CN115472813A - Preparation method of porous silicon/metal/carbon nano material composite anode material of lithium ion battery - Google Patents

Preparation method of porous silicon/metal/carbon nano material composite anode material of lithium ion battery Download PDF

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CN115472813A
CN115472813A CN202211168147.2A CN202211168147A CN115472813A CN 115472813 A CN115472813 A CN 115472813A CN 202211168147 A CN202211168147 A CN 202211168147A CN 115472813 A CN115472813 A CN 115472813A
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silicon
metal
porous silicon
carbon nano
lithium ion
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席风硕
李绍元
马文会
魏奎先
万小涵
陈正杰
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Kunming University of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a preparation method of a porous silicon/metal/carbon nano material composite cathode material of a lithium ion battery, belonging to the technical field of lithium ion battery cathodes. Crushing and finely grinding a silicon material to obtain silicon powder, cleaning with deionized water or an acid solution, carrying out solid-liquid separation, and drying the solid to obtain pretreated silicon powder; adding pretreated silicon powder into a hydrofluoric acid-alcohol mixed solution containing catalytic metal salt, depositing catalytic metal nanoparticles, adding an oxidant to perform metal-assisted chemical etching so as to introduce a porous structure on the silicon powder and embed the catalytic metal nanoparticles, performing solid-liquid separation, and drying solids to obtain a porous silicon/catalytic metal composite material; and placing the porous silicon/catalytic metal composite material in a CVD (chemical vapor deposition) furnace, vacuumizing or introducing protective gas to drive air in the furnace chamber, opening a deposition gas-carrier gas inlet valve to perform chemical vapor deposition carbon, and performing air cooling to room temperature to obtain the porous silicon/metal/carbon nano material composite anode material.

Description

Preparation method of porous silicon/metal/carbon nano material composite anode material of lithium ion battery
Technical Field
The invention relates to a preparation method of a porous silicon/metal/carbon nano material composite cathode material of a lithium ion battery, belonging to the technical field of lithium ion battery cathodes.
Background
In the current lithium ion battery material system, the traditional low theoretical specific capacity (372 mAh/g) of the graphite negative electrode causes an obvious bottleneck in the aspect of improving the energy density of the lithium battery, and the silicon material is considered to be the preferred material of the next generation of high specific capacity lithium battery negative electrode by virtue of the advantages of high theoretical specific capacity, moderate working voltage, rich resource storage capacity, high safety and the like. However, the silicon material undergoes huge volume expansion and is prone to undergo side reaction with an electrolyte during charge and discharge to form an unstable SEI film, which leads to reduction of electrochemical performance and capacity fading of the silicon negative electrode. In addition, silicon materials also have a problem of low conductivity. Due to the problems, when the silicon-based material is used as a negative electrode of a lithium battery, the capacity loss is fast, the initial coulombic efficiency is low, and the electrochemical performance is poor. Researchers find that the problems of volume expansion and poor conductivity of the silicon negative electrode material can be effectively solved by carrying out porous design and composite treatment on the silicon material. The porous silicon is a unique structure, and the internal void space provides additional space for the volume expansion of the silicon negative electrode and effectively releases the stress and strain caused by volume change, thereby being beneficial to maintaining the stability of the electrode structure without pulverization. The introduction of conductive materials such as carbon or metal materials into the silicon-based materials or the formation of silicon-based alloys with the conductive materials is also a mainstream method for improving the poor conductivity and electrochemical properties of silicon materials, mainly because the carbon and metal have good conductivity, the electronic conductivity of silicon can be effectively improved, and a buffer space is provided for the volume expansion of silicon to a certain extent, so that the electrochemical properties of the silicon-based negative electrode materials are improved.
