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CN113422014A - Polyaniline-coated tin dioxide composite negative electrode material and preparation method thereof - Google Patents

Polyaniline-coated tin dioxide composite negative electrode material and preparation method thereof Download PDF

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CN113422014A
CN113422014A CN202110659218.8A CN202110659218A CN113422014A CN 113422014 A CN113422014 A CN 113422014A CN 202110659218 A CN202110659218 A CN 202110659218A CN 113422014 A CN113422014 A CN 113422014A
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tin dioxide
polyaniline
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composite negative
dioxide composite
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赖春艳
赵杏云
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Shanghai University of Electric Power
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H01M4/366—Composites as layered products
    • 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
    • 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
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Abstract

The invention relates to a polyaniline-coated tin dioxide composite negative electrode material and a preparation method thereof, belonging to the field of lithium ion batteries. The preparation method comprises the following steps: step 1, adding pure-phase tin dioxide into a solvent, adding aniline and doping acid, and stirring to obtain a mixture A; and step 2, dropwise adding an aqueous solution of an oxidant into the mixture A, standing, filtering, and drying to obtain the polyaniline-coated tin dioxide composite negative electrode material. The method has simple steps and mild conditions, and the prepared composite material has stronger circulation stability compared with pure-phase tin dioxide, so the composite material has wide application prospect in the lithium ion battery.

Description

Polyaniline-coated tin dioxide composite negative electrode material and preparation method thereof
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a polyaniline-coated tin dioxide composite negative electrode material and a preparation method thereof.
Background
With the rapid development of society, the supply of energy cannot meet the emerging demand due to the increase in energy consumption, which exacerbates the shortage of energy, and thus, the storage and conversion of energy play an important role in overcoming the energy challenge. The ideal high-efficiency energy storage and conversion device has the advantages of high energy density, high power density, stable cycle life and the like.
Compared with other energy storage devices, the lithium ion battery has the characteristics of high energy density, long cycle life, no memory effect, environmental friendliness and the like, and has successfully realized commercialization. Currently, research on the positive electrode material of the lithium ion battery is greatly advanced, the negative electrode material is also one of the main factors determining the energy density of the lithium ion battery, however, the commercial graphite negative electrode is limited to a low theoretical capacity (372mAh/g) and cannot meet the higher capacity requirement, and therefore, the negative electrode material with higher capacity needs to be searched.
Tin-based materials are potential candidates for replacing graphite anodes, such as tin dioxide (SnO)2) Has received extensive research attention due to its high theoretical capacity of 782mAh/g, low intercalation potential and environmental friendliness. However, tin dioxide as a negative electrode of a lithium ion battery has a large volume effect in the charging and discharging processes, an SEI film is continuously generated, and poor conductivity per se often causes large capacity fading, which hinders commercial application of the tin dioxide. In order to improve SnO2The commonly adopted strategies comprise nanocrystallization, alloying, ion doping, composite modification on the surface of the material and the like. In the presence of SnO2In the composite conductive material, widely used materials comprise carbon materials, metal compounds and the like, wherein the metal compounds have abundant resources and multi-electron redox capability, but have the defects of low conductivity and easy self-aggregation. In order to advance the commercialization of tin dioxide as the negative electrode of the lithium ion battery, more diversified solutions for the above problems should be provided, and the composite modification of tin dioxide by using the conductive polymer can effectively improve the above problems and enhance the electrochemical performance.
Disclosure of Invention
The present invention is made to solve the above problems, and an object of the present invention is to provide a polyaniline-coated tin dioxide composite negative electrode material and a method for preparing the same.
