CN112582615B - One-dimensional porous silicon-carbon composite negative electrode material, preparation method and application thereof - Google Patents

One-dimensional porous silicon-carbon composite negative electrode material, preparation method and application thereof Download PDF

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CN112582615B
CN112582615B CN202011434647.7A CN202011434647A CN112582615B CN 112582615 B CN112582615 B CN 112582615B CN 202011434647 A CN202011434647 A CN 202011434647A CN 112582615 B CN112582615 B CN 112582615B
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CN112582615A (en
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葛传长
仰永军
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Guangdong Kaijin New Energy Technology Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386Silicon or alloys based on silicon
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/18Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M2004/021Physical characteristics, e.g. porosity, surface area
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M2004/022Electrodes made of one single microscopic fiber
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M2004/026Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027Negative electrodes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention relates to the field of battery cathode materials, in particular to a one-dimensional porous silicon-carbon composite cathode material, a preparation method and application thereof, compared with the prior art, the preparation process is simple, extra coating modification is not needed, and the large-scale production is easy; the formation of porous silicon is induced in situ by a metallothermic reduction and etching method, so that the stability of silicon active components can be obviously improved while high reversible capacity is obtained, the intrinsic expansion effect of silicon is improved, and the problems of particle pulverization, structural collapse and the like are avoided; the carbon fiber matrix with small diameter and uniform thickness can be obtained through polymer matrix electrostatic spinning, so that the buffering effect can be better provided for silicon, and the electronic conductivity is improved. The porous silicon/carbon composite negative electrode material has the first reversible specific capacity of more than 750mAh/g, and the first circulating coulombic efficiency of more than 86 percent, has excellent circulating stability, overcomes the problem of poor electrochemical stability of the traditional silicon-carbon negative electrode material, and has wide market in the fields of energy storage and electric automobiles.

Description

One-dimensional porous silicon-carbon composite negative electrode material, preparation method and application thereof
Technical Field
The invention relates to the field of battery cathode materials, in particular to a one-dimensional porous silicon-carbon composite cathode material, a preparation method and application thereof.
Background
In recent years, with the rapid development of new industrial technologies such as electric vehicles, the demand for high-performance power lithium ion batteries is also pressing. The improvement in performance of lithium ion batteries depends to a large extent on the increase in energy density and cycle life of the lithium intercalation materials. In the research of new anode materials, silicon is attracting more and more attention because of its highest theoretical lithium intercalation capacity (4200 mAh/g). However, under the condition of high-degree lithium intercalation, the silicon-based material has a serious volume expansion problem, so that the cycling stability of the electrode is greatly reduced. The carbon material is used as a buffer framework, and the important research direction of the silicon-carbon material is to compositely improve the mechanical instability of the silicon material in the lithium intercalation and deintercalation process.
Currently, silicon-carbon composite materials are generally prepared by pyrolysis, mechanical mixing/high-energy ball milling and other methods, but the silicon particles are embedded in a compact carbon matrix, structural fracture is easy to occur due to volume expansion of silicon during charge and discharge, and mechanical stress is generated between a silicon-carbon active layer and a rigid copper current collector layer, so that silicon materials are pulverized and peeled off, the battery capacity is sharply reduced, and the cycle capacity is very poor. For example, in patent CN108933250A, a preparation process of a silicon-carbon composite negative electrode material uses silicon powder and porous carbon for composite coating treatment to obtain the silicon-carbon negative electrode material, but the method is limited by the size of the silicon powder and the dispersion process, and it is difficult to really achieve the purpose of inserting the silicon powder into the porous carbon. Patent CN105609730B discloses a preparation method of a silicon/carbon/graphite negative electrode material, which is to spray-dry and pyrolyze silicon powder, an organic carbon source, and graphite to obtain the silicon/carbon/graphite composite negative electrode material, but the first efficiency and cycle performance of the material are not good. Therefore, the development of a novel preparation method of the silicon-carbon composite material is still an important problem to be solved by domestic negative electrode enterprises at present.
In order to effectively relieve the problems of material pulverization, structure collapse and pole piece separation caused by volume expansion of silicon in the charging and discharging processes, the invention provides a one-dimensional porous silicon/carbon composite negative electrode material and a preparation method thereof.