At present, the silicon-carbon composite cathode prepared by doping a small amount of silicon into a graphite material is preliminarily applied to industrialization, but the capacity of the silicon-carbon composite cathode is improved to a limited extent. Researchers compound silicon materials with carbon nanomaterials (carbon nanotubes, graphene and the like) according to unique microstructures and excellent physical and chemical properties of the carbon nanomaterials to improve the electrochemical properties of silicon-based negative electrodes. For example, in the high-first-efficiency graphene composite silicon-carbon negative electrode material, the preparation method thereof and the battery, the graphene material is introduced to try to improve the first coulomb efficiency of the prepared silicon-carbon negative electrode material; according to the porous spherical graphene-coated silicon negative electrode composite material and the preparation method thereof, on the basis of introducing a graphene material, graphene is further modified into porous spherical graphene to coat a silicon material to form a high-performance silicon-based composite negative electrode material; in the silicon-carbon nanotube composite negative electrode material and the preparation method thereof, the introduction of the carbon nanotube has obvious effect of improving the electrochemical performance of the silicon negative electrode. Some problems of the silicon-based negative electrode of the lithium ion battery at present can be effectively overcome by introducing the carbon nano material, but part of the carbon nano material has the problem of poor conductivity and the methods often lack good synergy, so that the silicon/carbon nano composite negative electrode material is still difficult to be applied on a large scale.
Disclosure of Invention
The invention provides a preparation method of a porous silicon/metal/carbon nano-material composite cathode material of a lithium ion battery aiming at the problems of poor conductivity and poor electrochemical performance of a silicon/carbon nano-composite cathode material, and the preparation method skillfully utilizes a metal-assisted chemical etching method to realize the introduction of a porous structure and the embedding of catalytic metal nano-particles into a silicon material in one step; the porous silicon/metal/carbon nano material composite material is prepared by carrying out carbon source chemical vapor deposition on the porous silicon/metal composite material and growing a carbon nano material under the action of catalytic metal, so that the silicon-based negative electrode material of the lithium ion battery with excellent electrochemical performance is obtained.
A preparation method of a porous silicon/metal/carbon nano material composite negative electrode material of a lithium ion battery comprises the following specific steps:
(1) Crushing and finely grinding the silicon material to obtain silicon powder, cleaning with deionized water or an acid solution, carrying out solid-liquid separation, and drying the solid to obtain pretreated silicon powder;
(2) Adding pretreated silicon powder into a hydrofluoric acid-alcohol mixed solution containing catalytic metal salt, depositing catalytic metal nano particles, adding an oxidant to perform metal-assisted chemical etching so as to introduce a porous structure on the silicon powder and embed the catalytic metal nano particles, performing solid-liquid separation, and drying the solid to obtain a porous silicon/catalytic metal composite material;
(3) And (3) placing the porous silicon/catalytic metal composite material in a CVD furnace, vacuumizing or introducing protective gas to drive the air in the furnace chamber to be clean, opening a deposition gas-carrier gas inlet valve to perform chemical vapor deposition of carbon, and performing air cooling to room temperature to obtain the porous silicon/metal/carbon nano material composite cathode material.
The silicon material in the step (1) is high-purity silicon, industrial silicon or regenerated silicon material, and the particle size of the silicon powder is 0.01-10 mu m.
The regenerated silicon material comprises silicon wafer cutting waste materials in the photovoltaic industry, waste photovoltaic modules, waste silicon slag and organic silicon waste materials.
The concentration of the acid solution in the step (1) is 0.1-10 mol/L.
The acid solution is HCl and H 2 SO 4 、HNO 3 One or more of HF and acetic acid.
The catalytic metal salt in the step (2) is Co (NO) 3 ) 2 、CoSO 4 、AgNO 3 、Fe(NO 3 ) 3 、NiSO 4 、Ni(NO 3 ) 2 、C 2 H 2 NiO 4 、Cu(NO 3 ) 2 、CuCl 2 Or CuSO 4 The alcohol is methanol, ethanol or ethylene glycol, and the oxidant is H 2 O 2 、HNO 3 、KMnO 4 Or Na 2 S 2 O 8 。
In the step (2), the concentration of the catalytic metal salt is 0.01-10 mol/L, the concentration of the alcohol is 5-50 wt%, the concentration of HF is 0.1-10 mol/L, the concentration of the oxidant is 0.01-10 mol/L, and the liquid-solid ratio mL/g of the hydrofluoric acid-alcohol mixed solution to the silicon powder is (3-60): 1.
The deposition temperature in the step (2) is 0-80 ℃.