The invention provides a polyaniline-coated tin dioxide composite negative electrode material which is characterized by having the following chemical formula: SnO2@ PANI, wherein the coating amount of the polyaniline is 10-30 percent of the mass of the tin dioxide, and is preferably 23 percent。
The invention provides a preparation method of a polyaniline-coated tin dioxide composite negative electrode material, which is used for preparing the polyaniline-coated tin dioxide composite negative electrode material and has the characteristics that the preparation method comprises the following steps: step 1, adding pure-phase tin dioxide into a solvent, adding aniline and doping acid, and stirring to obtain a mixture A; and step 2, dropwise adding an aqueous solution of an oxidant into the mixture A, standing, filtering, and drying to obtain the polyaniline-coated tin dioxide composite negative electrode material.
In the preparation method of the polyaniline-coated tin dioxide composite negative electrode material provided by the invention, the preparation method also has the following characteristics: wherein the mol ratio of the doping acid to the aniline is (0.2-0.3): 1, preferably 0.25: 1.
in the preparation method of the polyaniline-coated tin dioxide composite negative electrode material provided by the invention, the preparation method also has the following characteristics: wherein the molar ratio of the aniline to the oxidant is (1-2): 1, preferably 1: 1.
in the preparation method of the polyaniline-coated tin dioxide composite negative electrode material provided by the invention, the preparation method also has the following characteristics: wherein the concentration of the oxidizing agent is 0.02mol/L to 0.04mol/L, preferably 0.03 mol/L.
In the preparation method of the polyaniline-coated tin dioxide composite negative electrode material provided by the invention, the preparation method also has the following characteristics: wherein the oxidant is ammonium persulfate.
In the preparation method of the polyaniline-coated tin dioxide composite negative electrode material provided by the invention, the preparation method also has the following characteristics: wherein the doping acid is benzene tetracarboxylic acid.
In the preparation method of the polyaniline-coated tin dioxide composite negative electrode material provided by the invention, the preparation method also has the following characteristics: wherein, in the step 1, the solvent is deionized water.
In the preparation method of the polyaniline-coated tin dioxide composite negative electrode material provided by the invention, the preparation method also has the following characteristics: wherein, in the step 2, the standing temperature is 0-5 ℃, and the reaction time is 10-15 h, preferably 12 h.
In the preparation method of the polyaniline-coated tin dioxide composite negative electrode material provided by the invention, the preparation method also has the following characteristics: in the step 2, the solvent for suction filtration is any one or more of deionized water, methanol or acetone.
Action and Effect of the invention
According to the preparation method of the polyaniline-coated tin dioxide composite negative electrode material, the preparation method comprises the following steps: step 1, adding pure-phase tin dioxide into a solvent, adding aniline and doping acid, and stirring to obtain a mixture A; and step 2, dropwise adding an aqueous solution of an oxidant into the mixture A, standing, filtering, and drying to obtain the polyaniline-coated tin dioxide composite negative electrode material. Because the method has simple steps and mild conditions, the obtained composite material has stronger cycle stability compared with pure-phase tin dioxide, and has wide application prospect in lithium ion batteries.
Drawings
FIG. 1 is an XRD pattern of a phase pure standard card of the present invention and a negative electrode material prepared in example 1;
fig. 2 is SEM images of the anode materials prepared in comparative example 1 and example 1 of the present invention;
FIG. 3 is a graph showing charge and discharge curves at 100mA/g of the negative electrode materials prepared in comparative example 1 and example 1 according to the present invention; and
FIG. 4 is a cycle chart at 100mA/g of the anode materials prepared in comparative example 1 and examples 1 to 5 of the present invention.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the embodiment and the accompanying drawings are combined to specifically describe the polyaniline-coated tin dioxide composite negative electrode material and the preparation method thereof.
