CN108736001B - Spherical porous silicon oxide negative electrode material and preparation method and application thereof - Google Patents

Spherical porous silicon oxide negative electrode material and preparation method and application thereof Download PDF

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CN108736001B
CN108736001B CN201810534418.9A CN201810534418A CN108736001B CN 108736001 B CN108736001 B CN 108736001B CN 201810534418 A CN201810534418 A CN 201810534418A CN 108736001 B CN108736001 B CN 108736001B
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porous silicon
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CN108736001A (en
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姜春海
邹智敏
李嘉琦
张旭
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Xiamen University of Technology
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
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    • H—ELECTRICITY
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    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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    • 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
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    • 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
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Abstract

The invention relates to a spherical porous silicon oxide negative electrode material, a preparation method and application thereof, wherein the spherical porous silicon oxide negative electrode material is of a core-shell structure, the core is hollow and porous silicon oxide of a spherical structure, and the shell is a spherical coating layer formed by nitrogen-doped carbon, and the preparation method comprises the following steps: preparation of MnO2Flower ball and preparation of silica coated MnO2And (5) carrying out ball-spinning to obtain the nitrogen-doped carbon-coated spherical porous silicon oxide material. The material is used as the cathode of a lithium ion battery, and when the current density is 0.5A/g and the voltage range is 0.01-3V, the specific capacity is kept at 410-425 milliampere hours/g (mAh/g) after the cycle is carried out for 300 times, and the coulombic efficiency is 99.95-99.99%.

Description

Spherical porous silicon oxide negative electrode material and preparation method and application thereof
Technical Field
The invention relates to the technical field of lithium ion battery cathode materials, in particular to a spherical porous silicon oxide cathode material and a preparation method and application thereof.
Background
The development of rechargeable lithium ion batteries with higher energy density and longer cycle life is of great interest to meet various energy storage requirements in portable electronic, hybrid and electric vehicles, as well as grid-level energy storage systems. Graphite is the most widely applied negative electrode material in commercial lithium ion batteries, but the theoretical specific capacity of the graphite is only 372mAh/g, and the high energy requirement cannot be met. In recent years, silicon-based materials have gained much attention as negative electrode materials for high energy density lithium ion batteries. Among them, the nano silicon oxide is considered as a novel anode material with good application prospect due to the advantages of wide raw material source, low cost, easy preparation, environmental protection, high specific capacity and the like.
At present, the main problem limiting the application of the silicon oxide negative electrode material is that the electrode structure is damaged and mechanically pulverized due to huge volume expansion (280-300%) in the charging and discharging processes, so that the electrode materials and the electrode material and a current collector are separated, further conductive contact is lost, and the capacity is rapidly attenuated. Therefore, how to improve the cycle performance of the silicon-based anode material is the focus of research at present.
Compounding silicon oxide with carbon materials is a major approach to solve the above problems. Generally, SiOx/C composites can be obtained by polymerizing organic precursors (such as methacryl and triethoxysilane) followed by carbonization. In addition, porous SiO can also be prepared by taking polyvinylpyrrolidone (PVP), Cetyl Trimethyl Ammonium Bromide (CTAB), Tetraethoxysilane (TEOS) and cane sugar as raw materials and performing sol-gel assisted carbonization treatmentx/C(1<x<2) A composite material. However, the processes described above all result in a solid carbon-coated silica structure. The carbon shell has no reserved space for accommodating the volume expansion of the silicon oxide in the lithium charging and discharging process.
In order to obtain a silicon oxide structure with a reserved space, HF is generally adopted to etch silicon dioxide in the prior art, such as CN107623113A and CN106299323A, and the above patent method uses highly corrosive HF, so that the requirements on equipment are high, the operation is difficult, and the method is not environment-friendly. Silicon-aluminum alloy is also selected as a silicon source, and then aluminum is removed under an acidic condition to achieve the purpose of pore forming, such as CN 106848199A.
Disclosure of Invention
The invention aims to solve the problems of the prior art and provides a spherical porous silicon oxide negative electrode material, a preparation method and application thereof.