The deposition gas in the step (3) is CH 4 、C 2 H 6 、C 3 H 8 、C 4 H 10 、CO 2 、CO、CH 2 O、C 2 H 2 、C 2 H 4 、C 4 H 8 、C 3 H 6 、C 3 H 4 The carrier gas is one or more of hydrogen, argon or nitrogen, and the carbon nanotube structure material is easily generated when the carrier gas contains hydrogen; the mass concentration of the deposition gas in the deposition gas-carrier gas is 1-50 wt%, and the flow rate of the deposition gas-carrier gas is 10-500 mL/min.
The chemical vapor deposition temperature is 300-1100 ℃, and the time is 0.5-10 h.
The CVD furnace is provided with a rotating device, and the rotating speed in the chemical vapor deposition process is 0-60 r/min.
The CVD furnace has a plasma function and a fluidized bed function, and the protective gas is argon or nitrogen.
The preparation principle of the porous silicon/metal/carbon nano material composite anode material is as follows:
after the catalytic metal salt is dissolved in the mixed solution system, depositing catalytic metal particles on the surface of the silicon substrate to form a galvanic cell between the silicon substrate and the catalytic metal; in the primary battery system, the catalytic metal is a micro cathode, the silicon substrate is an anode, an oxidant in the etching solution is reduced under the action of the catalytic metal, silicon in contact with the bottom of the catalytic metal is oxidized, electrons provided by the oxidation of the silicon further promote the reduction of oxidized species, so that a spontaneous electrochemical reaction is formed on the surface of the silicon, the continuous progress of the oxidation-reduction reaction causes the continuous oxidation of the silicon substrate at the bottom of the catalytic metal, the oxidized silicon is further dissolved under the action of hydrofluoric acid, so that catalytic metal particles continuously 'sink' into the silicon substrate, and a porous structure is formed on the silicon substrate and embedded with the catalytic metal. In the CVD vapor deposition process, under the action of the catalytic metal, the carbon source gas is converted into the carbon nano material and effectively grows on the porous silicon to form the porous silicon/metal/carbon nano material composite material.
The invention has the beneficial effects that:
(1) The invention skillfully utilizes a metal-assisted chemical etching method to realize the introduction of a porous structure and the effective and uniform embedding of catalytic metal in the silicon material in one step; the catalytic metal embedded into the silicon material can promote the direct growth of the carbon nanostructure material on the porous silicon material, and further improve the conductivity of the silicon-based negative electrode material;
(2) According to the invention, the MACE etching technology is skillfully integrated into the CVD preparation of the silicon-based composite anode material, the conditions are controllable, the equipment requirement is simple, the operation is easy, the batch production is easy to realize, the high-efficiency preparation of the high-performance porous silicon/metal/carbon nano-material composite anode material of the lithium ion battery can be realized, and the electrochemical performance of the silicon-based anode material is obviously improved.
Drawings
FIG. 1 is a transmission electron microscope topography of the porous silicon/copper/graphene composite anode material of example 1;
FIG. 2 is a transmission electron microscope topography of the porous silicon/nickel/graphene-carbon nanotube composite anode material of example 2;
FIG. 3 is a transmission electron microscope topography of the porous silicon/silver/graphene composite anode material of example 3;
FIG. 4 is a transmission electron microscope topography of the porous silicon/cobalt/graphene-carbon nanotube composite anode material of example 4;
FIG. 5 is a transmission electron microscope topography of the porous silicon/iron/graphene-carbon nanotube composite anode material of example 5.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Example 1: a preparation method of a porous silicon/metal/carbon nano material composite negative electrode material of a lithium ion battery comprises the following specific steps:
(1) Crushing and finely grinding high-purity silicon to obtain silicon powder with the particle size of less than 1 mu m, washing with deionized water, carrying out solid-liquid separation, and drying the solid to obtain pretreated silicon powder;
