CN112563468A - Lithium ion battery cathode nanofiber composite material and preparation method and application thereof - Google Patents

Lithium ion battery cathode nanofiber composite material and preparation method and application thereof Download PDF

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CN112563468A
CN112563468A CN202011324288.XA CN202011324288A CN112563468A CN 112563468 A CN112563468 A CN 112563468A CN 202011324288 A CN202011324288 A CN 202011324288A CN 112563468 A CN112563468 A CN 112563468A
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solution
lithium ion
precursor
nanofiber
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CN112563468B (en
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韩文杰
秦显营
罗丹
李宝华
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Shenzhen Graphene Innovation Center Co ltd
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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
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/626—Metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a lithium ion battery cathode nanofiber composite material and a preparation method and application thereof, wherein the method comprises the following steps: using a catalyst containing SnO2Preparing SnO (SnO) from second solution of/C nanosphere precursor and third solution containing nickel acetylacetonate through coaxial electrostatic spinning2a/C @ Ni nanofiber precursor; the SnO2SnO is obtained by oxidizing and carbonizing a/C @ Ni nanofiber precursor2a/C @ Ni nanofiber composite, namelyA negative electrode nano-fiber composite material of a lithium ion battery. SnO of the present invention2the/C @ Ni nanofiber composite material is used as a lithium ion battery cathode material, the conductivity and the structural stability are remarkably improved, and the composite material has good electrochemical stability and rate capability and commercial application value.

Description

Lithium ion battery cathode nanofiber composite material and preparation method and application thereof
Technical Field
The invention relates to the technical field of nano materials, in particular to a lithium ion battery cathode nanofiber composite material and a preparation method and application thereof.
Background
Tin dioxide (SnO)2) The lithium ion battery cathode material is considered to be the most promising material to replace the commercial graphite cathode material, becomes one of the materials of the next generation of novel lithium ion battery cathode material, and has the advantages of high theoretical specific capacity, wide environmental storage, environmental friendliness, no pollution, higher safety and the like. However, SnO2The inherent poor electron transport performance of the material, and the severe volume expansion and contraction during the charge and discharge process, which causes SnO2The phenomena of pulverization and secondary agglomeration are continuously generated in the charge and discharge processes of the material, so that the electrochemical activity is lost, and the performance is rapidly attenuated.
To solve SnO2In view of the above problems of the negative electrode material, many researches and attempts have been made to combine the negative electrode material with a carbon material to prepare a nano structure, a hollow or porous structure, etc., but the current manufacturing method has high preparation cost and is difficult to realize large-scale commercial production; in addition, in the prior art, the problems of poor electrochemical stability and rate capability of the prepared battery cathode material and the like are urgently needed to be further improved.
Disclosure of Invention
Therefore, the invention provides a lithium ion battery cathode nanofiber composite material and a preparation method and application thereof.
In order to achieve the above purpose, the invention provides the following technical scheme:
the embodiment of the invention provides a preparation method of a lithium ion battery cathode nanofiber composite material, which comprises the following steps: using a catalyst containing SnO2Preparing SnO (SnO) from second solution of/C nanosphere precursor and third solution containing nickel acetylacetonate through coaxial electrostatic spinning2a/C @ Ni nanofiber precursor;
the SnO2Oxidizing a/C @ Ni nanofiber precursorAnd carbonizing to obtain SnO2the/C @ Ni nano-fiber composite material is the lithium ion battery negative electrode nano-fiber composite material.
In one embodiment of the invention, the SnO2The preparation method of the/C nanosphere precursor comprises the following steps:
adding potassium stannate into water, stirring and carrying out ultrasonic treatment until the potassium stannate is completely dissolved to obtain a potassium stannate solution, adding glucose, continuously stirring until the potassium stannate is completely dissolved to obtain a first solution, adding the first solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in an explosion-proof oven at 180 ℃, reacting for 4 hours, washing, centrifuging and drying a reaction product to obtain the SnO2a/C nanosphere precursor.
Wherein, in the first solution, the mass fraction of the potassium stannate is 1-10%, and the mass ratio of the glucose to the potassium stannate is 0.5-10.
In an embodiment of the present invention, the second solution is prepared by:
adding Polyacrylonitrile (PAN) into N, N-Dimethylformamide (DMF), stirring at 80 deg.C for 30min to dissolve completely, adding the SnO2And stirring the/C nanosphere precursor for 30min to obtain the second solution.