Disclosure of Invention
In order to solve the technical problems, the invention provides a one-dimensional porous silicon-carbon composite negative electrode material, which is characterized in that porous silicon is used as an active ingredient, and silicon/carbon composite fibers are prepared by adopting electrostatic spinning, so that the transmission distance of lithium ions can be effectively shortened, the problem of silicon expansion in the lithium intercalation process is solved, the electrochemical performance of the material is improved, active silicon particles are protected, and the preparation method of the high-performance silicon-carbon composite material and the silicon-carbon composite material are provided, so that the structural stability and the cycling stability of an electrode are greatly improved.
The invention also provides a preparation method of the one-dimensional porous silicon-carbon composite negative electrode material, which has the advantages of simple and feasible process, stable product performance and good application prospect.
The invention adopts the following technical scheme:
a preparation method of a one-dimensional porous silicon-carbon composite anode material comprises the following steps:
(1) mixing nano SiO 2 Mixing with surfactant and high molecular polymer, adding into dispersant, ultrasonically stirring at room temperature for dispersion to obtain spinning solution, and electrostatic spinning to obtain SiO 2 A polymer composite fiber;
(2) SiO obtained in the step (1) 2 The polymer composite fiber is oxidized without melting, then is pre-carbonized at 400-600 ℃ under the protection of inert gas, and is cooledTo obtain SiO 2 A carbon composite fiber;
(3) mixing active metal powder with the SiO obtained in the step (2) according to a certain mass ratio 2 Mixing the/carbon composite fiber, and then reducing part of SiO in the mixed fiber by a thermal reduction method under inert gas 2 Reducing the silicon into a silicon simple substance, and obtaining Si/SiO by acid washing, water washing and drying 2 A carbon composite fiber material;
(4) carrying out hydrofluoric acid pickling, water washing and drying on the Si/carbon composite fiber obtained in the step (3) to remove redundant SiO 2 Forming a structure embedded with porous silicon nano particles in the carbon fiber, finally carrying out high-temperature heat treatment at the temperature of 600-1000 ℃ for 4-8 hours in an inert atmosphere, and cooling to room temperature to obtain the one-dimensional porous silicon/carbon composite cathode material.
The technical proposal is further improved in that in the step (1), the nano SiO is 2 The particle size of (A) is 50-1000 nm; the nano SiO 2 The purity of (A) is more than 99.9%; the surfactant is 1 or the combination of at least 2 of hexadecyl trimethyl ammonium bromide, ethylene glycol, nonylphenol polyoxyethylene ether, hexadecyl pyridine bromide, gamma-aminopropyl triethoxysilane, gamma-glycidyl ether oxypropyl trimethoxysilane, gamma- (methacryloyloxy) propyl trimethoxysilane, 3-methacryloyloxypropyl methyldiethoxysilane or 3-methacryloyloxypropyl methyldimethoxysilane; the high molecular polymer is 1 or the combination of at least 2 of linear high softening point (250-280 ℃) asphalt, polyacrylonitrile, polystyrene, polyvinylpyrrolidone, polyvinyl butyral, polyvinyl alcohol, polymethyl methacrylate, polyvinylidene fluoride, polyurethane and polyimide; the dispersing agent is 1 or the combination of at least 2 of water, ethanol, N-dimethylformamide, tetrahydrofuran, acetone, carbon trichloride and N, N-dimethylacetamide.
The technical proposal is further improved in that in the step (1), the nano SiO is 2 The mass ratio of the surfactant to the high molecular polymer is 10-60:0.5-3: 100; the mass fraction concentration of the high molecular polymer in the spinning solution is 5-15%; the ultrasonic stirring dispersion is carried out at room temperature, the ultrasonic power is more than 50W, and the stirring is carried outThe time is more than 8 h; the electrostatic spinning conditions are as follows: the distance between the injector and the collector is 8-15cm, the voltage is 10-20kV, the diameter of the needle is 0.3-0.8mm, the extrusion rate is 0.5-5.0mL/h, and the collector is metal foil.