(2) Adding the pretreated silicon powder into the catalyst containing metal salt (Cu (NO) 3 ) 2 ) In the hydrofluoric acid-ethanol mixed solution, catalytic metal nano-copper particles are deposited at the temperature of 20 ℃, and then oxidant (0.5 mol/L H) is added 2 O 2 ) Metal assisted chemical etching is carried out to introduce a porous structure on the silicon powder and embed catalytic metal nano copper particlesCarrying out solid-liquid separation on particles, and drying the solid to obtain the porous silicon/catalytic metal composite material; wherein the catalytic metal salt (Cu (NO) in the hydrofluoric acid-ethanol mixed solution 3 ) 2 ) The concentration of the acid is 1mol/L, HF, the concentration of the acid is 4mol/L, the ethanol content is 15wt%, and the liquid-solid ratio mL of the hydrofluoric acid-ethanol mixed solution to the silicon powder is 8:1;
(3) Placing the porous silicon/catalytic metal composite material in a CVD furnace, evacuating and purging the air in the furnace chamber, opening a deposition gas-carrier gas inlet valve, and introducing into the CVD furnace at a flow rate of 10mL/min to remove CH 10wt% 4 Carrying out chemical vapor deposition on the mixed gas of 90wt% of argon for 2h at the temperature of 600 ℃ and the rotation rate of 10r/min, and air-cooling to room temperature to obtain the porous silicon/copper/graphene composite anode material;
the topography of the porous silicon/copper/graphene composite material under a transmission electron microscope is shown in fig. 1, and as can be seen from fig. 1, a large amount of graphene material grows on the porous silicon, and meanwhile, copper nanoparticles are distributed in the silicon;
an electrode plate prepared from the porous silicon/copper/graphene composite material, a conductive agent carbon black and a sodium alginate binder according to a mass ratio of 70; the first discharge capacity is up to 2538mAh/g, the first coulombic efficiency can be up to 85.6%, the reversible capacity after 100 cycles still keeps 2103mAh/g, the capacity retention rate is up to 82.9%, and the battery has excellent battery performance.
Example 2: a preparation method of a porous silicon/metal/carbon nano material composite negative electrode material of a lithium ion battery comprises the following specific steps:
(1) Crushing and finely grinding high-purity silicon to obtain silicon powder with the particle size smaller than 1 mu m, soaking and cleaning the silicon powder for 30min by adopting hydrofluoric acid with the concentration of 1mol/L, cleaning the silicon powder by using deionized water, carrying out solid-liquid separation, and drying the solid to obtain pretreated silicon powder;
(2) Adding the pretreated silicon powder into the catalyst-containing metal salt (Ni (NO) 3 ) 2 ) Depositing catalytic metal nano nickel particles in the hydrofluoric acid-methanol mixed solution at the temperature of 60 ℃, and adding an oxidant (1 mol/L HNO) 3 ) Metal assisted chemical etching to introduce porosity on silicon powderEmbedding catalytic metal nano nickel particles into the structure, performing solid-liquid separation, and drying the solid to obtain a porous silicon/catalytic metal composite material; wherein the catalytic metal salt (Ni (NO) in the hydrofluoric acid-methanol mixed solution 3 ) 2 ) The concentration of 2mol/L, HF is 4mol/L, the methanol content is 20wt%, and the liquid-solid ratio mL of the hydrofluoric acid-methanol mixed solution to the silicon powder is 10;
(3) Placing the porous silicon/catalytic metal composite material in a CVD furnace, vacuumizing to drive out the air in the furnace cavity, opening a deposition gas-carrier gas inlet valve, and introducing the gas at a flow rate of 500mL/min to the atmosphere containing 2.5wt% 2 H 6 Carrying out chemical vapor deposition on a mixed gas of 7.5wt% of hydrogen and 90wt% of argon for 10 hours at the temperature of 300 ℃ without rotation, and air-cooling to room temperature to obtain a porous silicon/nickel/graphene-carbon nanotube composite cathode material;
the morphology of the porous silicon/nickel/graphene-carbon nanotube composite material under a transmission electron microscope is shown in fig. 2, and as can be seen from fig. 2, graphene and carbon nanotube materials grow on porous silicon, and nickel particles are distributed in the silicon;
an electrode slice prepared from the porous silicon/nickel/graphene-carbon nanotube composite material, a conductive agent carbon black and a sodium alginate binder according to a mass ratio of 70; the first discharge capacity is 2328mAh/g, the first coulombic efficiency is 84.2%, the reversible capacity after 100 cycles still keeps 1984mAh/g, the capacity retention rate is 85.2%, and the battery performance is excellent.