In one embodiment of the invention, in the second solution, the mass fraction of polyacrylonitrile is 1% -30%, and the SnO is2The mass ratio of the/C nanosphere precursor to the polyacrylonitrile is 0.1-5.
In an embodiment of the present invention, the third solution is prepared by:
adding polyvinylpyrrolidone (PVP) into N, N-Dimethylformamide (DMF), stirring at 60 deg.C for 30min until PVP is completely dissolved, adding nickel acetylacetonate, and stirring for 30min to obtain a third solution;
wherein, in the third solution, the PVP accounts for 10-30% by mass; the mass ratio of the nickel acetylacetonate to the PVP is 0.01-5.
In one embodiment of the present invention, the coaxial electrospinning conditions are:
the inner layer is filled with the second solution, the outer layer is filled with the third solution, and the voltage is5-50kV, and the receiving speed of the roller is 0-100r min-1Push-injection pushing speed of 0.1-10mL h-1The distance between the electrospinning needle head and the receiver is 5-30cm, and the electrospinning time is 1-100 h.
In one embodiment of the present invention, the oxidation treatment process is:
the SnO2The precursor of the/C @ Ni nano-fiber is put in the air at the temperature of 1-10 ℃ for min-1The temperature rising speed is gradually increased to 150-300 ℃, and the temperature is kept for 0.5-3 h.
In one embodiment of the present invention, the carbonization process is:
oxidizing the treated SnO2Putting the/C @ Ni nanofiber precursor in an inert gas atmosphere at the temperature of 1-20 ℃ for min-1The temperature rising speed is gradually raised to 500-1000 ℃, and the temperature is kept for 0.5-5 h.
The lithium ion battery cathode nanofiber composite material prepared by the method also belongs to the protection scope of the invention.
The invention also provides the application of the lithium ion battery cathode nanofiber composite material in any one of the following processes, (1) preparing a battery or a battery electrode material; (2) preparing an energy storage element; (3) an electronic device is prepared.
SnO of embodiments of the invention2SnO in/C @ Ni nano-fiber composite material2the/C nanospheres are uniformly dispersed in the carbon fibers, a large number of Ni nanoparticles are dispersed on the surfaces of the fibers, the composite material fibers are mutually crosslinked to form a stable carbon skeleton matrix, a good multi-point contact network is formed, the graphitization degree of the carbon matrix is further improved due to the addition of the Ni nanoparticles, and meanwhile, the Ni also has good conductivity and provides a quick channel for electron transmission, and SnO (SnO) is a metal oxide semiconductor material2The gaps among the/C nanospheres are SnO2The volume expansion in the charging and discharging process provides space, and the carbon fiber coated on the surface is SnO2The volume expansion of the composite material provides buffer, and the integral stability of the composite material is ensured.
The invention has the following advantages:
SnO of the present invention2The preparation method of the/C @ Ni nano-fiber composite material is simple, the repeatability is high, and the SnO2the/C @ Ni nano-fiber composite material is prepared from SnO with the diameter of about 50nm2SnO self-assembled by primary nanoparticles of C and C2the/C nanospheres are uniformly dispersed in the carbon nanofibers, and the carbon nanofiber network provides good conductive network and skeleton support for the composite material and is SnO2The volume expansion of the material in the charge and discharge process provides buffer, the addition of the surface layer nano Ni particles further improves the graphitization degree of the carbon fiber, and the good conductivity of Ni obviously improves the conductivity of the composite material matrix.
SnO of the present invention2the/C @ Ni nano-fiber composite material as a lithium ion battery cathode material has excellent electrochemical performance, good electrochemical stability and rate capability and high commercial application value.
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. It should be apparent that the drawings in the following description are merely exemplary, and that other embodiments can be derived from the drawings provided by those of ordinary skill in the art without inventive effort.
The structures, ratios, sizes, and the like shown in the present specification are only used for matching with the contents disclosed in the specification, so as to be understood and read by those skilled in the art, and are not used to limit the conditions that the present invention can be implemented, so that the present invention has no technical significance, and any structural modifications, changes in the ratio relationship, or adjustments of the sizes, without affecting the effects and the achievable by the present invention, should still fall within the range that the technical contents disclosed in the present invention can cover.
FIG. 1 shows the SnO prepared by hydrothermal method in the preparation method of the nano-fiber composite material of the invention2TEM photograph of/C nanosphere precursor, the SnO2SnO with/C nanosphere precursor nanosphere size of about 50nm2The secondary particles with the diameter of about 500nm are assembled by the/C primary particles;
FIG. 2 is SnO prepared by coaxial electrostatic spinning in an embodiment of the invention2/C @ Ni nanofiber precursor and carbonized SnO2SEM photograph of/C @ Ni nano-fiber composite material, wherein (a, b) is SnO2SEM picture of the/C @ Ni nanofiber precursor; (c, d) is SnO2SEM picture of/C @ Ni nanofiber composite.