< example 1>
A preparation method of a polyaniline-coated tin dioxide composite negative electrode material comprises the following steps:
step 1, adding pure-phase tin dioxide into a solvent, adding aniline and doping acid, and stirring to obtain a mixture A, wherein the method comprises the following specific steps:
the preparation method of the pure-phase tin dioxide comprises the following steps:
weighing 5g of SnCl2·2H2O, grinding, placing in a porcelain boat, transferring the porcelain boat into a tube furnace, heating to 500 ℃ at the speed of 5 ℃/min in the air atmosphere, keeping the temperature for 2 hours, cooling to room temperature, taking out and grinding to obtain tin dioxide, namely pure-phase SnO2。
Taking 0.2g of pure-phase tin dioxide, uniformly dispersing in deionized water by ultrasonic, adding 0.0455g of 1,2,4, 5-benzenetetracarboxylic acid and 65ul of aniline, uniformly stirring at room temperature to obtain a mixture A, placing the mixture A in an ice bath environment, and keeping the environment temperature within 0-5 ℃.
And 2, dropwise adding an aqueous solution of an oxidant into the mixture A, standing, filtering, and drying to obtain the polyaniline-coated tin dioxide composite negative electrode material, wherein the method comprises the following specific steps:
slowly and dropwise adding 0.1612g of Ammonium Persulfate (APS) aqueous solution into the mixture A, uniformly stirring, standing for 12 hours, sequentially performing suction filtration and washing for 3 times by using deionized water and methanol acetone respectively, finally cleaning by using acetone to remove oligoaniline and excessive APS, placing the obtained product into an oven to be dried to obtain green powder, grinding for 1 hour by using a mortar to obtain a composite product SnO2@ PANI with the polyaniline coating amount of 23%,
in this example, the molar stoichiometric ratio of 1,2,4, 5-benzenetetracarboxylic acid, aniline, ammonium persulfate was 0.25: 1: 1.
< example 2>
A preparation method of a polyaniline-coated tin dioxide composite negative electrode material comprises the following steps:
step 1, adding pure-phase tin dioxide into a solvent, adding aniline and doping acid, and stirring to obtain a mixture A, wherein the method comprises the following specific steps:
taking 0.3g of pure-phase tin dioxide prepared in example 1, ultrasonically and uniformly dispersing the pure-phase tin dioxide in deionized water, adding 0.049g of 1,2,4, 5-benzenetetracarboxylic acid and 70ul of aniline, uniformly stirring the mixture at room temperature to obtain a mixture A, and placing the mixture A in an ice bath environment to keep the environment temperature within 0-5 ℃.
And 2, dropwise adding an aqueous solution of an oxidant into the mixture A, standing, filtering, and drying to obtain the polyaniline-coated tin dioxide composite negative electrode material, wherein the method comprises the following specific steps:
slowly and dropwise adding 0.1736g of Ammonium Persulfate (APS) aqueous solution into the mixture A, uniformly stirring, standing for 12 hours, sequentially performing suction filtration and washing for 3 times by using deionized water and methanol acetone respectively, finally cleaning by using acetone to remove oligoaniline and excessive APS, placing the obtained product into an oven to be dried to obtain green powder, grinding for 1 hour by using a mortar to obtain a composite product SnO with the polyaniline coating amount of 15 percent2@PANI，
In this example, the molar stoichiometric ratio of 1,2,4, 5-benzenetetracarboxylic acid, aniline, ammonium persulfate was 0.25: 1: 1.
< example 3>
A preparation method of a polyaniline-coated tin dioxide composite negative electrode material comprises the following steps:
step 1, adding pure-phase tin dioxide into a solvent, adding aniline and doping acid, and stirring to obtain a mixture A, wherein the method comprises the following specific steps:
taking 0.3g of pure-phase tin dioxide prepared in example 1, ultrasonically and uniformly dispersing the pure-phase tin dioxide in deionized water, adding 0.059g of 1,2,4, 5-benzenetetracarboxylic acid and 84ul of aniline, uniformly stirring the mixture at room temperature to obtain a mixture A, and placing the mixture A in an ice bath environment to keep the environment temperature within 0-5 ℃.
