treatment temperature (450 ℃). The black powder obtained after the heat treatment is Ni3Sn4A carbon-based nanosphere structure composite material.
FIG. 5 shows Ni prepared in example 43Sn4Composite material with base nano-sphere structure and Sn @ C composite material used as lithium ion battery in contrast with composite materialThe result of electrochemical lithium storage large current cycle performance of the cathode material. Ni in comparison to a comparative Sn @ C composite3Sn4The composite material with the base nano-sphere structure has higher electrochemical lithium storage capacity and better cycle stability, and is 1A g-1After charging and discharging for 500 cycles under the current density of (1), the lithium ion battery still can give 542.8mAh g-1Exhibits excellent electrochemical lithium storage performance.
Example 5
Ni prepared from nickel nitrate, stannous sulfate, polyvinylpyrrolidone (PVP) and glycerol as raw materials3Sn4The steps of the composite material with the base nanometer ball structure are as follows:
(1) 0.6mmol of nickel nitrate, 0.6mmol of stannous sulfate and 1.3g of polyvinylpyrrolidone (PVP) are respectively weighed.
(2) And adding the weighed reaction raw materials into a small beaker, adding 8mL of glycerol and 40mL of isopropanol, and performing ultrasonic treatment for 90min to disperse and dissolve the substances in the mixed solvent to form a light green reaction clear solution.
(3) The light green reaction clear liquid is transferred into a stainless steel reaction kettle with a Teflon lining and reacts for 4 hours in a high-temperature oven at 180 ℃.
(4) After the reaction is finished, the reaction kettle is naturally cooled to room temperature, and the obtained light green powder is washed by absolute ethyl alcohol for a plurality of times and is dried at 70 ℃ overnight.
(5) And (2) carrying out heat treatment on the obtained light green powder in a tube furnace under the argon atmosphere, wherein the heat treatment conditions are as follows: the temperature is raised to 250 ℃ at the heating rate of 5 ℃/min, and after the heat treatment is carried out for 1h at the heat treatment temperature (250 ℃), the temperature is raised to 450 ℃ at the same heating rate (5 ℃/min), and the heat treatment is carried out for 2h at the heat treatment temperature (450 ℃). The black powder obtained after the heat treatment is Ni3Sn4A composite material with a base nanosphere structure.
Example 6
Ni prepared from nickel chloride, stannous sulfate, polyvinylpyrrolidone (PVP) and glycerol as raw materials3Sn4The steps of the composite material with the base nanometer ball structure are as follows:
(1) 0.6mmol of nickel chloride, 0.3mmol of stannous sulfate and 1g of polyvinylpyrrolidone (PVP) are weighed respectively.
(2) And adding the weighed reaction raw materials into a small beaker, adding 8mL of glycerol and 40mL of isopropanol, and performing ultrasonic treatment for 90min to disperse and dissolve the substances in the mixed solvent to form a light green reaction clear solution.
(3) The light green reaction clear liquid is transferred into a stainless steel reaction kettle with a Teflon lining and reacts for 6 hours in a high-temperature oven at the temperature of 200 ℃.
(4) After the reaction is finished, the reaction kettle is naturally cooled to room temperature, and the obtained light green powder is washed by absolute ethyl alcohol for a plurality of times and is dried at 70 ℃ overnight.
(5) And (2) carrying out heat treatment on the obtained light green powder in a tube furnace under the argon atmosphere, wherein the heat treatment conditions are as follows: the temperature is raised to 250 ℃ at the heating rate of 2 ℃/min, and after the heat treatment is carried out for 1h at the heat treatment temperature (250 ℃), the temperature is raised to 450 ℃ at the same heating rate (2 ℃/min), and the heat treatment is carried out for 2h at the heat treatment temperature (450 ℃). The black powder obtained after the heat treatment is Ni3Sn4A composite material with a base nanosphere structure.
Example 7
Ni prepared from nickel sulfate, stannous sulfate, polyvinylpyrrolidone (PVP) and glycerol3Sn4The steps of the composite material with the base nanometer ball structure are as follows:
(1) 0.6mmol of nickel sulfate, 0.6mmol of stannous sulfate and 1.3g of polyvinylpyrrolidone (PVP) are weighed respectively.
(2) And adding the weighed reaction raw materials into a small beaker, adding 8mL of glycerol and 40mL of isopropanol, and performing ultrasonic treatment for 90min to disperse and dissolve the substances in the mixed solvent to form a light green reaction clear solution.
(3) The light green reaction clear liquid is transferred into a stainless steel reaction kettle with a Teflon lining and reacts for 4 hours in a high-temperature oven at 180 ℃.