The invention is realized by MnO2Depositing a silicon oxide layer on the surface of the porous ball, and then utilizing pyrrole and MnO2Redox polymerization of (B) consuming MnO2And meanwhile, the porous polypyrrole-coated spherical porous silicon oxide is obtained. Consumption of MnO by redox reaction2Compared with the conventional acid etching technology, the method is easier to operate, can be completed by conventional equipment, and is more environment-friendly in process. Meanwhile, polypyrrole is deposited on the surface of the silicon oxide, and further through carbonization treatment,the spherical porous silicon oxide coated by porous polypyrrole can be converted into the spherical porous silicon oxide coated by nitrogen-doped carbon. Wherein the silicon oxide may be SiO2Or partially reduced SiOx(<1x<2)。
MnO coated with silicon oxide in step 3) of the invention2The globules are dispersed in an aqueous solution of an acid which acts to donate protons, promote polymerization of pyrrole monomers, and control pyrrole and MnO2In a proportion to ensure complete dissolution of MnO2An intermediate layer.
The specific scheme is as follows:
the spherical porous silicon oxide negative electrode material is in a core-shell structure, the core is hollow and porous silicon oxide in a spherical structure, and the shell is a spherical coating layer formed by nitrogen-doped carbon.
Furthermore, the mass content of nitrogen in the spherical porous silicon oxide negative electrode material is 1.5-2%, and the mass content of carbon is 40-50%.
Furthermore, the thickness of silicon oxide in the spherical porous silicon oxide negative electrode material is 4-10 nm, and the thickness of the carbon coating layer is 20 nm.
Furthermore, when the current density of the spherical porous silicon oxide negative electrode material is 0.5A/g and the voltage range is 0.01-3V, the specific capacity after the circulation for 300 times is 410-425 milliampere hours/g (mAh/g), and the coulombic efficiency is 99.0-99.99%.
The invention also provides a preparation method of the spherical porous silicon oxide negative electrode material, which comprises the following steps:
step 1): dissolving potassium permanganate in deionized water, adding concentrated acid, heating for reaction, filtering, washing and drying reaction products to obtain MnO2Flower ball;
step 2): MnO obtained in the step 1)2Dispersing the flower balls into a mixed solution of deionized water and ethanol to obtain a solution A; dissolving silicate ester to obtain solution B; dropwise adding the solution B into the solution A while stirring the solution A, standing the reaction system, and then filtering, washing and drying to obtain MnO coated with silicon oxide2Flower ball;
step 3): MnO coated with the silicon oxide obtained in the step 2)2Dispersing the ball into an aqueous acid solution, and dropwise adding pyrrole monomer under stirring, wherein the dosage of the pyrrole monomer is as follows: MnO in step 2)2The dosage of the flower ball is 0.5-1 ml: 0.5-1 g, continuously stirring, filtering, washing with deionized water, and drying to obtain powder;
step 4): carbonizing the powder obtained in the step 3) for 1-3 h at 500-900 ℃ under the protection of inert gas to obtain the spherical porous nitrogen-doped carbon-coated silicon oxide negative electrode material.
Further, the step 1) is to dissolve potassium permanganate into deionized water at a concentration of 5-10 g/L, add 1-2 ml of concentrated acid into each 1g of potassium permanganate, seal, react at 80 ℃ for 10 hours, filter reaction products, wash with deionized water, and dry to obtain MnO2Flower ball;
optionally, the concentrated acid in the step 1) is concentrated hydrochloric acid, concentrated nitric acid or concentrated sulfuric acid.
Further, the silicate in the step 2) is tetraethoxysilane or methyl silicate.
Further, the step 2) is to use MnO obtained in the step 1)2MnO of 1g for flower ball2The ball was dispersed in 100ml of a mixed solution of ethanol and deionized water, wherein ethanol: dropwise adding concentrated ammonia water to adjust the pH to 8-12 to obtain a solution A, wherein the mass ratio of the deionized water is 25: 15; dissolving ethyl orthosilicate into an ethanol solution according to the volume ratio of 1: 2-5 to obtain a solution B; dropwise adding the solution B into the solution A while stirring the solution A, wherein the mass ratio of the solution A to the solution B is 8:1, standing the solution for more than 4 hours after the reaction is carried out for 30min, and then filtering, washing and drying to obtain MnO coated with silicon oxide2And (5) flower balls.
