CN112436117A - Sn-P-CNT composite material - Google Patents

Sn-P-CNT composite material Download PDF

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CN112436117A
CN112436117A CN202011316905.1A CN202011316905A CN112436117A CN 112436117 A CN112436117 A CN 112436117A CN 202011316905 A CN202011316905 A CN 202011316905A CN 112436117 A CN112436117 A CN 112436117A
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composite material
red phosphorus
cnt composite
carrying
lithium ion
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CN112436117B (en
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孙黎
司浩臣
李泽琼
张元星
张以河
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China University of Geosciences Beijing
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China University of Geosciences Beijing
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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
    • H01M4/366—Composites as layered products
    • 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
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—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
    • H01M4/62—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
    • 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 composite materials, particularly relates to a Sn-P-CNT composite material, and further discloses application of the composite material in preparation of a lithium ion battery cathode material. According to the Sn-P-CNT composite material, the carbon nano tubes are uniformly wound on the surface of the massive red phosphorus loaded with the tin nano crystals to form a coating structure, so that the problem that the volume expansion of the red phosphorus and the metal tin is large in the charging and discharging process when the red phosphorus and the metal tin are used as the negative electrode material of the lithium ion battery in the prior art is effectively solved. The Sn-P-CNT composite material disclosed by the invention is used as a lithium ion battery negative electrode material, so that the specific capacity and the cyclic charge and discharge stability of the lithium ion battery negative electrode material can be obviously improved. The preparation method of the Sn-P-CNT composite material is simple and easy to implement, clean and environment-friendly, has the advantages of easily controlled reaction process and stable performance of reaction products, and is suitable for industrial popularization.

Description

Sn-P-CNT composite material
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a Sn-P-CNT composite material with a carbon nano tube uniformly wound on the surface of massive red phosphorus loaded with tin nano crystals, and further discloses application of the composite material in preparing a lithium ion battery cathode material.
Background
Energy is an important foundation stone for operation and development of human society, and an efficient energy storage system is a core pillar of modern sustainable renewable energy industry, consumer electronics industry and traffic industry. Compared with the traditional storage battery, the lithium ion battery has the advantages of high open circuit voltage, long cycle life, high safety performance, low self-discharge rate, no memory effect, environmental friendliness and the like. Since the sony corporation invented a commercial lithium ion battery in 1991, the lithium ion battery has been dominant in the portable electronic device market, and has become the mainstream product of mobile power sources. At present, lithium ion batteries have been widely used in the fields of mobile communication, portable laptop computers, video cameras, portable instruments and meters, and the like. However, through the development of decades, the performance of the positive and negative electrode materials of practical lithium ion batteries is close to the theoretical limit, but it is still difficult to meet the increasingly high requirements of the energy storage system in the current society. Therefore, the search for new high capacity density electrode materials becomes the key to increasing energy density of lithium ion batteries.
As a known negative electrode material, metallic tin is also prone to generate huge volume expansion during the insertion and extraction of lithium ions, and is prone to cause pulverization and agglomeration of the electrode material, so that the service life and capacity of the lithium ion battery are rapidly reduced. The current common method is to compound tin with other substances to fully exert the advantages of high volume specific capacity and high quality specific capacity of the tin, so as to obtain the lithium ion battery cathode material with higher performance.
In addition, among a plurality of known negative electrode materials, red phosphorus is purplish red or slightly brown amorphous powder, has the advantages of luster, high specific capacity (2596mAh/g), low cost, good environmental compatibility and the like, and becomes a material which is concerned in a plurality of electrode materials. At present, red phosphorus as a lithium ion battery cathode material mainly has the problem that the volume expansion of the red phosphorus is large (up to 490%) in the whole charging and discharging process, so that the red phosphorus is generally required to be compounded with other materials mainly comprising carbon materials, so that the volume expansion effect of the red phosphorus is limited.
Among the known carbon materials, the carbon nanotubes can form a three-dimensional bound network structure, can be used for winding and crosslinking red phosphorus and tin together, and can be used for effectively binding and limiting the volume expansion of the red phosphorus and the tin, and simultaneously improving the electrical conductivity and the surface chemical activity of the whole material, so that the tin-red phosphorus modified composite material with higher stability is obtained.