And 2, dropwise adding an aqueous solution of an oxidant into the mixture A, standing, filtering, and drying to obtain the polyaniline-coated tin dioxide composite negative electrode material, wherein the method comprises the following specific steps:
slowly and dropwise adding 0.2110g of Ammonium Persulfate (APS) aqueous solution into the mixture A, uniformly stirring, standing for 12 hours, sequentially performing suction filtration and washing for 3 times by using deionized water and methanol acetone, finally cleaning by using acetone to remove oligoaniline and excessive APS, placing the obtained product into an oven to be dried to obtain green powder, grinding for 1 hour by using a mortar to obtain a composite product SnO with the polyaniline coating amount of 20 percent2@PANI，
In this example, the molar stoichiometric ratio of 1,2,4, 5-benzenetetracarboxylic acid, aniline, ammonium persulfate was 0.25: 1: 1.
< example 4>
A preparation method of a polyaniline-coated tin dioxide composite negative electrode material comprises the following steps:
step 1, adding pure-phase tin dioxide into a solvent, adding aniline and doping acid, and stirring to obtain a mixture A, wherein the method comprises the following specific steps:
taking 0.3g of pure-phase tin dioxide prepared in example 1, ultrasonically and uniformly dispersing the pure-phase tin dioxide in deionized water, adding 0.073g of 1,2,4, 5-benzenetetracarboxylic acid and 105ul of aniline, uniformly stirring the mixture at room temperature to obtain a mixture A, and placing the mixture A in an ice bath environment to keep the environment temperature within 0-5 ℃.
And 2, dropwise adding an aqueous solution of an oxidant into the mixture A, standing, filtering, and drying to obtain the polyaniline-coated tin dioxide composite negative electrode material, wherein the method comprises the following specific steps:
slowly and dropwise adding 0.2637g of Ammonium Persulfate (APS) aqueous solution into the mixture A, uniformly stirring, standing for 12 hours, sequentially performing suction filtration and washing for 3 times by using deionized water and methanol acetone, finally cleaning by using acetone to remove oligoaniline and excessive APS, placing the obtained product into an oven to be dried to obtain green powder, grinding for 1 hour by using a mortar to obtain a composite product SnO with the polyaniline coating amount of 25 percent2@PANI，
In this example, the molar stoichiometric ratio of 1,2,4, 5-benzenetetracarboxylic acid, aniline, ammonium persulfate was 0.25: 1: 1.
< example 5>
A preparation method of a polyaniline-coated tin dioxide composite negative electrode material comprises the following steps:
step 1, adding pure-phase tin dioxide into a solvent, adding aniline and doping acid, and stirring to obtain a mixture A, wherein the method comprises the following specific steps:
taking 0.2g of pure-phase tin dioxide prepared in example 1, ultrasonically and uniformly dispersing the pure-phase tin dioxide in deionized water, adding 0.0595g of 1,2,4, 5-benzenetetracarboxylic acid and 85ul of aniline, uniformly stirring the mixture at room temperature to obtain a mixture A, and placing the mixture A in an ice bath environment to keep the environmental temperature within 0-5 ℃.
And 2, dropwise adding an aqueous solution of an oxidant into the mixture A, standing, filtering, and drying to obtain the polyaniline-coated tin dioxide composite negative electrode material, wherein the method comprises the following specific steps:
slowly and dropwise adding 0.2108g of Ammonium Persulfate (APS) aqueous solution into the mixture A, uniformly stirring, standing for 12 hours, sequentially performing suction filtration and washing for 3 times by using deionized water and methanol acetone respectively, finally cleaning by using acetone to remove oligoaniline and excessive APS, placing the obtained product into an oven to be dried to obtain green powder, grinding for 1 hour by using a mortar to obtain a composite product SnO with the polyaniline coating amount of 30 percent2@PANI，
In this example, the molar stoichiometric ratio of 1,2,4, 5-benzenetetracarboxylic acid, aniline, ammonium persulfate was 0.25: 1: 1.