Further, the step 3) is to disperse the product obtained in the step 2) into a 0.5-1M aqueous solution of hydrochloric acid or nitric acid, and under the condition of stirring, according to MnO per gram21ml of pyrrole monomer is dripped, continuously stirred for 4 hours, filtered, washed by deionized water and dried to obtain powder.
The invention also protects the application of the spherical porous silicon oxide negative electrode material prepared by the preparation method of the spherical porous silicon oxide negative electrode material, and the spherical porous silicon oxide negative electrode material is used for lithium ion batteries.
Has the advantages that: 1) the invention uses the spherical manganese oxide flower ball which is formed by stacking nano sheets prepared by the oxidation-reduction reaction of potassium permanganate as a template, and ensures that silicon oxide has fine nano structure units, thereby being beneficial to lithium ion transmission.
2) The nitrogen-doped carbon material is coated on the surface of the silicon oxide, so that the conductivity of the silicon oxide cathode material can be improved, and the cycling stability and the rate capability of the electrode can be improved.
3) Coating the surface of the silica with a carbon shell can cause expansion within the carbon shell. The volume expansion of silicon oxide is restrained, and the microspheres with the core-shell structures have hollow structures, so that the problem of internal structure damage caused by the volume expansion of silicon can be prevented, active materials can be prevented from falling off from a current collector, and the cycle performance is improved.
Drawings
FIG. 1 is a scanning electron micrograph of spherical porous silica obtained in example 1.
FIG. 2 is a transmission electron micrograph of the spherical porous silica obtained in example 1.
FIG. 3 is a graph showing the constant current charge/discharge cycle characteristics at 0.5A/g of the spherical porous silica negative electrode material obtained in example 1.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
The preparation method of the spherical porous silicon oxide material comprises the following steps: 1) dissolving potassium permanganate into 1000ml of deionized water at the concentration of 5g/L, adding 2ml of concentrated hydrochloric acid into every 1g of potassium permanganate, sealing, reacting at 80 ℃ for 10 hours, filtering a reaction product, washing with deionized water, and drying to obtain MnO2Flower ball; 2) adding 1g of the obtained MnO2Dispersing the ball flower into 100ml of mixed solution of ethanol and deionized water (the volume ratio of the ethanol to the deionized water is 25:15), and dropwise adding 2ml of concentrated ammonia water to obtain solution A; dissolving 2ml of ethyl orthosilicate into 5ml of ethanol solution to obtain solution B; dropwise adding the solution B into the solution A while stirring, wherein the mass ratio of the solution A to the solution B is 8:1, standing the solution for more than 4 hours after the reaction is carried out for 30min, filtering, washing and drying to obtain the MnO coated with silicon oxide2Flower ball; 3) the resulting product was dispersed in 100ml of a 0.5M hydrochloric acid solution, with stirring, per gram of MnO2Adding pyrrole monomer dropwise corresponding to 0.5ml of pyrrole monomer, continuously stirring for 4h, filtering, washing with deionized water, and drying; 4) carbonizing the obtained powder at 900 ℃ for 1h under the protection of inert gas to obtain the spherical porous silicon oxide material.
Fig. 1 is a scanning electron micrograph of the obtained nitrogen-doped carbon-coated spherical porous silicon oxide material obtained in this example. As can be seen from FIG. 1, the obtained nitrogen-doped carbon-coated spherical porous silicon oxide material has a diameter of about 2 μm, an obvious porous structure and a good sphericity. Fig. 2 is a transmission electron micrograph of the obtained nitrogen-doped carbon-coated spherical porous silicon oxide material obtained in this example, which shows that the interior of the nitrogen-doped carbon-coated spherical porous silicon oxide material is a hollow structure.
The mass content of nitrogen in the prepared spherical porous silicon oxide material is 1.5%, the mass content of carbon is 42%, the spherical porous silicon oxide material is of a core-shell structure, the core is hollow and porous silicon oxide with a spherical structure, the thickness of the spherical porous silicon oxide material is 4-10 nm, a spherical coating layer formed by doping nitrogen in the silicon oxide surface with carbon is used as a shell, and the thickness of the spherical coating layer is 18-22 nm.