The further improvement of the technical proposal is that in the step (2), the oxidation without melting is performed by pre-oxidation for 1-6 hours at the temperature rise rate of 0.5-5 ℃/min to 200-300 ℃; the pre-carbonization is carried out by heating to 400-600 ℃ at a heating rate of 3-5 ℃/min under an inert atmosphere and preserving the heat for 2-6 hours.
The technical proposal is further improved in that in the step (3), the active metal powder is aluminum powder and/or magnesium powder; the mass ratio of the active metal powder to the SiO2 is 5-35: 100; the thermal reduction is carried out by heating to 400-800 ℃ under inert atmosphere for reaction for 2-6 hours; the acid washing and the water washing are carried out by adopting excessive hydrochloric acid solution to react for 1 to 3 hours at the temperature of between 40 and 60 ℃ under stirring, then pure water is used for stirring, washing and filtering until the pH value of the filtrate is between 6.5 and 7.0.
The technical proposal is further improved in that in the step (4), the hydrofluoric acid pickling and water washing adopt excessive hydrofluoric acid solution to stir and react for 0.5 to 2 hours at room temperature, and the residual SiO is removed 2 Then, the solution is stirred, washed and filtered by pure water until the pH value of the filtrate is 6.5-7.0.
The technical proposal is further improved in that in the step (3) and the step (4), the drying is carried out in a blast air or vacuum electric heating drying oven, the drying temperature is 80-120 ℃, and the drying time is 4-12 hours; in the step (4), the temperature of the high-temperature heat treatment is 600-1000 ℃; the heating rate is 3-10 ℃/min; the heat treatment time is 4-8 hours.
In the step (2), the step (3) and the step (4), the inert gas is 1 or at least 2 of nitrogen, helium, neon, argon, krypton and xenon.
The one-dimensional porous silicon-carbon composite negative electrode material is prepared by the preparation method.
An application of a one-dimensional porous silicon-carbon composite cathode material, which is applied to a lithium ion battery cathode material.
The invention has the beneficial effects that:
compared with the prior art, the preparation process is simple, does not need extra coating modification, and is easy for large-scale production; the formation of porous silicon is induced in situ by a metallothermic reduction and etching method, so that the stability of silicon active components can be obviously improved while high reversible capacity is obtained, the intrinsic expansion effect of silicon is improved, and the problems of particle pulverization, structural collapse and the like are avoided; the carbon fiber matrix with small diameter and uniform thickness can be obtained through polymer matrix electrostatic spinning, so that the buffering effect can be better provided for silicon, and the electronic conductivity is improved. The porous silicon/carbon composite anode material has the first reversible specific capacity of more than 750mAh/g, and the first circulating coulombic efficiency of more than 86 percent, has excellent circulating stability, overcomes the problem of poor electrochemical stability of the traditional silicon-carbon anode material, and has wide market in the fields of energy storage and electric automobiles.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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.
Example 1:
SiO with the grain diameter of 100nm 2 Adding cetyltrimethylammonium bromide and polyacrylonitrile (Mw180000) into N, N-dimethylformamide solvent according to the mass ratio of 20:1:100, keeping the solid content of polyacrylonitrile at 8%, then stirring for 12 hours under the ultrasonic power of 80W to obtain spinning solution, and obtaining SiO by adopting electrostatic spinning (the distance between an injector and a collector is 10cm, the voltage is 20kV, the diameter of a needle is 0.5mm, the extrusion rate is 3mL/h, and the collector is aluminum foil) 2 A/polyacrylonitrile composite fiber; taking down the fiber self-supporting body film block containing the silicon source, placing the fiber self-supporting body film block into a muffle furnace, and pre-oxidizing the fiber self-supporting body film block for 4 hours at 250 DEG CThen heating to 600 ℃ at the heating rate of 3 ℃/min under the protection of nitrogen for pre-carbonization for 2 hours to obtain SiO 2 A/carbon composite fiber precursor, and mixing the precursor with magnesium powder (wherein the magnesium powder and SiO in the precursor) 2 The mass ratio of (1) to (2) is 12:100), putting the mixture into an atmosphere furnace, heating the mixture to 750 ℃ in an argon atmosphere, keeping the temperature for 4 hours, washing the reaction product with excessive hydrochloric acid, washing the reaction product with water to be neutral (pH 7), and drying the reaction product to obtain a silicon-rich precursor; etching the silicon-rich precursor by hydrofluoric acid, washing the silicon-rich precursor to be neutral (pH is 7) by water, and drying to obtain a porous silicon/carbon precursor; and carbonizing the precursor at 950 ℃ for 4 hours under the protection of nitrogen, and cooling to room temperature to obtain the one-dimensional porous silicon/carbon composite anode material.