< comparative example 1>
Pure-phase SnO2The preparation method of the negative electrode material comprises the following steps:
weighing 5g of SnCl2·2H2O, grinding, placing in a porcelain boat, transferring the porcelain boat into a tube furnace, heating to 500 ℃ at the speed of 5 ℃/min in the air atmosphere, keeping the temperature for 2 hours, cooling to room temperature, taking out and grinding to obtain tin dioxide, namely pure-phase SnO2A material.
< test example 1>
X-ray diffraction test
Assembling the battery: when the negative electrode materials prepared in comparative example 1 and examples 1 to 5 are used for battery assembly, the specific steps are as follows:
step 1, using the composite material obtained in the embodiments 1 to 5 as a raw material to prepare a lithium ion battery positive pole piece:
uniformly mixing the composite material, acetylene black and a binder (CMC) in a mass ratio of 8: 1 with a proper amount of deionized water to obtain slurry, uniformly coating the slurry on a copper foil by using a coating machine, and carrying out vacuum drying for 12 hours at 80 ℃. Punching the pole piece into a circular pole piece (the diameter is 14mm) for assembling the CR2016 type button cell;
step 2, taking a lithium sheet material as a negative electrode sheet;
and 3, assembling the positive and negative plates in a glove box by using the Celgard2400 polypropylene film as a diaphragm and using 1M LiPF6/EC + DMC + EMC (volume ratio of 1:1:1) as electrolyte. The assembly sequence of the button cell is as follows: positive electrode casing/test pole piece/electrolyte/diaphragm/metallic lithium piece/foam nickel/negative electrode casing. And (5) packaging the battery by using a sealing machine, and carrying out electrochemical test.
The test method comprises the following steps: the 23 wt% polyaniline-coated tin dioxide composite anode material obtained in example 1 was tested using an X-ray diffractometer model D8Advance manufactured by Bruker, germany, and the XRD pattern obtained is shown in fig. 1.
It can be seen from FIG. 1 that the composite material sample synthesized in example 1 has the same diffraction peak of tetragonal rutile SnO as the standard card2(JCPDSNo.21-1250), which indicates that the coating of tin dioxide by polyaniline does not change the crystal structure of the pure phase.
< test example 2>
Scanning test of electron microscope
The test method comprises the following steps: the Nidoku SU1500 field emission electron microscope is used for carrying out electron microscope test on the comparative example 1 and the example 1 to obtain pure-phase SnO2And SnO2SEM comparison of @ PANI.
Fig. 2a and 2b are SEM images of the anode materials prepared in comparative example 1 and example 1 of the present invention, respectively.
As shown in fig. 2a, 2b, compared to pure phase SnO2Particle surface, composite SnO2The surface of @ PANI is rougher, and the coating effect of polyaniline plays a role in inhibiting the volume effect of tin dioxide, so that the circulation stability is improved. Thus, composite SnO prepared in example 12@ PANI an electrode material with good electrochemical properties.
< test example 3>
Charge and discharge test
The test method comprises the following steps: pure-phase SnO obtained in comparative example 12Negative electrode material, 23 wt% polyaniline-coated tin dioxide composite negative electrode obtained in example 1After the material is used as a positive pole piece to prepare a button cell, a charge-discharge test is carried out at a constant temperature of 25 ℃ and a current density of 100mA/g by using a LAND cell testing instrument of blue electronic corporation of Wuhan City, the charge-discharge voltage range is 0-2.5V, and the charge-discharge result is shown in figure 3.
FIGS. 3a and 3b are graphs of charging and discharging of the pure-phase tin dioxide material obtained in comparative example 1 and 23 wt% polyaniline-coated tin dioxide composite negative electrode material obtained in example 1 at 100mA/g current density for 1 st, 10 th and 20 th times, respectively, after the materials are assembled into a battery.