At present, the process of compounding red phosphorus with other materials is mainly divided into two types: one is that red phosphorus and other materials are mechanically mixed by a ball milling process, however, the carbon nano tube is easy to break in the ball milling process to cause fragmentation, so that the red phosphorus cannot be effectively bound; secondly, red phosphorus is sublimated at the temperature higher than 300 ℃ through high-temperature treatment, and phosphorus vapor is uniformly deposited in pores of other materials, but the method has the defects that white phosphorus formed in the process of cooling the phosphorus is flammable and has certain danger, and carbon disulfide and other toxic substances are needed for removing the white phosphorus, so that the potential safety hazard is large. Moreover, some methods for compounding red phosphorus and other materials often have strict requirements on reaction conditions such as high temperature and high pressure, long reaction time, atmosphere protection and the like, and the reaction process is too complicated and has certain dangers.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide a Sn-P-CNT composite material, wherein the composite material effectively solves the problem that red phosphorus and metallic tin expand greatly in volume in the charging and discharging process when being used as a lithium ion battery cathode material in the prior art by uniformly winding carbon nanotubes on the surface of massive red phosphorus loaded with tin nanocrystals, and can remarkably improve the specific capacity and the cycling charging and discharging stability of the lithium ion battery cathode material;
the second technical problem to be solved by the invention is to provide a preparation method of the Sn-P-CNT composite material, which is simple and feasible and has low cost;
the third technical problem to be solved by the invention is to provide the use of the Sn-P-CNT composite material for preparing the negative electrode material of the lithium ion battery.
In order to solve the above technical problems, the present invention provides a method for preparing a Sn-P-CNT composite material, comprising the steps of:
(1) dispersing red phosphorus in an aqueous solution for cell crushing, carrying out solid-liquid separation on reactants, washing, and carrying out freeze drying to obtain red phosphorus powder for later use;
(2) dispersing the red phosphorus powder and the carbon nano tube in SnCl-containing solution4·5H2O, then carrying out cell crushing on the mixture;
(3) taking NaBH4Dissolving in an alcohol solvent, and dropwise adding into the mixture prepared in the step (2), uniformly mixing, and carrying out a composite reaction;
(4) and carrying out suction filtration and washing on the reactant, and then carrying out freeze drying treatment to obtain the required Sn-P-CNT composite material.
In the preparation method of the Sn-P-CNT composite material, in the step (1):
the aqueous solution comprises deionized water or an aqueous alcohol solution; the aqueous alcohol solution comprises a methanol solution and/or an ethanol solution;
controlling the volume content of deionized water in the aqueous alcohol solution to be 20% -100%;
controlling the dispersion concentration of the red phosphorus in the aqueous solvent to be 0.5-5 mg/mL.
Preferably, in the step (1), before the cell pulverization step, a step of adding the red phosphorus to the aqueous solution and grinding the red phosphorus is further included.
In the step (1), the washing step is washing with deionized water several times.
The preparation method of the Sn-P-CNT composite material comprises the following steps (2):
the alcohol solvent comprises an ethanol solvent and/or a methanol solvent;
controlling the dispersion concentration of the carbon nano tube in the alcohol solvent to be 0.2-1 mg/mL;
controlling the dispersion concentration of the red phosphorus powder in the alcohol solvent to be 0.5-5 mg/mL;
controlling the SnCl4·5H2The concentration of O in the alcohol solvent is 1-10 mg/mL;
controlling the red phosphorus powder and SnCl4·5H2The mass ratio of tin in O is 1: 4-4: 1.
the preparation method of the Sn-P-CNT composite material comprises the following steps (3):
the alcohol solvent comprises an ethanol solvent and/or a methanol solvent;
controlling the NaBH4The dispersion concentration in the alcohol solvent is 1-10 mg/mL.
In the step (3), a step of performing ultrasonic treatment in the composite reaction process is further included. Specifically, the power of ultrasonic treatment is controlled to be 100-300W, and the ultrasonic treatment time is 10-120 min.
In the step (3), the mixing step further comprises magnetic stirring for 10-120 min.
In the step (1) and the step (2), the power of the cell crushing step is 5-50W, and the time of the cell crushing step is 30-120 min.
In the step (1) and/or (4), the freeze drying step is vacuum freeze drying at-50 to-80 ℃; optionally freezing the resultant reaction product at-80 ℃ prior to said freeze-drying step.
In the step (1) and/or (4), the time of the freeze drying step is controlled to be 12-48 h.
In the step (4), the washing step specifically comprises washing with ethanol for 3 times, and then washing with deionized water for 3-5 times.
The invention also discloses the Sn-P-CNT composite material prepared by the method. In the Sn-P-CNT composite material, tin nanocrystals are uniformly loaded on an amorphous red phosphorus block, and the surface of the Sn-P composite material is further wound and encircled by carbon nanotubes to form a coating structure.