Detailed Description
The present invention is described in terms of particular embodiments, other advantages and features of the invention will become apparent to those skilled in the art from the following disclosure, and it is to be understood that the described embodiments are merely exemplary of the invention and that it is not intended to limit the invention to the particular embodiments disclosed. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Polyacrylonitrile (PAN) with the molecular weight of 150000 and polyvinylpyrrolidone (PVP) with the molecular weight of 1300000 are adopted in the embodiment of the invention, and other chemical agents are analytically pure agents and are not treated;
in the embodiment of the invention, the types of the adopted electrostatic spinning equipment are as follows: TL-Pro-BM.
Example 1 preparation of negative electrode nanofiber composite for lithium ion batteries
The preparation method of the lithium ion battery cathode nanofiber composite material provided by the embodiment comprises the following steps:
step one, preparation of a first solution
3.5g of potassium stannate (K)2[Sn(OH)6]) Adding into 80ml water, ultrasonic treating, stirring to dissolve potassium stannate completely, adding 6g glucose into the potassium stannate solution, and stirring until glucose is dissolved completely to obtain a first solution.
Step two, SnO2Preparation of/C nanosphere precursor
Adding the first solution into a hydrothermal synthesis reaction kettle with the capacity of 100mL, placing the hydrothermal synthesis reaction kettle in an explosion-proof hydrothermal oven at 180 ℃, preserving heat for 4 hours, cooling, cleaning, centrifuging and drying a reaction productPreparing to obtain SnO2a/C nanosphere precursor. As shown in FIG. 1, is SnO2TEM image of/C nanosphere precursor.
Step three, preparation of second solution
Adding 1.8g of polyacrylonitrile into 20ml of N, N-dimethylformamide, heating and stirring at 80 ℃ until the polyacrylonitrile is completely dissolved, and then adding 4g of SnO2And continuously stirring the/C nanosphere precursor to uniformly disperse the precursor to obtain a second solution.
Step four, preparation of third solution
Adding 3g of polyvinylpyrrolidone into 20ml of N, N-dimethylformamide, heating and stirring at 60 ℃ until the polyvinylpyrrolidone is completely dissolved, then adding 0.8g of nickel acetylacetonate into the polyvinylpyrrolidone solution, and continuously stirring to completely dissolve the acetylacetone to prepare a third solution.
Step five, coaxial electrostatic spinning
In this step, the types of the electrostatic spinning equipment adopted are: TL-Pro-BM. Wherein the inner solution of the coaxial electrostatic spinning is a second solution, the outer solution is a third solution, and the advancing speed of the inner solution is 1mL h-1The advancing speed of the external solution was 1.5mL h-1The electrospinning voltage is 20kV, and the receiving speed of the roller is 30 rpm-1The distance between the electrospinning needle head and the receiver is 18cm, the electrospinning time is 10h, and SnO is obtained2the/C @ Ni nanofiber precursor is shown in figure 2, wherein (a and b) are SnO2SEM picture of/C @ Ni nanofiber precursor.
Step six, SnO2Oxidation treatment of/C @ Ni nanofiber precursor
SnO prepared by coaxial electrostatic spinning2The oxidation treatment is carried out on the/C @ Ni nanofiber precursor, and the specific process is as follows:
SnO2Putting the/C @ Ni nanofiber precursor in air at 10 ℃ for min-1The temperature rising speed is gradually increased to 250 ℃, and the temperature is kept constant for 2 hours to obtain oxidized SnO2a/C @ Ni nanofiber precursor.
Step seven, oxidized SnO2Carbon as precursor of/C @ Ni nanofiberChemical treatment
For oxidized SnO2The carbonization treatment process of the/C @ Ni nanofiber precursor is as follows:
oxidizing SnO2Putting the/C @ Ni nanofiber precursor in inert gas at 5 ℃ for min-1The temperature is gradually increased to 600 ℃ at the temperature rising speed, and the temperature is kept for 3 hours to obtain SnO2The invention relates to a/C @ Ni nano-fiber composite material, in particular to a lithium ion battery cathode nano-fiber composite material.