Example 2:
SiO with the grain diameter of 100nm 2 Adding gamma-aminopropyltriethoxysilane and polyvinylpyrrolidone (Mw1300000) into an ethanol solvent according to the mass ratio of 30:1:100, keeping the solid content of polyacrylonitrile to be 8%, stirring for 12 hours under the ultrasonic power of 80W to obtain a spinning solution, and obtaining SiO by adopting electrostatic spinning (the distance between an injector and a collector is 10cm, the voltage is 20kV, the diameter of a needle is 0.5mm, the extrusion rate is 5mL/h, and the collector is an aluminum foil) 2 A polyacrylonitrile composite fiber; taking down the whole fiber self-supporting body membrane containing a silicon source, placing the whole fiber self-supporting body membrane into a muffle furnace, pre-oxidizing the whole fiber self-supporting body membrane for 4 hours at 250 ℃, then heating the whole fiber self-supporting body membrane to 600 ℃ at a heating rate of 3 ℃/min under the protection of nitrogen, and pre-carbonizing the whole fiber self-supporting body membrane for 2 hours to obtain SiO 2 A/carbon composite fiber precursor, and mixing the precursor with magnesium powder (wherein the magnesium powder and SiO in the precursor) 2 The mass ratio of 15:100), placing the mixture into an atmosphere furnace, heating the mixture to 750 ℃ in an argon atmosphere, keeping the temperature for 4 hours, washing the reaction product with excessive hydrochloric acid, washing the reaction product with water to be neutral (pH 7) and drying the reaction product to obtain a silicon-rich precursor; etching the silicon-rich precursor by hydrofluoric acid, washing the silicon-rich precursor to be neutral (pH is 7) by water, and drying to obtain a porous silicon/carbon precursor; and carbonizing the precursor at 950 ℃ for 4 hours under the protection of nitrogen, and cooling to room temperature to obtain the one-dimensional porous silicon/carbon composite anode material.
Example 3:
SiO with the grain diameter of 100nm 2 Gamma-aminopropyltriethoxysilane,Adding polyvinyl alcohol (Mw120000) into ethanol solvent at a mass ratio of 40:1:100, keeping the solid content of polyacrylonitrile at 8%, stirring at 80W ultrasonic power for 12 hr to obtain spinning solution, and performing electrostatic spinning (injector-collector distance is 10cm, voltage is 20kV, needle diameter is 0.5mm, extrusion rate is 3mL/h, collector is aluminum foil) to obtain SiO 2 A/polyacrylonitrile composite fiber; taking down the whole fiber self-supporting body membrane containing a silicon source, placing the whole fiber self-supporting body membrane into a muffle furnace, pre-oxidizing the whole fiber self-supporting body membrane for 4 hours at 250 ℃, then heating the whole fiber self-supporting body membrane to 600 ℃ at a heating rate of 3 ℃/min under the protection of nitrogen, and pre-carbonizing the whole fiber self-supporting body membrane for 2 hours to obtain SiO 2 A/carbon composite fiber precursor, and magnesium powder (wherein the magnesium powder and SiO in the precursor) 2 The mass ratio of the components is 20:100), putting the mixture into an atmosphere furnace, heating the mixture to 750 ℃ in an argon atmosphere, keeping the temperature for 4 hours, washing the reaction product with excessive hydrochloric acid, washing the reaction product with water to be neutral (pH is 7), and drying the reaction product to obtain a silicon-rich precursor; etching the silicon-rich precursor by hydrofluoric acid, washing the silicon-rich precursor to be neutral (pH is 7) and drying to obtain a porous silicon/carbon precursor; and carbonizing the precursor at 950 ℃ for 4 hours under the protection of nitrogen, and cooling to room temperature to obtain the one-dimensional porous silicon/carbon composite anode material.