The invention also discloses the use of the Sn-P-CNT composite material in the preparation of a lithium ion battery cathode material, a lithium ion battery cathode and a lithium ion battery.
The invention also discloses a lithium ion battery cathode prepared by taking the Sn-P-CNT composite material as a cathode material and a lithium ion battery.
According to the Sn-P-CNT composite material, the carbon nano tubes are uniformly wound on the surface of the massive red phosphorus loaded with the tin nano crystals to form a coating structure, so that the problem that the volume expansion of the red phosphorus and the metal tin is large in the charging and discharging process when the red phosphorus and the metal tin are used as the negative electrode material of the lithium ion battery in the prior art is effectively solved. The Sn-P-CNT composite material disclosed by the invention is used as a lithium ion battery negative electrode material, so that the specific capacity and the cyclic charge and discharge stability of the lithium ion battery negative electrode material can be obviously improved. The preparation method of the Sn-P-CNT composite material is simple and easy to implement, clean and environment-friendly, has the advantages of easily controlled reaction process and stable performance of reaction products, and is suitable for industrial popularization.
Drawings
In order that the present disclosure may be more readily and clearly understood, the following detailed description of the present disclosure is provided in connection with specific embodiments thereof and the accompanying drawings, in which,
FIG. 1 is a low-magnification SEM image of an intermediate Sn-P prepared in example 1 of the present invention;
FIG. 2 is a high power SEM photograph of intermediate Sn-P prepared in example 1 of the present invention;
FIG. 3 is an XRD plot of a Sn-P-CNT composite prepared in example 1 of the present invention;
FIG. 4 is a low-magnification SEM image of a Sn-P-CNT composite material prepared in example 1 of the present invention;
FIG. 5 is a high power SEM image of a Sn-P-CNT composite material prepared in example 1 of the present invention;
FIG. 6 is a TEM image of a Sn-P-CNT composite prepared in example 1 of the present invention;
FIG. 7 is a graph showing the charge and discharge cycle characteristics of a lithium ion battery using the Sn-P-CNT composite material of example 1 as a composite electrode and a conventional red phosphorus electrode.
Detailed Description
Example 1
The Sn-P-CNT composite material described in this example was prepared as follows:
(1) adding 250mg of commercial red phosphorus block into 2mL of deionized water, fully grinding in a mortar, further dispersing the obtained product in 50mL of deionized water, carrying out cell crushing under the power of 5W, centrifuging the obtained product, washing with deionized water for several times, freezing at-80 ℃, and then transferring to a freeze dryer for freeze drying at-50 ℃ for 48 hours to obtain red phosphorus powder;
(2) 49.3mg of SnCl4·5H2Dissolving O in 40mL ethanol, mixing, weighing 60mg red phosphorus powder and 18.75mg carbon nanotube, and adding into the SnCl-containing solution4·5H2O in ethanol solution, and crushing the mixed solution cells for 0.5h to obtain an intermediate Sn-P; the low-magnification SEM image and the high-magnification SEM image of the intermediate Sn-P are respectively shown in attached figures 1-2;
(3) 50mg of NaBH4Dissolving in 10mL of ethanol, uniformly mixing, quickly dripping into the mixed solution prepared in the step (2), stirring for 10min by strong magnetic force at room temperature, and performing ultrasonic treatment for 15min at the power of 100W to perform composite reaction;
(4) and (3) carrying out suction filtration on the reacted mixed solution, washing the product with ethanol for 3 times, washing with deionized water for 3-5 times, and carrying out freeze drying at-50 ℃ to obtain the required Sn-P-CNT composite material.
The XRD curve diagram, the low-power SEM image, the high-power SEM image and the TEM image of the Sn-P-CNT composite material are respectively shown in attached figures 3-6.
And (3) preparing a composite electrode by using the Sn-P-CNT composite material according to a conventional method to serve as a lithium ion battery electrode, assembling a button type half battery by using simple substance lithium as the other electrode, measuring the charge-discharge cycle performance of the prepared lithium ion battery as shown in figure 7, and simultaneously performing performance comparison by using red phosphorus as a negative electrode material.