SnO2the/C @ Ni nano-fiber composite material is assembled into a 2032 type button half cell in a glove box in a high-purity argon atmosphere. The half-cell is subjected to cycle performance test at room temperature, and the charge-discharge current density of the button half-cell is 0.1A g-1Circulating for 200 circles, wherein the charging and discharging voltage is 0.01-1.5V; at 2.0A g-1The multiplying power performance test is carried out under the high current density, and the charging and discharging voltage range is 0.01-1.5V.
SnO prepared in this example2the/C @ Ni nano-fiber composite material is used as a lithium ion battery negative electrode material for testing, and the test result is as follows: at 0.1A g-1The reversible specific capacity of the first loop is 874mAh g under the current density-1The coulombic efficiency is 66.2 percent, and the reversible specific capacity is 832mAh g after the circulation for 200 times-1The capacity retention rate was 95.1%, the rate capability was 2.0A g-1The reversible specific capacity is 348.5mAh g-1。
Example 2 preparation of negative electrode nanofiber composite for lithium ion batteries
The preparation method of the lithium ion battery cathode nanofiber composite material provided by the embodiment comprises the following steps:
step one, preparation of a first solution
3.5g of potassium stannate (K)2[Sn(OH)6]) Adding the mixture into 80ml of water, performing ultrasonic treatment and stirring to completely dissolve potassium stannate, then adding 6g of glucose into the potassium stannate solution, and stirring until the glucose is completely dissolved to prepare a first solution.
Step two, SnO2Preparation of/C nanosphere precursor
Adding the first solution into a containerPutting the hydrothermal reaction kettle in a hydrothermal reaction kettle with the volume of 100mL into an explosion-proof hydrothermal oven with the temperature of 180 ℃, preserving the heat for 4 hours, cooling, cleaning, centrifuging and drying a reaction product to obtain SnO2a/C nanosphere precursor.
Step three, preparation of second solution
Adding 1.8g of polyacrylonitrile into 20ml of N, N-dimethylformamide, heating and stirring at 80 ℃ until the polyacrylonitrile is completely dissolved, and then adding 4g of SnO2And continuously stirring the/C nanosphere precursor to uniformly disperse the precursor to prepare a second solution.
Step four, preparation of third solution
Adding 3.2g of polyvinylpyrrolidone into 20ml of N, N-dimethylformamide, heating and stirring at 60 ℃ until the polyvinylpyrrolidone is completely dissolved, then adding 0.05g of nickel acetylacetonate, and continuing stirring to completely dissolve the nickel acetylacetonate to prepare a third solution.
Step five, coaxial electrostatic spinning
In this step, the types of the electrostatic spinning equipment adopted are: TL-Pro-BM. The inner solution of the coaxial electrostatic spinning is a second solution, the outer solution is a third solution, wherein the advancing speed of the inner solution is 1mL h-1The advancing speed of the external solution was 1.5mL h-1The electrospinning voltage is 20kV, and the receiving speed of the roller is 30 rpm-1The distance between the electrospinning needle head and the receiver is 18cm, the electrospinning time is 10h, and SnO is obtained2a/C @ Ni nanofiber precursor.
Step six, SnO2Oxidation treatment of/C @ Ni nanofiber precursor
SnO prepared by coaxial electrostatic spinning2The oxidation treatment process of the/C @ Ni nanofiber precursor comprises the following steps:
SnO2Putting the/C @ Ni nanofiber precursor in air at 10 ℃ for min-1The temperature rising speed is gradually increased to 250 ℃, and the temperature is kept constant for 2 hours to obtain oxidized SnO2a/C @ Ni nanofiber precursor.
Step seven, SnO2Carbonization treatment of/C @ Ni nanofiber precursor
For S after oxidationnO2The carbonization treatment process of the/C @ Ni nanofiber precursor comprises the following steps:
oxidizing SnO2Putting the/C @ Ni nanofiber precursor in inert gas at 5 ℃ for min-1The temperature is gradually increased to 600 ℃ at the temperature rising speed, and the temperature is kept for 3 hours to obtain SnO2The invention relates to a/C @ Ni nano-fiber composite material, in particular to a lithium ion battery cathode nano-fiber composite material.
SnO prepared by Using this example2the/C @ Ni nano-fiber composite material is assembled into a 2032 type button half cell in a glove box in a high-purity argon atmosphere. The half-cell is subjected to cycle performance test at room temperature, and the charge-discharge current density is 0.1A g-1Circulating for 200 circles, wherein the charging and discharging voltage is 0.01-1.5V; at 2.0A g-1The multiplying power performance test is carried out under the high current density, and the charging and discharging voltage range is 0.01-1.5V.