Example 4:
SiO with the particle size of 200nm 2 Adding cetyltrimethylammonium bromide and polyacrylonitrile (Mw180000) into N, N-dimethylformamide solvent according to the mass ratio of 40:1:100, keeping the solid content of polyacrylonitrile at 8%, then stirring for 12 hours under the ultrasonic power of 80W to obtain spinning solution, and obtaining SiO by adopting electrostatic spinning (the distance between an injector and a collector is 10cm, the voltage is 20kV, the diameter of a needle is 0.5mm, the extrusion rate is 5mL/h, and the collector is aluminum foil) 2 A/polyacrylonitrile composite fiber; taking down the whole fiber self-supporting body membrane containing a silicon source, placing the whole fiber self-supporting body membrane into a muffle furnace, pre-oxidizing the whole fiber self-supporting body membrane for 4 hours at 250 ℃, then heating the whole fiber self-supporting body membrane to 600 ℃ at a heating rate of 3 ℃/min under the protection of nitrogen, and pre-carbonizing the whole fiber self-supporting body membrane for 2 hours to obtain SiO 2 A/carbon composite fiber precursor, and mixing the precursor with magnesium powder (wherein the magnesium powder and SiO in the precursor) 2 In a mass ratio of 20:100), placing the mixture into an atmosphere furnace, heating the mixture to 750 ℃ in an argon atmosphere, keeping the temperature for 4 hours, and passing the reaction product through a reaction furnaceWashing with hydrochloric acid, washing with water to neutrality (pH 7), and drying to obtain silicon-rich precursor; etching the silicon-rich precursor by hydrofluoric acid, washing the silicon-rich precursor to be neutral (pH is 7) by water, and drying to obtain a porous silicon/carbon precursor; and carbonizing the precursor at 950 ℃ for 4 hours under the protection of nitrogen, and cooling to room temperature to obtain the one-dimensional porous silicon/carbon composite anode material.
Example 5:
SiO with the grain diameter of 300nm 2 Adding cetyltrimethylammonium bromide and polyacrylonitrile (Mw180000) into N, N-dimethylformamide solvent according to the mass ratio of 40:1:100, keeping the solid content of polyacrylonitrile at 8%, then stirring for 12 hours under the ultrasonic power of 80W to obtain spinning solution, and obtaining SiO by adopting electrostatic spinning (the distance between an injector and a collector is 10cm, the voltage is 20kV, the diameter of a needle is 0.5mm, the extrusion rate is 3mL/h, and the collector is aluminum foil) 2 A/polyacrylonitrile composite fiber; taking down the whole fiber self-supporting body membrane containing a silicon source, placing the whole fiber self-supporting body membrane into a muffle furnace, pre-oxidizing the whole fiber self-supporting body membrane for 4 hours at 250 ℃, then heating the whole fiber self-supporting body membrane to 600 ℃ at a heating rate of 3 ℃/min under the protection of nitrogen, and pre-carbonizing the whole fiber self-supporting body membrane for 2 hours to obtain SiO 2 A/carbon composite fiber precursor, and mixing the precursor with magnesium powder (wherein the magnesium powder and SiO in the precursor) 2 The mass ratio of the components is 20:100), putting the mixture into an atmosphere furnace, heating the mixture to 750 ℃ in an argon atmosphere, keeping the temperature for 4 hours, washing the reaction product with excessive hydrochloric acid, washing the reaction product with water to be neutral (pH is 7), and drying the reaction product to obtain a silicon-rich precursor; etching the silicon-rich precursor by hydrofluoric acid, washing the silicon-rich precursor to be neutral (pH is 7) and drying to obtain a porous silicon/carbon precursor; and carbonizing the precursor at 950 ℃ for 4 hours under the protection of nitrogen, and cooling to room temperature to obtain the one-dimensional porous silicon/carbon composite anode material.