Example 2
The Sn-P-CNT composite material described in this example was prepared as follows:
(1) adding 150mg of commercial red phosphorus block into 2mL of deionized water, fully grinding in a mortar, further dispersing the obtained product in 50mL of deionized water, carrying out cell crushing under the power of 10W, centrifuging the obtained product, washing with deionized water for several times, freezing at-80 ℃, and then transferring to a freeze dryer for freeze drying at-50 ℃ for 48 hours to obtain red phosphorus powder;
(2) 93.61mg of SnCl4·5H2Dissolving O in 40mL ethanol, mixing, weighing 45mg red phosphorus powder and 18.75mg carbon nanotube, and adding into the SnCl-containing solution4·5H2O in ethanol solution, and crushing the cells of the mixed solution for 0.5 h;
(3) 50mg of NaBH4Dissolving in 10mL of ethanol, uniformly mixing, quickly dripping into the mixed solution prepared in the step (2), stirring for 10min by strong magnetic force at room temperature, and performing ultrasonic treatment for 15min at the power of 150W to perform composite reaction;
(4) and (3) carrying out suction filtration on the reacted mixed solution, washing the product with ethanol for 3 times, washing with deionized water for 3-5 times, and carrying out freeze drying at-50 ℃ to obtain the required Sn-P-CNT composite material.
Example 3
The Sn-P-CNT composite material described in this example was prepared as follows:
(1) fully grinding a commercial red phosphorus block 100mg in a mortar by adding 2mL of deionized water, further dispersing the obtained product in 50mL of deionized water, carrying out cell crushing under the power of 20W, centrifuging the obtained product, washing the product with deionized water for several times, freezing the product at the temperature of minus 80 ℃, and then transferring the product to a freeze dryer for freeze drying for 24 hours at the temperature of minus 80 ℃ to obtain red phosphorus powder;
(2) 137.92mg ofSnCl4·5H2Dissolving O in 40mL ethanol, mixing, weighing 30mg red phosphorus powder and 18.75mg carbon nanotube, and adding into the SnCl-containing solution4·5H2O in ethanol solution, and crushing the cells of the mixed solution for 0.5 h;
(3) mixing 68mg of NaBH4Dissolving in 10mL of ethanol, uniformly mixing, quickly dripping into the mixed solution prepared in the step (2), stirring for 10min by strong magnetic force at room temperature, and performing ultrasonic treatment for 15min at 200W for composite reaction;
(4) and (3) carrying out suction filtration on the reacted mixed solution, washing the product with ethanol for 3 times, washing with deionized water for 3-5 times, and carrying out freeze drying at-80 ℃ to obtain the required Sn-P-CNT composite material.
Example 4
The Sn-P-CNT composite material described in this example was prepared as follows:
(1) adding 2mL of deionized water into 25mg of a commercial red phosphorus block, fully grinding the commercial red phosphorus block in a mortar, further dispersing the obtained product in 50mL of deionized water, carrying out cell crushing under the power of 30W, centrifuging the obtained product, washing the product with deionized water for several times, freezing the product at the temperature of minus 80 ℃, and then transferring the product to a freeze dryer for freeze drying for 48 hours at the temperature of minus 50 ℃ to obtain red phosphorus powder;
(2) 182.22mg of SnCl4·5H2Dissolving O in 40mL ethanol, mixing, weighing 15mg red phosphorus powder and 18.75mg carbon nanotube, and adding into the SnCl-containing solution4·5H2O in ethanol solution, and crushing the cells of the mixed solution for 0.5 h;
(3) 90mg of NaBH4Dissolving in 10mL of ethanol, uniformly mixing, quickly dripping into the mixed solution prepared in the step (2), stirring for 10min by strong magnetic force at room temperature, and performing ultrasonic treatment for 15min at the power of 250W to perform composite reaction;
(4) and (3) carrying out suction filtration on the reacted mixed solution, washing the product with ethanol for 3 times, washing with deionized water for 3-5 times, and carrying out freeze drying at-50 ℃ to obtain the required Sn-P-CNT composite material.
Example 5
The Sn-P-CNT composite material described in this example was prepared as follows:
(1) fully grinding a commercial red phosphorus block 100mg in a mortar by adding 2mL of deionized water, further dispersing the obtained product in 50mL of deionized water, carrying out cell crushing under the power of 40W, centrifuging the obtained product, washing the product with deionized water for several times, freezing the product at the temperature of minus 80 ℃, and then transferring the product to a freeze dryer for freeze drying for 12 hours at the temperature of minus 70 ℃ to obtain red phosphorus powder;
(2) adding 100mg of SnCl4·5H2Dissolving O in 100mL ethanol, mixing, weighing 50mg red phosphorus powder and 20mg carbon nanotube, and adding into the SnCl-containing solution4·5H2O in ethanol solution, and crushing the mixed solution cells for 0.5h to obtain an intermediate Sn-P;
(3) 25mg of NaBH4Dissolving in 25mL of ethanol, uniformly mixing, quickly dripping into the mixed solution prepared in the step (2), stirring for 10min by strong magnetic force at room temperature, and performing ultrasonic treatment for 15min at the power of 300W to perform composite reaction;
(4) and (3) carrying out suction filtration on the reacted mixed solution, washing the product with ethanol for 3 times, washing with deionized water for 3-5 times, and carrying out freeze drying at-70 ℃ to obtain the required Sn-P-CNT composite material.