SnO prepared in this example2the/C @ Ni nano-fiber composite material is used as a lithium ion battery negative electrode material for testing, and the test result is as follows: at 0.1A g-1The reversible specific capacity of the first loop is 885mAh g under the current density-1The coulombic efficiency is 67 percent, and the reversible specific capacity is 805mAh g after the circulation for 200 times-1The capacity retention rate was 91.0%, and the rate capability was 2.0A g-1The reversible specific capacity is 280mAh g-1。
Example 3 preparation of negative electrode nanofiber composite for lithium ion batteries
The preparation method of the lithium ion battery negative electrode nanofiber composite material provided by the embodiment comprises the following steps:
step one, preparation of a first solution
3.5g of potassium stannate (K)2[Sn(OH)6]) Adding into 80ml water, ultrasonic treating, stirring to dissolve potassium stannate completely, adding 6g glucose into the above solution, stirring until glucose is dissolved completely, and preparing to obtain first solution.
Step two, SnO2Preparation of/C nanosphere precursor
Adding the first solution with the volume of 100mL into a hydrothermal reaction kettle, and placing the hydrothermal reaction kettle at 180 ℃ in an explosion-proof hydrothermal mannerIn an oven, after heat preservation for 4 hours, cooling, cleaning, centrifuging and drying a reaction product to obtain SnO2a/C nanosphere precursor.
Step three, preparation of second solution
Adding 1.8g of polyacrylonitrile into 20ml of N, N-dimethylformamide, heating and stirring at 80 ℃ until the polyacrylonitrile is completely dissolved, and then adding 4g of SnO2And continuously stirring the/C nanosphere precursor to uniformly disperse the precursor to prepare a second solution.
Step four, preparation of third solution
Adding 3g of polyvinylpyrrolidone into 20ml of N, N-dimethylformamide, heating and stirring at 60 ℃ until the polyvinylpyrrolidone is completely dissolved, then adding 3g of nickel acetylacetonate, and continuously stirring to completely dissolve the nickel acetylacetonate to prepare a third solution.
Step five, coaxial electrostatic spinning
In this step, the types of the electrostatic spinning equipment adopted are: TL-Pro-BM. The inner solution of the coaxial electrostatic spinning is a second solution, the outer solution is a third solution, wherein the advancing speed of the inner solution is 0.1mL h-1The advancing speed of the external solution was 0.15mL h-1The electrospinning voltage is 20kV, and the receiving speed of the roller is 30 rpm-1The distance between the electrospinning needle head and the receiver is 18cm, the electrospinning time is 10h, and SnO is obtained2a/C @ Ni nanofiber precursor.
Step six, SnO2Oxidation treatment of/C @ Ni nanofiber precursor
SnO prepared by coaxial electrostatic spinning2The oxidation treatment process of the/C @ Ni nanofiber precursor comprises the following steps:
SnO2putting the/C @ Ni nanofiber precursor in air at 10 ℃ for min-1The temperature rising speed is gradually increased to 250 ℃, and the temperature is kept constant for 2 hours to obtain oxidized SnO2a/C @ Ni nanofiber precursor.
Step seven, oxidized SnO2Carbonization treatment of/C @ Ni nanofiber precursor
For oxidized SnO2The carbonization treatment process of the/C @ Ni nanofiber precursor comprises the following steps:
oxidizing SnO2The precursor of the/C @ Ni nano-fiber is put in inert gas at 5 ℃ for min-1The temperature is gradually increased to 600 ℃ at the temperature rising speed, and the temperature is kept for 3 hours to obtain SnO2The invention relates to a/C @ Ni nano-fiber composite material, in particular to a lithium ion battery cathode nano-fiber composite material.
The prepared SnO2the/C @ Ni nano-fiber composite material is assembled into a 2032 type button half cell in a glove box in a high-purity argon atmosphere. The half-cell is subjected to cycle performance test at room temperature, and the charge-discharge current density is 0.1A g-1Circulating for 200 circles, wherein the charging and discharging voltage is 0.01-1.5V; at 2.0A g-1The multiplying power performance test is carried out under the high current density, and the charging and discharging voltage range is 0.01-1.5V.