As can be seen in FIGS. 3a and 3b, SnO2And SnO2The specific discharge capacity at the first time of the @ PANI material is 1493.7mAh/g and 1532.5mAh/g respectively, the corresponding coulombic efficiency is 65.23 percent and 53.40 percent, the larger irreversible capacity loss is caused by the SEI film generation, and SnO is generated in 10 th and 20 th cycles2Specific discharge capacity of 892.1 and 804.6mAh/g, and SnO2The specific discharge capacity of the @ PANI composite material is 715.7mAh/g and 651.9mAh/g, and the overlap ratio of the 10 th and 20 th curves of the composite material is higher than that of the charge-discharge curve of the pure-phase material, which indicates that the composite material has higher capacity retention rate.
< test example 4>
Charge and discharge cycle test
The test method comprises the following steps: after the pure-phase stannous sulfide material obtained in comparative example 1 and the polyaniline-coated tin dioxide composite negative electrode materials obtained in examples 1 to 5 of 23 wt%, 15 wt%, 20 wt%, 25 wt% and 30 wt% were assembled into a battery, a charge-discharge cycle test was performed at a voltage of 0 to 2.5V and a current density of 100 mA/g.
FIG. 4 is a cycle chart at 100mA/g of the anode materials prepared in comparative example 1 and examples 1 to 5 of the present invention.
As can be seen from fig. 4, the initial discharge capacity of the electrode material was reduced after coating with polyaniline, but the capacity of the composite materials of examples 1-5 was greatly reduced compared to comparative example 1, and it can be seen that the pure-phase tin dioxide material of comparative example 1, the polyaniline-coated tin dioxide composite materials of examples 1-5 respectively had specific capacities of 4.9mAh/g, 594mAh/g, 157.3mAh/g, 341.1mAh/g, 459.6mAh/g, and 255.6mAh/g after 100 cycles, which all showed better cycle stability compared to the pure-phase tin dioxide, wherein the capacity retention of example 1 compared to examples 2-5 was the best. Therefore, the polyaniline coating can effectively improve the cycling stability of tin dioxide as a lithium ion battery, when the polyaniline content is 23 wt%, the composite material has the best cycling performance, the reversible specific capacity of 594mAh/g can be maintained after 100 cycles, and the good cycling stability is shown.
Effects and effects of the embodiments
According to the preparation method of the polyaniline-coated tin dioxide composite negative electrode material, the preparation method comprises the following steps: step 1, adding pure-phase tin dioxide into a solvent, adding aniline and doping acid, and stirring to obtain a mixture A; and step 2, dropwise adding an aqueous solution of an oxidant into the mixture A, standing, filtering, and drying to obtain the polyaniline-coated tin dioxide composite negative electrode material. Because the method has simple steps and mild conditions, the obtained composite material has stronger cycle performance compared with pure-phase tin dioxide, and has wide application prospect in lithium ion batteries.
Further, in this embodiment, the polyaniline is used to coat the tin dioxide particles, so that the conductivity of the active material can be improved, the carboxyl group in the polyaniline can enhance the connection between the active material and the conductive carbon, and prevent the active material from being separated from the conductive matrix, the coating effect of the polyaniline can also inhibit the volume expansion of the tin dioxide, reduce the phenomenon of continuous generation and thickening of the SEI film, and improve the electrochemical performance of the tin dioxide as the negative electrode material of the lithium ion battery.
The above embodiments are preferred examples of the present invention, and are not intended to limit the scope of the present invention.