The nitrogen-doped carbon-coated spherical porous silicon oxide prepared under the conditions of example 1 is used as an electrode material of a lithium ion battery. Coating the prepared nitrogen-doped carbon on spherical porous silicon oxide, conductive carbon black and sodium alginate binder according to the weight ratio of 80: 10: 10, mixing, grinding and coating on a copper foil current collector; drying at 90 deg.C for 12h, and cutting into electrode slice with diameter of 12 mm; in an argon protective glove box, lithium is used as a counter electrode, and 1MLiPF dissolved in Ethylene Carbonate (EC) and dimethyl carbonate (DMC) (the volume ratio of the EC to the DMC is 1: 1) is used4Is used as electrolyte and is assembled into button lithiumThe ion half-cell was tested. As shown in fig. 3, the specific capacity of the nitrogen-doped carbon-coated spherical porous silicon oxide negative electrode material prepared under the conditions of example 1 was maintained at 420 milliampere-hour/gram (mAh/g) after 300 cycles at a current density of 0.5A/g and a voltage range of 0.01-3V, and the coulombic efficiency was 99.99%.
Example 2
The preparation method of the spherical porous silicon oxide material comprises the following steps: 1) dissolving potassium permanganate into 1000ml of deionized water at the concentration of 10g/L, adding 2ml of concentrated nitric acid into every 1g of potassium permanganate, sealing, reacting at 80 ℃ for 10 hours, filtering the reaction product, washing with deionized water, and drying to obtain MnO2Flower ball; 2) adding 1g of the obtained MnO2Dispersing the ball flower into 100ml of mixed solution of ethanol and deionized water (the volume ratio of the ethanol to the deionized water is 25:15), and dropwise adding 2ml of concentrated ammonia water to obtain solution A; dissolving 2ml of methyl silicate into 6ml of ethanol solution to obtain solution B; dropwise adding the solution B into the solution A while stirring, wherein the mass ratio of the solution A to the solution B is 8:1, standing the solution for more than 4 hours after the reaction is carried out for 30min, filtering, washing and drying to obtain the MnO coated with silicon oxide2Flower ball; 3) the resulting product was dispersed in 100ml of 1M nitric acid solution, while stirring, as MnO per gram2Adding pyrrole monomer dropwise corresponding to 1ml of pyrrole monomer, continuously stirring for 4h, filtering, washing with deionized water, and drying; 4) carbonizing the obtained powder at 500 ℃ for 3h under the protection of inert gas to obtain the spherical porous silicon oxide material.
The mass content of nitrogen in the prepared spherical porous silicon oxide material is 2%, the mass content of carbon is 45%, the spherical porous silicon oxide material is of a core-shell structure, the core is hollow and porous, the thickness of the spherical porous silicon oxide material is 4-10 nm, and a spherical coating layer formed by doping carbon with nitrogen on the surface of the silicon oxide material is used as a shell, and the thickness of the spherical coating layer is 18-22 nm.
The battery charge and discharge experiment was performed according to the method of example 1, and the specific capacity was maintained at 418 milliampere-hour/gram (mAh/g) and the coulombic efficiency was 99.8% after 300 cycles at a current density of 0.5A/g and a voltage range of 0.01-3V.
Example 3
The preparation method of the spherical porous silicon oxide material comprises the following steps: 1) will be highPotassium manganate is dissolved in 1000ml of deionized water at the concentration of 8g/L, 1ml of concentrated sulfuric acid is added according to each 1g of potassium permanganate, then the mixture is sealed and reacts for 10 hours at the temperature of 80 ℃, and then the reaction product is filtered, washed by the deionized water and dried to obtain MnO2Flower ball; 2) adding 1g of the obtained MnO2Dispersing the ball flower into 100ml of mixed solution of ethanol and deionized water (the volume ratio of the ethanol to the deionized water is 25:15), and dropwise adding 2ml of concentrated ammonia water to obtain solution A; dissolving 2ml of ethyl orthosilicate into 10ml of ethanol solution to obtain solution B; dropwise adding the solution B into the solution A while stirring, wherein the mass ratio of the solution A to the solution B is 8:1, standing the solution for more than 4 hours after the reaction is carried out for 30min, filtering, washing and drying to obtain the MnO coated with silicon oxide2Flower ball; 3) the resulting product was dispersed in 100ml of a 0.5M hydrochloric acid solution, with stirring, per gram of MnO2Adding pyrrole monomer dropwise corresponding to 0.5ml of pyrrole monomer, continuously stirring for 4h, filtering, washing with deionized water, and drying; 4) carbonizing the obtained powder at 600 ℃ for 2h under the protection of inert gas to obtain the spherical porous silicon oxide material.