SnO prepared by the invention2the/C @ Ni nano-fiber composite material is used as a lithium ion battery negative electrode material for testing, and the test result is as follows: at 0.1A g-1The reversible specific capacity of the first loop is 725mAh g under the current density-1The coulombic efficiency is 69 percent, and the reversible specific capacity after 200 times of circulation is 696mAh g-1The capacity retention rate was 96%, and the rate capability was 2.0A g-1The reversible specific capacity is 294mAh g-1。
Example 4 preparation of negative electrode nanofiber composite for lithium ion batteries
The preparation method of the lithium ion battery cathode nanofiber composite material provided by the embodiment of the invention comprises the following steps:
step one, preparation of a first solution
3.5g of potassium stannate (K)2[Sn(OH)6]) Adding into 80ml water, ultrasonic treating, stirring to dissolve potassium stannate completely, adding 6g glucose into the above solution, and stirring until glucose is dissolved completely to obtain first solution.
Step two, SnO2Preparation of/C nanosphere precursor
Adding the first solution into a hydrothermal reaction kettle with the capacity of 100mL, placing the hydrothermal reaction kettle in an explosion-proof hydrothermal oven at 180 ℃, preserving heat for 4 hours, cooling, cleaning, centrifuging and drying a reaction product to obtain SnO2a/C nanosphere precursor.
Step three, preparation of second solution
Adding 1.8g of polyacrylonitrile into 20ml of N, N-dimethylformamide, heating and stirring at 80 ℃ until the polyacrylonitrile is completely dissolved, and then adding 2g of SnO2And continuously stirring the/C nanosphere precursor to uniformly disperse the precursor to obtain a second solution.
Step four, preparation of third solution
Adding 3g of polyvinylpyrrolidone into 20ml of N, N-dimethylformamide, heating and stirring at 60 ℃ until the polyvinylpyrrolidone is completely dissolved, then adding 0.8g of nickel acetylacetonate, and continuing stirring to completely dissolve the nickel acetylacetonate to obtain a third solution.
Step five, coaxial electrostatic spinning
In this step, the types of the electrostatic spinning equipment adopted are: TL-Pro-BM. The inner solution of the coaxial electrostatic spinning is a second solution, the outer solution is a third solution, wherein the advancing speed of the inner solution is 1mL h-1The advancing speed of the external solution was 1.5mL h-1The electrospinning voltage is 20kV, and the receiving speed of the roller is 30 rpm-1The distance between the electrospinning needle head and the receiver is 18cm, the electrospinning time is 10h, and SnO is obtained2a/C @ Ni nanofiber precursor.
Step six, SnO2Oxidation treatment of/C @ Ni nanofiber precursor
SnO prepared by coaxial electrostatic spinning2The oxidation treatment process of the/C @ Ni nanofiber precursor comprises the following steps:
SnO2Putting the/C @ Ni nanofiber precursor in air at 10 ℃ for min-1The temperature rising speed is gradually increased to 250 ℃, and the temperature is kept constant for 2 hours to obtain oxidized SnO2a/C @ Ni nanofiber precursor.
Step seven, oxidized SnO2Carbonization treatment of/C @ Ni nanofiber precursor
For oxidized SnO2The carbonization treatment process of the/C @ Ni nanofiber precursor comprises the following steps:
oxidizing SnO2Putting the/C @ Ni nanofiber precursor into inert gasAt 5 ℃ for min-1The temperature is gradually increased to 600 ℃ at the temperature rising speed, and the temperature is kept for 3 hours to obtain SnO2The invention relates to a/C @ Ni nano-fiber composite material, in particular to a lithium ion battery cathode nano-fiber composite material.
The prepared SnO2the/C @ Ni nano-fiber composite material is assembled into a 2032 type button half cell in a glove box in a high-purity argon atmosphere. The half-cell is subjected to cycle performance test at room temperature, and the charge-discharge current density is 0.1A g-1Circulating for 200 circles, wherein the charging and discharging voltage is 0.01-1.5V; at 2.0A g-1The multiplying power performance test is carried out under the high current density, and the charging and discharging voltage range is 0.01-1.5V.
SnO prepared by the invention2the/C @ Ni nano-fiber composite material is used as a lithium ion battery negative electrode material for testing, and the test result is as follows: at 0.1A g-1The reversible specific capacity of the first loop is 496mAh g under the current density-1The coulombic efficiency is 72 percent, and the reversible specific capacity after 200 times of circulation is 481mAh g-1The capacity retention rate is 97%, and the rate capability is that the current density is 2.0A g-1The reversible specific capacity is 363mAh g-1。
Example 5 lithium ion battery negative electrode nanofiber composite and electrochemical performance test
The preparation method of the lithium ion battery cathode nanofiber composite material of the embodiment specifically comprises the following steps:
step one, preparation of a first solution
3.5g of potassium stannate (K)2[Sn(OH)6]) Adding into 80ml water, ultrasonic treating, stirring to dissolve potassium stannate completely, adding 6g glucose into the above solution, and stirring until glucose is dissolved completely to obtain first solution.