Example 3: a preparation method of a porous silicon/metal/carbon nano material composite negative electrode material of a lithium ion battery comprises the following specific steps:
(1) Crushing and finely grinding high-purity silicon to obtain silicon powder with the particle size of less than 1 mu m, cleaning with deionized water, carrying out solid-liquid separation, and drying the solid to obtain pretreated silicon powder;
(2) Adding the pretreated silicon powder into the catalyst-containing metal salt (AgNO) 3 ) In the hydrofluoric acid-ethanol mixed solution, catalytic metal nano silver particles are deposited at the temperature of 0 ℃, and then oxidant (0.5 mol/L Na) is added 2 S 2 O 8 ) Carrying out metal-assisted chemical etching to introduce a porous structure on the silicon powder and embed catalytic metal nano silver particles, carrying out solid-liquid separation, and drying the solid to obtain a porous silicon/catalytic metal composite material; wherein the catalytic metal salt (AgNO) is in the mixed solution of hydrofluoric acid and ethanol 3 ) The concentration of the acid is 0.01mol/L, HF, the concentration of the acid is 4mol/L, the ethanol content is 5wt%, and the liquid-solid ratio mL of the hydrofluoric acid-ethanol mixed solution to the silicon powder is 5:1;
(3) Placing the porous silicon/catalytic metal composite material in a CVD furnace, introducing nitrogen to drive out the air in the furnace cavity, opening a deposition gas-carrier gas inlet valve, introducing the gas at a flow rate of 200mL/min to the atmosphere containing 15wt% CH 4 Carrying out chemical vapor deposition on the mixed gas of 85wt% of nitrogen for 0.5h at the temperature of 1100 ℃ and at the rotation rate of 20r/min, and air-cooling to room temperature to obtain the porous silicon/silver/graphene nano material composite negative electrode material;
the morphology of the porous silicon/silver/graphene composite material under a transmission electron microscope is shown in fig. 3, and as can be seen from fig. 3, a large amount of graphene materials grow on the porous silicon, and meanwhile, the silver nanoparticles are distributed in the silicon;
an electrode plate prepared from the porous silicon/silver/graphene composite material, a conductive agent carbon black and a sodium alginate binder according to a mass ratio of 70; the first discharge capacity is up to 2745mAh/g, the first coulombic efficiency is up to 87.6%, the reversible capacity after 100 cycles still keeps 2333mAh/g, the capacity retention rate is up to 85.0%, and the battery has excellent battery performance.
Example 4: a preparation method of a porous silicon/metal/carbon nano material composite negative electrode material of a lithium ion battery comprises the following specific steps:
(1) Crushing and finely grinding high-purity silicon to obtain silicon powder with the particle size of less than 5 microns, soaking and cleaning the silicon powder for 30min by adopting hydrofluoric acid with the concentration of 2mol/L, cleaning the silicon powder by using deionized water, carrying out solid-liquid separation, and drying the solid to obtain pretreated silicon powder;
(2) Adding the pretreated silicon powder into the catalyst containing metal salt (Co (NO) 3 ) 2 ) In the mixed solution of hydrofluoric acid and glycol at a temperature of 80 DEG CCatalytic metal nanometer cobalt particles are added with an oxidant (0.5 mol/L H) 2 O 2 ) Carrying out metal-assisted chemical etching to introduce a porous structure on the silicon powder and embed catalytic metal nano cobalt particles, carrying out solid-liquid separation, and drying the solid to obtain a porous silicon/catalytic metal composite material; wherein the metal salt (Co (NO) is catalyzed in the hydrofluoric acid-ethylene glycol mixed solution 3 ) 2 ) The concentration of 1mol/L, HF acid is 6mol/L, the content of ethylene glycol is 10wt%, and the liquid-solid ratio mL of the hydrofluoric acid-ethylene glycol mixed solution to the silicon powder is 20;
(3) Placing the porous silicon/catalytic metal composite material in a CVD furnace, vacuumizing to drive out the air in the furnace cavity, opening a deposition gas-carrier gas inlet valve, introducing the gas at a flow rate of 100mL/min to the atmosphere containing 5wt% 2 H 2 Carrying out chemical vapor deposition on a mixed gas of 15wt% of hydrogen and 80wt% of argon for 1h at the temperature of 800 ℃ and the rotation rate of 15r/min, and air-cooling to room temperature to obtain the porous silicon/cobalt/graphene-carbon nanotube composite anode material;
the morphology of the porous silicon/cobalt/graphene-carbon nanotube composite material under a transmission electron microscope is shown in fig. 4, and as can be seen from fig. 4, graphene and carbon nanotube materials grow on porous silicon, and cobalt particles are distributed on the silicon;
an electrode slice prepared from the porous silicon/cobalt/graphene-carbon nanotube composite material, a conductive agent carbon black and a sodium alginate binder according to a mass ratio of 70; the first discharge capacity is up to 1985mAh/g, the first coulombic efficiency is up to 81.4%, the reversible capacity after 100 cycles still keeps 1653mAh/g, the capacity retention rate is up to 83.3%, and the battery performance is excellent.