(4) After the reaction is finished, the reaction kettle is naturally cooled to room temperature, and the obtained light green powder is washed by absolute ethyl alcohol for a plurality of times and is dried at 70 ℃ overnight.
(5) Under the atmosphere of argon gas, the reaction kettle is,the obtained light green powder was heat-treated in a tube furnace under the following conditions: the temperature is raised to 250 ℃ at the heating rate of 5 ℃/min, and after the heat treatment is carried out for 1h at the heat treatment temperature (250 ℃), the temperature is raised to 450 ℃ at the same heating rate (5 ℃/min), and the heat treatment is carried out for 2h at the heat treatment temperature (450 ℃). The black powder obtained after the heat treatment is Ni3Sn4A composite material with a base nanosphere structure.
Example 8
Ni prepared from nickel acetate, stannous sulfate, polyvinylpyrrolidone (PVP) and glycerol as raw materials3Sn4The steps of the composite material with the base nanometer ball structure are as follows:
(1) 0.3mmol of nickel acetate, 0.6mmol of stannous sulfate and 1g of polyvinylpyrrolidone (PVP) are respectively weighed.
(2) And adding the weighed reaction raw materials into a small beaker, adding 8mL of glycerol and 40mL of isopropanol, and performing ultrasonic treatment for 90min to disperse and dissolve the substances in the mixed solvent to form a light green reaction clear solution.
(3) The light green reaction clear solution is transferred into a stainless steel reaction kettle with a Teflon lining and reacted for 4 hours in a high-temperature oven at the temperature of 150 ℃.
(4) After the reaction is finished, the reaction kettle is naturally cooled to room temperature, and the obtained light green powder is washed by absolute ethyl alcohol for a plurality of times and is dried at 70 ℃ overnight.
(5) And (2) carrying out heat treatment on the obtained light green powder in a tube furnace under the argon atmosphere, wherein the heat treatment conditions are as follows: the temperature is raised to 250 ℃ at the heating rate of 1 ℃/min, heat treatment is carried out for 1-2 h at the heat treatment temperature (250 ℃), then the temperature is raised to 450 ℃ at the same heating rate (1 ℃/min), and heat treatment is carried out for 2-4 h at the heat treatment temperature (450 ℃). The black powder obtained after the heat treatment is Ni3Sn4A composite material with a base nanosphere structure.
Example 9
Ni prepared from nickel nitrate, stannous chloride, polyvinylpyrrolidone (PVP) and glycerol as raw materials3Sn4The steps of the composite material with the base nanometer ball structure are as follows:
(1) 0.3mmol of nickel nitrate, 0.6mmol of stannous chloride and 1g of polyvinylpyrrolidone (PVP) are respectively weighed.
(2) And adding the weighed reaction raw materials into a small beaker, adding 8mL of glycerol and 40mL of isopropanol, and performing ultrasonic treatment for 60min to disperse and dissolve the substances in the mixed solvent to form a light green reaction clear solution.
(3) The light green reaction clear liquid is transferred into a stainless steel reaction kettle with a Teflon lining and reacts for 6 hours in a high-temperature oven at 180 ℃.
(4) After the reaction is finished, the reaction kettle is naturally cooled to room temperature, and the obtained light green powder is washed by absolute ethyl alcohol for a plurality of times and is dried at 70 ℃ overnight.
(5) And (2) carrying out heat treatment on the obtained light green powder in a tube furnace under the argon atmosphere, wherein the heat treatment conditions are as follows: the temperature is raised to 250 ℃ at the heating rate of 2 ℃/min, heat treatment is carried out for 1-2 h at the heat treatment temperature (250 ℃), then the temperature is raised to 450 ℃ at the same heating rate (2 ℃/min), and heat treatment is carried out for 2-4 h at the heat treatment temperature (450 ℃). The black powder obtained after the heat treatment is Ni3Sn4A composite material with a base nanosphere structure.
Example 10
Ni prepared from nickel nitrate, stannous chloride, polyvinylpyrrolidone (PVP) and glycerol as raw materials3Sn4The steps of the composite material with the base nanometer ball structure are as follows:
(1) 0.6mmol of nickel nitrate, 0.3mmol of stannous chloride and 1g of polyvinylpyrrolidone (PVP) are respectively weighed.
(2) And adding the weighed reaction raw materials into a small beaker, adding 8mL of glycerol and 40mL of isopropanol, and performing ultrasonic treatment for 90min to disperse and dissolve the substances in the mixed solvent to form a light green reaction clear solution.