Step two, SnO2Preparation of/C nanosphere precursor
Adding the first solution into a hydrothermal reaction kettle with the capacity of 100mL, placing the hydrothermal reaction kettle in an explosion-proof hydrothermal oven at 180 ℃, preserving heat for 4 hours, cooling, cleaning, centrifuging and drying a reaction product to prepare SnO2a/C nanosphere precursor.
Step three, preparation of second solution
Adding 1.8g of polyacrylonitrile into 20ml of N, N-dimethylformamide, heating and stirring at 80 ℃ until the polyacrylonitrile is completely dissolved, and then adding 9g of SnO2And continuously stirring the/C nanosphere precursor to uniformly disperse the precursor to obtain a second solution.
Step four, preparation of third solution
Adding 3g of polyvinylpyrrolidone into 20ml of N, N-dimethylformamide, heating and stirring at 60 ℃ until the polyvinylpyrrolidone is completely dissolved, then adding 0.8g of nickel acetylacetonate, and continuing stirring to completely dissolve the nickel acetylacetonate to obtain a third solution.
Step five, coaxial electrostatic spinning
In this step, the types of the electrostatic spinning equipment adopted are: TL-Pro-BM. The inner solution of the coaxial electrostatic spinning is a second solution, the outer solution is a third solution, wherein the advancing speed of the inner solution is 1mL h-1The advancing speed of the external solution was 1.5mL h-1The electrospinning voltage is 20kV, and the receiving speed of the roller is 30 rpm-1The distance between the electrospinning needle head and the receiver is 18cm, the electrospinning time is 10h, and SnO is obtained2a/C @ Ni nanofiber precursor.
Step six, SnO2Oxidation treatment of/C @ Ni nanofiber precursor
SnO prepared by coaxial electrostatic spinning2The oxidation treatment process of the/C @ Ni nanofiber precursor comprises the following steps:
SnO2Putting the/C @ Ni nanofiber precursor in air at 10 ℃ for min-1The temperature rising speed is gradually increased to 250 ℃, and the temperature is kept constant for 2 hours to obtain oxidized SnO2a/C @ Ni nanofiber precursor.
Step seven, oxidized SnO2Carbonization treatment of/C @ Ni nanofiber precursor
For oxidized SnO2The carbonization treatment process of the/C @ Ni nanofiber precursor comprises the following steps:
oxidizing SnO2The precursor of the/C @ Ni nano-fiber is put in inert gas at 5 ℃ for min-1Gradually heating to 600 ℃ at the heating speed, and keeping the temperature for 3 hours to obtainSnO2The invention relates to a/C @ Ni nano-fiber composite material, in particular to a lithium ion battery cathode nano-fiber composite material.
The prepared SnO2the/C @ Ni nano-fiber composite material is assembled into a 2032 type button half cell in a glove box in a high-purity argon atmosphere. The half-cell is subjected to cycle performance test at room temperature, and the charge-discharge current density is 0.1A g-1Circulating for 200 circles, wherein the charging and discharging voltage is 0.01-1.5V; at 2.0A g-1The multiplying power performance test is carried out under the high current density, and the charging and discharging voltage range is 0.01-1.5V.
SnO of the present invention2the/C @ Ni nano-fiber composite material is used as a lithium ion battery negative electrode material for testing, and the test result is as follows: at 0.1A g-1Under the current density, the reversible specific capacity of the first loop is 997mAh g-1The coulombic efficiency is 52 percent, and the reversible specific capacity is 561mAh g after circulation for 200 times-1The capacity retention rate is 56%, and the rate capability is that the current density is 2.0A g-1The reversible specific capacity is 354mAh g-1。
Comparative example
In this comparative example, the difference from example 1 is that: at SnO2In the preparation process of the/C nanofiber composite material, nickel acetylacetonate is not added in the process of preparing the third solution, and the rest is the same as that of the embodiment 1.