Example 5: a preparation method of a porous silicon/metal/carbon nano material composite negative electrode material of a lithium ion battery comprises the following specific steps:
(1) Crushing and finely grinding industrial silicon to obtain silicon powder with the particle size of less than 1 mu m, washing with deionized water, carrying out solid-liquid separation, and drying the solid to obtain pretreated silicon powder;
(2) Adding the pretreated silicon powder into the catalyst-containing metal salt (Fe)(NO 3 ) 3 ) Depositing catalytic metal nano-iron particles in the hydrofluoric acid-ethanol mixed solution at the temperature of 40 ℃, and adding an oxidant (1 mol/L KMnO) 4 ) Carrying out metal-assisted chemical etching to introduce a porous structure on the silicon powder and embed catalytic metal nano iron particles, carrying out solid-liquid separation, and drying the solid to obtain a porous silicon/catalytic metal composite material; wherein the catalytic metal salt (Fe (NO) in the hydrofluoric acid-ethanol mixed solution 3 ) 3 ) The concentration of the acid is 0.5mol/L, HF, the concentration of the acid is 6mol/L, the ethanol content is 10wt%, and the liquid-solid ratio mL of the hydrofluoric acid-ethanol mixed solution to the silicon powder is 5:1;
(3) Placing the porous silicon/catalytic metal composite material in a CVD furnace, introducing argon to drive the air in the furnace cavity, opening a deposition gas-carrier gas inlet valve, introducing the gas at a flow rate of 50mL/min to the atmosphere containing 2.5wt% 2 H 2 Performing chemical vapor deposition on 17.5wt% of hydrogen and 80wt% of mixed gas for 1h at the temperature of 800 ℃ and the rotation rate of 60r/min, and performing air cooling to room temperature to obtain the porous silicon/iron/graphene-carbon nanotube composite anode material;
the morphology of the porous silicon/iron/graphene-carbon nanotube composite material under a transmission electron microscope is shown in fig. 5, and as can be seen from fig. 5, graphene and carbon nanotube materials grow on porous silicon, and iron particles are distributed on the silicon;
an electrode slice prepared from the porous silicon/iron/graphene-carbon nanotube composite material, a conductive agent carbon black and a sodium alginate binder according to a mass ratio of 70; the first discharge capacity is up to 1932mAh/g, the first coulombic efficiency is up to 82.3%, the reversible capacity after 100 cycles still keeps 1598mAh/g, the capacity retention rate is up to 82.7%, and the battery has excellent battery performance.
While the present invention has been described in detail with reference to the specific embodiments thereof, the present invention is not limited to the embodiments described above, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.