(3) The light green reaction clear liquid is transferred into a stainless steel reaction kettle with a Teflon lining and reacts for 6 hours in a high-temperature oven at 180 ℃.
(4) After the reaction is finished, the reaction kettle is naturally cooled to room temperature, and the obtained light green powder is washed by absolute ethyl alcohol for a plurality of times and is dried at 70 ℃ overnight.
(5) Under argon atmosphere in the tubeAnd (3) carrying out heat treatment on the obtained light green powder in a formula furnace, wherein the heat treatment conditions are as follows: the temperature is raised to 250 ℃ at the heating rate of 2 ℃/min, heat treatment is carried out for 1-2 h at the heat treatment temperature (250 ℃), then the temperature is raised to 450 ℃ at the same heating rate (2 ℃/min), and heat treatment is carried out for 2-4 h at the heat treatment temperature (450 ℃). The black powder obtained after the heat treatment is Ni3Sn4A composite material with a base nanosphere structure.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by using the contents of the present specification and the accompanying drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.

Claims (8)

1. A preparation method of a nickel-tin alloy-based nanosphere structure composite material is characterized by comprising the following steps:
weighing nickel salt, tin salt and polyvinylpyrrolidone;
step (2) dispersing all reaction raw materials weighed in the step (1) in a mixed solvent of glycerol and isopropanol, and fully dissolving and dispersing under an ultrasonic condition to form light green reaction clear liquid;
transferring the light green reaction clear liquid in the step (2) to a stainless steel reaction kettle with a Teflon lining, carrying out solvothermal reaction in an oven, and after the reaction is finished, carrying out centrifugal separation to obtain a precipitate which is a nickel-tin diglyceride material;
step (4) taking the nickel-tin diglyceride obtained in the step (3) as a precursor, carrying out heat treatment in a tube furnace protected by argon atmosphere, and obtaining the nickel-tin alloy based composite material with the nanosphere structure after the heat treatment;
the nickel-tin alloy-based nanosphere structure composite material is nanospheres with the particle size of 300-500 nm, the nanospheres are formed by self-assembling partial graphene-based carbon matrix and nickel-tin alloy-based nanoparticles embedded in the carbon matrix, the particle size of the nickel-tin alloy-based nanoparticles is 10-60 nm, and partial graphite-tin alloy-based nanoparticles are embedded in the carbon matrixThe graphene-based carbon matrix has 3-6 graphene layers at the interface of the nickel-tin alloy-based nano particles and carbon, and the nickel-tin alloy-based nano particles are uniformly dispersed in the partial graphene-based carbon matrix; wherein the nickel-tin alloy is Ni3Sn4。
2. The method for preparing the nickel-tin alloy-based nanosphere structure composite material according to claim 1, wherein in the step (1), the molar ratio of the nickel salt to the tin salt is as follows: the ratio of nickel salt to tin salt is = 2: 1-1: 2, and the ratio of polyvinylpyrrolidone to total transition metal salt in the step (1) is as follows: polyvinylpyrrolidone: total transition metal salts =1 g: 0.9mmol, total transition metal salt is the sum of nickel and tin salts.
3. The method for preparing the nickel-tin alloy-based nanosphere structure composite material according to claim 1, wherein the nickel salt is one of nickel nitrate, nickel chloride, nickel sulfate and nickel acetate.
4. The method for preparing the nickel-tin alloy-based nanosphere structure composite material according to claim 1, wherein the tin salt is one of stannous chloride and stannous sulfate.
5. The method for preparing the nickel-tin alloy-based nanosphere structure composite material according to claim 1, wherein the volume ratio of the glycerol to the isopropanol in the mixed solvent is as follows: isopropanol = 1: 5.
6. The method for preparing a nickel-tin alloy-based nanosphere structure composite material according to claim 1, wherein the polyvinylpyrrolidone: mixed solvent = 1-1.5 g: 48 mL.
7. The method for preparing the nickel-tin alloy-based nanosphere structure composite material according to claim 1, wherein the temperature of the solvothermal reaction in the step (3) is 150-200 ℃, and the reaction time is 4-8 h.
8. The method for preparing a nickel-tin alloy-based nanosphere structure composite material according to claim 1, wherein the heat treatment conditions in step (4) are as follows: under the protection of argon atmosphere, firstly heating to 250 ℃ at a heating rate of 1-5 ℃/min, carrying out heat treatment at the heat treatment temperature for 1-2 h, then heating to 450 ℃ at a heating rate of 1-5 ℃/min, and carrying out heat treatment at the heat treatment temperature for 2-4 h.
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