SnO prepared by this comparison2the/C nano-fiber composite material is used as the negative electrode material of the lithium ion battery to be tested and is 0.1A g-1The reversible specific capacity of the first loop is 906mAh g under the current density-1The coulombic efficiency is 65 percent, and the reversible specific capacity after 200 times of circulation is 796mAh g-1The capacity retention rate was 87.8%, the rate capability was 2.0A g-1The reversible specific capacity is 256mAh g-1。
The comparison between examples 1-3 and comparative example 1 shows that Ni nanoparticles have good promotion effect on the rate performance improvement of the composite material, and the results of examples 4-5 show that SnO is2The capacitance of the material can be effectively improved.
Although the invention has been described in detail above with reference to a general description and specific examples, it will be apparent to one skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (10)

1. A preparation method of a negative electrode nano-fiber composite material of a lithium ion battery is characterized in that,
the preparation method comprises the following steps: using a catalyst containing SnO2Preparing SnO (SnO) from second solution of/C nanosphere precursor and third solution containing nickel acetylacetonate through coaxial electrostatic spinning2a/C @ Ni nanofiber precursor;
the SnO2SnO is obtained by oxidizing and carbonizing a/C @ Ni nanofiber precursor2the/C @ Ni nano-fiber composite material is the lithium ion battery negative electrode nano-fiber composite material.
2. The method for preparing the negative nanofiber composite for lithium ion batteries according to claim 1,
the SnO2The preparation method of the/C nanosphere precursor comprises the following steps:
adding potassium stannate into water, stirring and carrying out ultrasonic treatment until the potassium stannate is completely dissolved to obtain a potassium stannate solution, adding glucose, stirring until the potassium stannate is completely dissolved to obtain a first solution, adding the first solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in an explosion-proof oven at 180 ℃, reacting for 4 hours, washing, centrifuging and drying a reaction product to obtain the SnO2a/C nanosphere precursor;
wherein, in the first solution, the mass fraction of the potassium stannate is 1-10%, and the mass ratio of the glucose to the potassium stannate is 0.5-10.
3. The method for preparing the negative nanofiber composite for lithium ion batteries according to claim 1,
the preparation method of the second solution comprises the following steps:
adding polyacrylonitrile into N, N-dimethyl formylStirring at 80 deg.C for 30min to dissolve completely in amine, and adding the SnO2And stirring the/C nanosphere precursor for 30min to obtain the second solution.
4. The method for preparing the negative nanofiber composite for lithium ion batteries according to claim 3,
in the second solution, the mass fraction of polyacrylonitrile is 1% -30%, and the SnO2The mass ratio of the/C nanosphere precursor to the polyacrylonitrile is 0.1-5.
5. The method for preparing the negative nanofiber composite for lithium ion batteries according to claim 1,
the preparation method of the third solution comprises the following steps:
adding polyvinylpyrrolidone into N, N-dimethylformamide, stirring at 60 ℃ for 30min until polyvinylpyrrolidone is completely dissolved, adding nickel acetylacetonate, and continuously stirring for 30min to obtain a third solution;
wherein, in the third solution, the mass percent of the polyvinylpyrrolidone is 10% -30%; the mass ratio of the nickel acetylacetonate to the polyvinylpyrrolidone is 0.01-5.
6. The method for preparing the negative nanofiber composite for lithium ion batteries according to claim 1,
the coaxial electrostatic spinning conditions are as follows:
the inner layer pipeline is filled with the second solution, the outer layer pipeline is filled with the third solution, the voltage is 5-50kV, and the receiving speed of the roller is 0-100r min-1Push-injection pushing speed of 0.1-10mL h-1The distance between the electrospinning needle head and the receiver is 5-30cm, and the electrospinning time is 1-100 h.
7. The method for preparing the negative nanofiber composite for lithium ion batteries according to claim 1,
the oxidation treatment process comprises the following steps:
the SnO2The precursor of the/C @ Ni nano-fiber is put in the air at the temperature of 1-10 ℃ for min-1The temperature rising speed is gradually increased to 150-300 ℃, and the temperature is kept for 0.5-3 h.
8. The method for preparing the negative nanofiber composite for lithium ion batteries according to claim 1,
the carbonization treatment process comprises the following steps:
oxidation treated SnO2The precursor of the/C @ Ni nano-fiber is put in inert gas at the temperature of 1-20 ℃ for min-1The temperature rising speed is gradually raised to 500-1000 ℃, and the temperature is kept for 0.5-5 h.
9. The lithium ion battery negative electrode nanofiber composite prepared by the method of any one of claims 1 to 8.
10. Use of the lithium ion battery negative electrode nanofiber composite of claim 9 in any of,
(1) preparing a battery or a battery electrode material;
(2) preparing an energy storage element;
(3) an electronic device is prepared.
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