Example 6
The Sn-P-CNT composite material described in this example was prepared as follows:
(1) fully grinding a commercial red phosphorus block 100mg in a mortar by adding 2mL of deionized water, further dispersing the obtained product in 50mL of deionized water, carrying out cell crushing under the power of 50W, centrifuging the obtained product, washing the product with deionized water for several times, freezing the product at the temperature of minus 80 ℃, and then transferring the product to a freeze dryer for freeze drying for 12 hours at the temperature of minus 50 ℃ to obtain red phosphorus powder;
(2) 1000mg of SnCl4·5H2Dissolving O in 100mL ethanol, mixing, weighing 500mg red phosphorus powder and 100mg carbon nanotube, and adding into the SnCl-containing solution4·5H2O in ethanol solution, and crushing the mixed solution cells for 0.5h to obtain an intermediate Sn-P；
(3) 250mg of NaBH4Dissolving in 25mL of ethanol, uniformly mixing, quickly dripping into the mixed solution prepared in the step (2), stirring for 10min by strong magnetic force at room temperature, and performing ultrasonic treatment for 15min at the power of 300W to perform composite reaction;
(4) and (3) carrying out suction filtration on the reacted mixed solution, washing the product with ethanol for 3 times, washing with deionized water for 3-5 times, and carrying out freeze drying at-50 ℃ to obtain the required Sn-P-CNT composite material.
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 therefrom are within the scope of the invention.

Claims (8)

1. The Sn-P-CNT composite material is characterized in that tin nanocrystals are uniformly loaded on an amorphous red phosphorus block, and the surface of the Sn-P composite material is further wound and encaged by carbon nanotubes to form a coating structure;
the preparation method of the composite material comprises the following steps:
(1) dispersing red phosphorus in an aqueous solution for cell crushing, carrying out solid-liquid separation on reactants, washing, and carrying out freeze drying to obtain red phosphorus powder for later use;
(2) dispersing the red phosphorus powder and the carbon nano tube in SnCl-containing solution4·5H2O, then carrying out cell crushing on the mixture;
(3) taking NaBH4Dissolving in an alcohol solvent, and dropwise adding into the mixture prepared in the step (2), uniformly mixing, and carrying out a composite reaction;
(4) and carrying out suction filtration and washing on the reactant, and then carrying out freeze drying treatment to obtain the required Sn-P-CNT composite material.
2. The Sn-P-CNT composite of claim 1, wherein in step (1):
the aqueous solution comprises deionized water or an aqueous alcohol solution;
controlling the volume content of deionized water in the aqueous alcohol solution to be 20% -100%;
controlling the dispersion concentration of the red phosphorus in the aqueous solution to be 0.5-5 mg/mL.
3. The Sn-P-CNT composite material of claim 1 or 2, further comprising a step of adding the red phosphorus to the aqueous solution for grinding before the cell pulverization step in the step (1).
4. The Sn-P-CNT composite of claim 3, wherein in step (2):
the alcohol solvent comprises an ethanol solution and/or a methanol solution;
controlling the dispersion concentration of the carbon nano tube in the alcohol solvent to be 0.2-1 mg/mL;
controlling the dispersion concentration of the red phosphorus powder in the alcohol solvent to be 0.5-5 mg/mL;
controlling the SnCl4·5H2The concentration of O in the alcohol solvent is 1-10 mg/mL;
controlling the red phosphorus powder and SnCl4·5H2The mass ratio of tin in O is 1: 4-4: 1.
5. the Sn-P-CNT composite of claim 4, wherein in step (3):
the alcohol solvent comprises an ethanol solvent and/or a methanol solvent;
controlling the NaBH4The dispersion concentration in the alcohol solvent is 1-10 mg/mL.
6. The Sn-P-CNT composite material of claim 5, wherein the step (3) further comprises a step of performing ultrasonic treatment during the composite reaction, and the power of the ultrasonic treatment is controlled to be 300W and 100W.
7. The Sn-P-CNT composite of claim 6, wherein in step (1) and/or (2), the cell pulverization step has a power of 5 to 50W.
8. The Sn-P-CNT composite material of claim 7, wherein in the steps (1) and/or (4), the freeze-drying step is vacuum freeze-drying at-50 to-80 ℃; optionally freezing the resultant reaction product at-80 ℃ prior to said freeze-drying step.
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