The mass content of nitrogen in the prepared spherical porous silicon oxide material is 1.8%, the mass content of carbon is 40%, the spherical porous silicon oxide material is of a core-shell structure, the core is hollow and porous silicon oxide with a spherical structure, the thickness of the spherical porous silicon oxide material is 4-10 nm, a spherical coating layer formed by doping nitrogen in the silicon oxide surface with carbon is used as a shell, and the thickness of the spherical coating layer is 18-22 nm.
The battery charge and discharge test was conducted in accordance with the method of example 1, and the specific capacity was maintained at 416 milliampere-hours/gram (mAh/g) after 300 cycles at a current density of 0.5A/g and a voltage of 0.01-3V, and the coulombic efficiency was 99.9%.
Example 4
The preparation method of the spherical porous silicon oxide material comprises the following steps: 1) dissolving potassium permanganate into 1000ml of deionized water at the concentration of 5g/L, adding 2ml of concentrated hydrochloric acid into every 1g of potassium permanganate, sealing, reacting at 80 ℃ for 10 hours, filtering a reaction product, washing with deionized water, and drying to obtain MnO2Flower ball; 2) adding 1g of the obtained MnO2Dispersing the ball into 100ml of mixed solution of ethanol and deionized water (the volume ratio of ethanol to deionized water is 25:15), and dropwise adding 2ml of concentrated ammonia water to obtain solution A(ii) a Dissolving 2ml of ethyl orthosilicate into 5ml of ethanol solution to obtain solution B; dropwise adding the solution B into the solution A while stirring, wherein the mass ratio of the solution A to the solution B is 8:1, standing the solution for more than 4 hours after the reaction is carried out for 30min, filtering, washing and drying to obtain the MnO coated with silicon oxide2Flower ball; 3) the resulting product was dispersed in 100ml of a 0.5M hydrochloric acid solution, with stirring, per gram of MnO2Adding pyrrole monomer dropwise corresponding to 1ml of pyrrole monomer, continuously stirring for 4h, filtering, washing with deionized water, and drying; 4) carbonizing the obtained powder at 700 ℃ for 1h under the protection of inert gas to obtain the spherical porous silicon oxide material.
The mass content of nitrogen in the prepared spherical porous silicon oxide material is 1.9%, the mass content of carbon is 50%, the spherical porous silicon oxide material is of a core-shell structure, the core is hollow and porous silicon oxide with a spherical structure, the thickness of the spherical porous silicon oxide material is 4-10 nm, a spherical coating layer formed by doping nitrogen in the silicon oxide surface with carbon is used as a shell, and the thickness of the spherical coating layer is 18-22 nm.
The battery charge and discharge test was conducted in accordance with the method of example 1, and the specific capacity was maintained at 425 milliamp-hours/gram (mAh/g) and a coulombic efficiency of 99.99% after 300 cycles at a current density of 0.5A/g and a voltage ranging from 0.01 to 3V.
Example 5
The preparation method of the spherical porous silicon oxide material comprises the following steps: 1) dissolving potassium permanganate into 1000ml of deionized water at the concentration of 5g/L, adding 2ml of concentrated hydrochloric acid into every 1g of potassium permanganate, sealing, reacting at 80 ℃ for 10 hours, filtering a reaction product, washing with deionized water, and drying to obtain MnO2Flower ball; 2) adding 1g of the obtained MnO2Dispersing the ball flower into 100ml of mixed solution of ethanol and deionized water (the volume ratio of the ethanol to the deionized water is 25:15), and dropwise adding 2ml of concentrated ammonia water to obtain solution A; dissolving 2ml of methyl silicate into 4ml of ethanol solution to obtain solution B; dropwise adding the solution B into the solution A while stirring, wherein the mass ratio of the solution A to the solution B is 8:1, standing the solution for more than 4 hours after the reaction is carried out for 30min, filtering, washing and drying to obtain the MnO coated with silicon oxide2Flower ball; 3) the resulting product was dispersed in 100ml of a 0.5M hydrochloric acid solution, with stirring, per gram of MnO2Corresponding to 0.8ml of pyrrole monomerDripping pyrrole monomer, continuously stirring for 4h, filtering, washing with deionized water, and drying; 4) carbonizing the obtained powder at 800 ℃ for 1h under the protection of inert gas to obtain the spherical porous silicon oxide material.