Comparative example:
SiO with the grain diameter of 300nm 2 Adding cetyltrimethylammonium bromide and polyacrylonitrile (Mw180000) into an N, N-dimethylformamide solvent according to the mass ratio of 30:1:100, keeping the solid content of the polyacrylonitrile at 8%, stirring for 12 hours under the ultrasonic power of 80W to obtain a spinning solution, performing electrostatic spinning (the distance between an injector and a collector is 10cm, the voltage is 20kV, the diameter of a needle is 0.5mm, the extrusion rate is 3 mL/h), and collectingAluminum foil) to obtain SiO 2 A polyacrylonitrile composite fiber; taking down the whole fiber self-supporting body film containing the silicon source, placing the whole fiber self-supporting body film into a muffle furnace to be pre-oxidized for 4 hours at 250 ℃, then heating to 600 ℃ at a heating rate of 3 ℃/min under the protection of nitrogen to be pre-carbonized for 2 hours to obtain SiO 2 A carbon composite fiber precursor; and carbonizing the precursor at 950 ℃ for 4 hours under the protection of nitrogen, and cooling to room temperature to obtain the contrast material.
The silicon/carbon composite materials in examples 1 to 5 and the comparative example were subjected to the first specific capacity, the first coulombic efficiency and the cycle performance test by the half-cell test method, and the results are shown in table 1. The testing method of the half cell comprises the following steps: the electrochemical performance test is carried out by adopting the following method: taking the materials prepared in the embodiments 1-5 and the comparative example as negative electrode materials, mixing the negative electrode materials with a thickening agent CMC, a binder SBR and a conductive agent (Super-P) according to a mass ratio of 85:2:3:10, adding a proper amount of deionized water as a dispersing agent to prepare slurry, coating the slurry on a copper foil, and rolling and vacuum drying the slurry to prepare a negative electrode sheet; a CR2032 button half cell was prepared by using 1mol/L LiPF6 three-component mixed solvent according to EC: DMC: EMC 1:1:1(V/V) and adding 5% VC mixed electrolyte, using Celgard polypropylene microporous membrane as a diaphragm and lithium sheet as a counter electrode in an argon-protected glove box. The charge and discharge test of the button cell is carried out on a LAND cell test system of Wuhanjinnuo electronic Limited company, and under the normal temperature condition, the constant current charge and discharge is firstly activated at 0.1C, and then the charge and discharge are cycled for 500 times at 1C, and the charge and discharge voltage is 0.005-2.0V.
TABLE 1
Figure BDA0002827948720000081
As can be seen from the examples in table 1, the reversible capacity of the silicon/carbon composite material of the present invention can be selectively controlled by the introduced amount of the silicon source, the capacity is higher than 750mAh/g, the first coulombic efficiency is higher than 86%, and after 500 charge-discharge cycles, the electrode capacity retention rate is higher than 84%, which is much higher than that of the comparative example.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.

Claims (10)

1. A preparation method of a one-dimensional porous silicon-carbon composite anode material is characterized by comprising the following steps:
(1) mixing nano SiO 2 Mixing with surfactant and high molecular polymer, adding into dispersant, ultrasonically stirring at room temperature for dispersion to obtain spinning solution, and electrostatic spinning to obtain SiO 2 A polymer composite fiber;
(2) SiO obtained in the step (1) 2 The polymer composite fiber is oxidized without melting, then is pre-carbonized at the temperature of 400-600 ℃ under the protection of inert gas, and SiO is obtained after temperature reduction 2 A carbon composite fiber; the oxidation non-melting is to pre-oxidize for 1-6 hours at the temperature rising rate of 0.5-5 ℃/min to 200-300 ℃ in the air atmosphere;
(3) mixing active metal powder with the SiO obtained in the step (2) according to a certain mass ratio 2 Mixing the/carbon composite fiber, and then reducing part of SiO in the mixed fiber by a thermal reduction method under inert gas 2 Reducing the silicon into a silicon simple substance, and then pickling, washing and mixingDrying to obtain Si/SiO 2 A carbon composite fiber material;
(4) the Si/SiO obtained in the step (3) 2 The/carbon composite fiber is subjected to hydrofluoric acid pickling, water washing and drying to remove redundant SiO 2 Forming a structure embedded with porous silicon nano particles in carbon fibers, finally carrying out high-temperature heat treatment at the temperature of 600-1000 ℃ for 4-8 hours in an inert atmosphere, and cooling to room temperature to obtain the one-dimensional porous silicon/carbon composite cathode material;
the nano SiO 2 The mass ratio of the surfactant to the high molecular polymer is 10-60:0.5-3: 100; the mass fraction concentration of the high molecular polymer in the spinning solution is 5-15%;
the active metal powder is aluminum powder and/or magnesium powder; the active metal powder and SiO 2 The mass ratio of (A) to (B) is 5-35: 100.