Claims (10)

1. A preparation method of a porous silicon/metal/carbon nano material composite cathode material of a lithium ion battery is characterized by comprising the following steps: the method comprises the following specific steps:
(1) Crushing and finely grinding the silicon material to obtain silicon powder, cleaning with deionized water or/and an acid solution, carrying out solid-liquid separation, and drying the solid to obtain pretreated silicon powder;
(2) Adding pretreated silicon powder into a hydrofluoric acid-alcohol mixed solution containing catalytic metal salt, depositing catalytic metal nano particles, adding an oxidant to perform metal-assisted chemical etching so as to introduce a porous structure on the silicon powder and embed the catalytic metal nano particles, performing solid-liquid separation, and drying the solid to obtain a porous silicon/catalytic metal composite material;
(3) And placing the porous silicon/catalytic metal composite material in a CVD (chemical vapor deposition) furnace, vacuumizing or introducing protective gas to drive air in the furnace chamber, opening a deposition gas-carrier gas inlet valve to perform chemical vapor deposition carbon, and performing air cooling to room temperature to obtain the porous silicon/metal/carbon nano material composite anode material.
2. The preparation method of the lithium ion battery porous silicon/metal/carbon nano-material composite anode material according to claim 1, characterized by comprising the following steps: the silicon material in the step (1) is high-purity silicon, industrial silicon or regenerated silicon material, and the particle size of the silicon powder is 0.01-10 mu m.
3. The preparation method of the porous silicon/metal/carbon nano-material composite anode material of the lithium ion battery according to claim 1, characterized by comprising the following steps: the concentration of the acid solution in the step (1) is 0.1-10 mol/L.
4. The preparation method of the porous silicon/metal/carbon nano-material composite anode material of the lithium ion battery according to claim 1 or 3, characterized by comprising the following steps: the acid solution is HCl or H 2 SO 4 、HNO 3 One or more of HF and acetic acid.
5. The preparation method of the lithium ion battery porous silicon/metal/carbon nano-material composite anode material according to claim 1, characterized by comprising the following steps: step (2) catalysisThe metal salt is Co (NO) 3 ) 2 、CoSO 4 、AgNO 3 、Fe(NO 3 ) 3 、NiSO 4 、Ni(NO 3 ) 2 、C 2 H 2 NiO 4 、Cu(NO 3 ) 2 、CuCl 2 Or CuSO 4 The alcohol is methanol, ethanol or ethylene glycol, and the oxidant is H 2 O 2 、HNO 3 、KMnO 4 Or Na 2 S 2 O 8 。
6. The preparation method of the porous silicon/metal/carbon nano-material composite anode material of the lithium ion battery according to claim 1, characterized by comprising the following steps: in the step (2), the concentration of the catalytic metal salt is 0.01-10 mol/L, the concentration of the alcohol is 5-50 wt%, the concentration of the HF is 0.1-10 mol/L, the concentration of the oxidant is 0.01-10 mol/L, and the liquid-solid ratio mL of the hydrofluoric acid-alcohol mixed solution to the silicon powder is (3-60) to 1.
7. The preparation method of the porous silicon/metal/carbon nano-material composite anode material of the lithium ion battery according to claim 1, characterized by comprising the following steps: the deposition temperature in the step (2) is 0-80 ℃.
8. The preparation method of the porous silicon/metal/carbon nano-material composite anode material of the lithium ion battery according to claim 1, characterized by comprising the following steps: the deposition gas in the step (3) is CH 4 、C 2 H 6 、C 3 H 8 、C 4 H 10 、CO 2 、CO、CH 2 O、C 2 H 2 、C 2 H 4 、C 4 H 8 、C 3 H 6 、C 3 H 4 The carrier gas is one or more of hydrogen, argon or nitrogen, the mass concentration of the deposition gas in the deposition gas-carrier gas is 1-50 wt%, and the flow rate of the deposition gas-carrier gas is 20-300 mL/min.
9. The preparation method of the porous silicon/metal/carbon nano-material composite anode material of the lithium ion battery according to claim 1 or 8, characterized by comprising the following steps: the chemical vapor deposition temperature is 300-1100 ℃, and the time is 0.5-10 h.
10. The preparation method of the lithium ion battery porous silicon/metal/carbon nano-material composite anode material according to claim 9, is characterized in that: the CVD furnace is provided with a rotating device, and the rotating speed in the chemical vapor deposition process is 0-60 r/min.
CN202211168147.2A 2022-09-23 2022-09-23 Preparation method of porous silicon/metal/carbon nano material composite anode material of lithium ion battery Pending CN115472813A (en)

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