The mass content of nitrogen in the prepared spherical porous silicon oxide material is 1.8%, the mass content of carbon is 48%, the spherical porous silicon oxide material is of a core-shell structure, the core is hollow and porous silicon oxide with a spherical structure, the thickness of the spherical porous silicon oxide material is 4-10 nm, a spherical coating layer formed by doping nitrogen in the silicon oxide surface with carbon is used as a shell, and the thickness of the spherical coating layer is 18-22 nm.
The battery charge and discharge test was performed according to the method of example 1, and the specific capacity was maintained at 420 milliampere-hour/gram (mAh/g) and the coulombic efficiency was 99.87% after 300 cycles at a current density of 0.5A/g and a voltage range of 0.01-3V.
Comparative example 1
The preparation method of the porous silicon oxide material comprises the following steps: 1) dissolving potassium permanganate into 1000ml of deionized water at the concentration of 5g/L, adding 2ml of concentrated hydrochloric acid into every 1g of potassium permanganate, sealing, reacting at 80 ℃ for 10 hours, filtering a reaction product, washing with deionized water, and drying to obtain MnO2Flower ball; 2) adding 1g of the obtained MnO2Dispersing the ball flower into 100ml of mixed solution of ethanol and deionized water (the volume ratio of the ethanol to the deionized water is 25:15), and dropwise adding 2ml of concentrated ammonia water to obtain solution A; dissolving 2ml of ethyl orthosilicate into 5ml of ethanol solution to obtain solution B; dropwise adding the solution B into the solution A while stirring, standing the solution for more than 4 hours after the reaction is carried out for 30min, filtering, washing and drying to obtain the MnO coated with the silicon oxide2Flower ball; 3) dispersing the obtained product into 100ml of 0.5M hydrochloric acid solution, dropwise adding 1ml of pyrrole monomer under the condition of stirring, continuously stirring for 4 hours, filtering, washing with deionized water, and drying; 4) carbonizing the obtained powder at 920 ℃ for 1h under the protection of inert gas to obtain the porous silicon oxide material.
The carbonization temperature can affect the graphitization degree and the nitrogen content of the carbon in the porous silicon oxide material, in the embodiment, the carbonization temperature is high, the graphitization degree is improved, but the loss of nitrogen element is serious, and the mass content of nitrogen in the material is 0.94%.
The button type lithium ion half cell is assembled according to the method in the example 1 and tested, and the result shows that the prepared nitrogen-doped carbon-coated spherical porous silicon oxide negative electrode material has the specific capacity of about 375 milliampere hours/g (mAh/g) after being cycled for 300 times at the current density of 0.5A/g and the voltage range of 0.01-3V, and the coulombic efficiency of 99.85 percent
Comparative example 2
The preparation method of the spherical porous silicon oxide material comprises the following steps: 1) dissolving 2ml of tetraethoxysilane into 5ml of ethanol solution, adding 1g of potassium permanganate, 2ml of concentrated hydrochloric acid and a proper amount of deionized water, sealing, reacting at 80 ℃ for 10 hours, filtering the reaction product, washing with deionized water, and drying to obtain the MnO coated with silicon oxide2(ii) a 2) Adding 1g of the obtained MnO2Dispersing the coated silicon oxide into 100ml of 0.5M hydrochloric acid solution, dropwise adding 1ml of pyrrole monomer under the condition of stirring, continuously stirring for 4 hours, filtering, washing with deionized water, and drying; 3) carbonizing the obtained powder at 900 ℃ for 1h under the protection of inert gas to obtain the porous silicon oxide material.