2. The preparation method of the one-dimensional porous silicon-carbon composite anode material as claimed in claim 1, wherein in the step (1), the nano SiO is 2 The particle size of (A) is 50-1000 nm; the nano SiO 2 The purity of (A) is more than 99.9%; the surfactant is 1 or the combination of at least 2 of hexadecyl trimethyl ammonium bromide, ethylene glycol, nonylphenol polyoxyethylene ether, hexadecyl pyridine bromide, gamma-aminopropyl triethoxysilane, gamma-glycidyl ether oxypropyl trimethoxysilane, gamma- (methacryloyloxy) propyl trimethoxysilane, 3-methacryloyloxypropyl methyldiethoxysilane or 3-methacryloyloxypropyl methyldimethoxysilane; the high molecular polymer is 1 or the combination of at least 2 of linear high-softening-point asphalt, polyacrylonitrile, polystyrene, polyvinylpyrrolidone, polyvinyl butyral, polyvinyl alcohol, polymethyl methacrylate, polyvinylidene fluoride, polyurethane and polyimide; the dispersing agent is 1 or the combination of at least 2 of water, ethanol, N-dimethylformamide, tetrahydrofuran, acetone, carbon trichloride and N, N-dimethylacetamide.
3. The preparation method of the one-dimensional porous silicon-carbon composite anode material according to claim 1, wherein in the step (1), the ultrasonic stirring dispersion is performed at room temperature, the ultrasonic power is greater than 50W, and the stirring time is greater than 8 h; the electrostatic spinning conditions are as follows: the distance between the injector and the collector is 8-15cm, the voltage is 10-20kV, the diameter of the needle is 0.3-0.8mm, the extrusion rate is 0.5-5.0mL/h, and the collector is metal foil.
4. The method for preparing a one-dimensional porous Si-C composite anode material as claimed in claim 1, wherein in the step (2), the pre-carbonization is performed by heating to 400-600 ℃ at a heating rate of 3-5 ℃/min under an inert atmosphere and maintaining the temperature for 2-6 hours.
5. The method for preparing a one-dimensional porous Si-C composite anode material as claimed in claim 1, wherein the thermal reduction is carried out by heating to 400-800 ℃ in an inert atmosphere for 2-6 hours; the acid washing and the water washing are carried out by adopting excessive hydrochloric acid solution to react for 1 to 3 hours at the temperature of between 40 and 60 ℃ under stirring, then pure water is used for stirring, washing and filtering until the pH value of the filtrate is between 6.5 and 7.0.
6. The method for preparing the one-dimensional porous silicon-carbon composite anode material according to claim 1, wherein in the step (4), the hydrofluoric acid pickling and water washing are performed by stirring and reacting an excessive hydrofluoric acid solution at room temperature for 0.5-2 hours to remove the remaining SiO 2 Then, the solution is stirred, washed and filtered by pure water until the pH value of the filtrate is 6.5-7.0.
7. The preparation method of the one-dimensional porous silicon-carbon composite anode material as claimed in claim 1, wherein in the steps (3) and (4), the drying is carried out in a blowing or vacuum electric heating drying oven, the drying temperature is 80-120 ℃, and the drying time is 4-12 hours; in the step (4), the temperature of the high-temperature heat treatment is 600-1000 ℃; the heating rate is 2 ℃/min; the heat treatment time is 4-8 hours.
8. The method for preparing a one-dimensional porous silicon-carbon composite anode material according to claim 1, wherein in the step (2), the step (3) and the step (4), the inert gas is 1 or a combination of at least 2 of nitrogen, helium, neon, argon, krypton and xenon.
9. A one-dimensional porous silicon-carbon composite anode material, which is characterized by being prepared by the preparation method of any one of claims 1 to 8.
10. The application of the one-dimensional porous silicon-carbon composite negative electrode material is characterized in that the one-dimensional porous silicon-carbon composite negative electrode material of claim 9 is applied to a lithium ion battery negative electrode material.
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