Claims (10)

1.一种聚苯胺包覆二氧化锡复合负极材料，其特征在于，化学式如下：1. a polyaniline-coated tin dioxide composite negative material, is characterized in that, chemical formula is as follows: SnO2@PANI，SnO 2 @PANI, 其中，聚苯胺的包覆量为二氧化锡质量的10％-30％。Wherein, the coating amount of polyaniline is 10%-30% of the mass of tin dioxide. 2.一种聚苯胺包覆二氧化锡复合负极材料的制备方法，用于制备权利要求1所述的聚苯胺包覆二氧化锡复合负极材料，其特征在于，包括如下步骤：2. a preparation method of polyaniline-coated tin dioxide composite negative material, for preparing the polyaniline-coated tin dioxide composite negative material of claim 1, is characterized in that, comprises the steps: 步骤1，将纯相二氧化锡加入溶剂中，并加入苯胺和掺杂酸，搅拌，得混合物A；以及Step 1, adding pure phase tin dioxide to the solvent, adding aniline and doping acid, stirring to obtain mixture A; and 步骤2，向所述混合物A中滴加氧化剂的水溶液，静置、抽滤、干燥，即得所述聚苯胺包覆二氧化锡复合负极材料。In step 2, an aqueous solution of an oxidant is added dropwise to the mixture A, and the mixture is left to stand, suction filtered, and dried to obtain the polyaniline-coated tin dioxide composite negative electrode material. 3.根据权利要求2所述的聚苯胺包覆二氧化锡复合负极材料的制备方法，其特征在于：3. the preparation method of polyaniline-coated tin dioxide composite negative material according to claim 2, is characterized in that: 其中，所述掺杂酸与所述苯胺的摩尔比为(0.2-0.3)：1。Wherein, the molar ratio of the doping acid to the aniline is (0.2-0.3):1. 4.根据权利要求2所述的聚苯胺包覆二氧化锡复合负极材料的制备方法，其特征在于：4. the preparation method of polyaniline-coated tin dioxide composite negative material according to claim 2, is characterized in that: 其中，所述苯胺与所述氧化剂的摩尔比为(1-2)：1。Wherein, the molar ratio of the aniline to the oxidant is (1-2):1. 5.根据权利要求2所述的聚苯胺包覆二氧化锡复合负极材料的制备方法，其特征在于：5. the preparation method of polyaniline-coated tin dioxide composite negative material according to claim 2, is characterized in that: 其中，所述氧化剂的浓度为0.02mol/L-0.04mol/L。Wherein, the concentration of the oxidant is 0.02mol/L-0.04mol/L. 6.根据权利要求5所述的聚苯胺包覆二氧化锡复合负极材料的制备方法，其特征在于：6. the preparation method of polyaniline-coated tin dioxide composite negative electrode material according to claim 5, is characterized in that: 其中，所述氧化剂为过硫酸铵。Wherein, the oxidant is ammonium persulfate. 7.根据权利要求2所述的聚苯胺包覆二氧化锡复合负极材料的制备方法，其特征在于：7. the preparation method of polyaniline-coated tin dioxide composite negative material according to claim 2, is characterized in that: 其中，所述掺杂酸为苯四羧酸。Wherein, the doping acid is benzenetetracarboxylic acid. 8.根据权利要求2所述的聚苯胺包覆二氧化锡复合负极材料的制备方法，其特征在于：8. the preparation method of polyaniline-coated tin dioxide composite negative material according to claim 2, is characterized in that: 其中，步骤1中，所述溶剂为去离子水。Wherein, in step 1, the solvent is deionized water. 9.根据权利要求2所述的聚苯胺包覆二氧化锡复合负极材料的制备方法，其特征在于：9. the preparation method of polyaniline-coated tin dioxide composite negative electrode material according to claim 2, is characterized in that: 其中，步骤2中，所述静置的温度为0℃-5℃，反应时间为10h-15h。Wherein, in step 2, the standing temperature is 0°C-5°C, and the reaction time is 10h-15h. 10.根据权利要求2所述的聚苯胺包覆二氧化锡复合负极材料的制备方法，其特征在于：10. the preparation method of polyaniline-coated tin dioxide composite negative electrode material according to claim 2, is characterized in that: 其中，步骤2中，所述抽滤用的溶剂为去离子水、甲醇或丙酮中的任意一种或多种。Wherein, in step 2, the solvent used for the suction filtration is any one or more of deionized water, methanol or acetone.
CN202110659218.8A 2021-06-15 2021-06-15 Polyaniline-coated tin dioxide composite negative electrode material and preparation method thereof Pending CN113422014A (en)

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