The button type lithium ion half cell is assembled according to the method in the embodiment 1 and tested, and the result shows that the prepared nitrogen-doped carbon-coated spherical porous silicon oxide negative electrode material has the specific capacity of about 392 milliampere hours/gram (mAh/g) after being cycled for 300 times at the current density of 0.5A/g and the voltage range of 0.01-3V, and the coulombic efficiency is 99.92 percent
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (6)

1. A preparation method of a spherical porous silicon oxide negative electrode material is provided, wherein the spherical porous silicon oxide negative electrode material is in a core-shell structure, the core is hollow and porous silicon oxide in a spherical structure, and the shell is a spherical coating layer formed by nitrogen-doped carbon; the mass content of nitrogen in the spherical porous silicon oxide negative electrode material is 1.5-2%, and the mass content of carbon is 40-50%; the thickness of silicon oxide in the spherical porous silicon oxide negative electrode material is 4-10 nm, and the thickness of a spherical coating layer formed by nitrogen-doped carbon is 18-22 nm, and the spherical porous silicon oxide negative electrode material is characterized in that: the method comprises the following steps:
step 1): dissolving potassium permanganate in deionized water, adding concentrated acid, heating for reaction, filtering, washing and drying reaction products to obtain MnO2Flower ball;
step 2): MnO obtained in the step 1)2Dispersing the flower balls into a mixed solution of deionized water and ethanol to obtain a solution A; dissolving silicate ester to obtain solution B; dropwise adding the solution B into the solution A while stirring the solution A, standing the reaction system, and then filtering, washing and drying to obtain MnO coated with silicon oxide2Flower ball;
step 3): MnO coated with the silicon oxide obtained in the step 2)2Dispersing the ball into an aqueous acid solution, and dropwise adding pyrrole monomer under stirring, wherein the dosage of the pyrrole monomer is as follows: MnO in step 2)2The dosage of the flower ball is 0.5-1 ml: 0.5-1 g, continuously stirring, filtering, washing with deionized water, and drying to obtain powder;
step 4): carbonizing the powder obtained in the step 3) for 1-3 h at 500-900 ℃ under the protection of inert gas to obtain the spherical porous nitrogen-doped carbon-coated silicon oxide negative electrode material.
2. The method for preparing a spherical porous silicon oxide anode material according to claim 1, characterized in that: the step 1) is dissolving potassium permanganate into deionized water at the concentration of 5-10 g/L, adding 1-2 ml of concentrated acid into each 1g of potassium permanganate, sealing, reacting at 80 ℃ for 10 hours, and then reacting the reaction productFiltering, washing with deionized water, and drying to obtain MnO2Flower ball;
optionally, the concentrated acid in the step 1) is concentrated hydrochloric acid, concentrated nitric acid or concentrated sulfuric acid.
3. The method for preparing a spherical porous silicon oxide anode material according to claim 1, characterized in that: the silicate in the step 2) is ethyl orthosilicate or methyl silicate.
4. The method for preparing a spherical porous silicon oxide anode material according to claim 1, characterized in that: the step 2) is to use MnO obtained in the step 1)2MnO of 1g for flower ball2The ball was dispersed in 100ml of a mixed solution of ethanol and deionized water, wherein ethanol: dropwise adding concentrated ammonia water to adjust the pH to 8-12 to obtain a solution A, wherein the mass ratio of the deionized water is 25: 15; dissolving ethyl orthosilicate into an ethanol solution according to the volume ratio of 1: 2-5 to obtain a solution B; dropwise adding the solution B into the solution A while stirring the solution A, wherein the mass ratio of the solution A to the solution B is 8:1, standing the solution for more than 4 hours after the reaction is carried out for 30min, and then filtering, washing and drying to obtain MnO coated with silicon oxide2And (5) flower balls.
5. The method for preparing a spherical porous silicon oxide anode material according to claim 1, characterized in that: the step 3) is to disperse the product obtained in the step 2) into a 0.5-1M hydrochloric acid or nitric acid aqueous solution, and under the condition of stirring, MnO per gram21ml of pyrrole monomer is dripped, continuously stirred for 4 hours, filtered, washed by deionized water and dried to obtain powder.
6. Use of the spherical porous silicon oxide negative electrode material prepared by the preparation method of the spherical porous silicon oxide negative electrode material according to any one of claims 1 to 5 in a lithium ion battery.
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