CN107863517B - Silicon nanotube composite negative electrode material for lithium battery and preparation method - Google Patents

Silicon nanotube composite negative electrode material for lithium battery and preparation method Download PDF

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CN107863517B
CN107863517B CN201711082847.9A CN201711082847A CN107863517B CN 107863517 B CN107863517 B CN 107863517B CN 201711082847 A CN201711082847 A CN 201711082847A CN 107863517 B CN107863517 B CN 107863517B
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lithium battery
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CN107863517A (en
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陈庆
廖健淞
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Hubei Guanyu New Material Technology Co ltd
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Chengdu New Keli Chemical Science Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to the technical field of lithium batteries, in particular to a silicon nanotube composite negative electrode material for a lithium battery and a preparation method thereof.

Description

Silicon nanotube composite negative electrode material for lithium battery and preparation method
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a silicon nanotube composite negative electrode material for a lithium battery and a preparation method thereof.
Background
The global new energy automobile industry will present the trend of rapid industrialization under the big background that the technology is continuously mature and the government supporting policy is continuously fallen to the ground, and in addition, the industries such as electric tools, electric bicycles, new energy sources and the like will keep the trend of rapid development under the background of low-carbon economy. With the rapid development of wind power, photovoltaic power stations and smart power grids, a high-efficiency and clean large-scale power storage technology is urgently needed, and a novel secondary battery is highly concerned by a power system and requires wide resources, high cost performance, environmental friendliness, long service life and easiness in maintenance. Therefore, an electric energy storage technology with high performance, low cost and high safety is one of the key technologies for realizing sustainable development of energy in China.
Lithium ion batteries are currently the most widely used secondary batteries, and graphite is usually used as a negative electrode material. Because the specific capacity of the graphite cathode is low and the theoretical specific capacity is only 372mAh/g, the design requirement of the high-energy density lithium ion battery is difficult to meet. The high specific capacity negative electrode materials for lithium ion batteries reported at present mainly comprise silicon-based composite materials, oxides, vanadium oxides, tin-based compounds and the like. However, the battery using these negative electrode materials has poor cycle performance, and generally, the capacity rapidly decreases after several tens of charge and discharge. Therefore, whether the lithium ion battery can be applied or not, and the preparation technology of the high-performance negative electrode material is one of the key problems to be solved firstly. The silicon cathode has extremely high theoretical specific capacity which can reach 4200mAh/g, and the energy density of the lithium ion battery can be greatly improved through the application of the silicon cathode, so that the silicon cathode is expected to be applied to the fields of power automobiles, energy storage galvanic pile and the like in a large scale. However, the silicon negative electrode is easily pulverized due to the volume effect generated by the intercalation and deintercalation of lithium ions during the charging and discharging processes, resulting in rapid capacity fading. In order to solve this problem, a silicon-carbon composite method or the like is generally used. In patents with application numbers 201310265626.0, 201210520708.0, 201210534860.4, 201310101854.4, 201110421436.4 and 201010256875.X, a silicon-carbon composite material is prepared by simply mechanically mixing a silicon material and graphene, and then performing suction filtration or spraying and other simple means. The above materials can be understood as a mechanical mixture rather than a composite material, and thus the electrochemical performance of the silicon-graphene material is still not high. The nano approach is one of the most important methods for improving the structure and performance of the silicon cathode material at present, and plays roles in relieving the volume effect of the silicon material and improving the electronic conductivity of the material respectively. In recent years, nano silicon materials have exhibited good electrochemical properties, but the distance from commercial application is still not small, and especially the cycling performance of nano silicon is still difficult to meet the practical requirement.
Disclosure of Invention
Aiming at the defects of large volume change and low charge-discharge efficiency of the lithium battery cathode material in the prior art in the charge-discharge process, the invention aims to provide the silicon nanotube composite cathode material for the lithium battery and the preparation method thereof, which increase Li ion de-intercalation channels, refine crystal grains and reduce the generation of side reactions in the Li ion de-intercalation process, thereby improving the coulombic efficiency of the cathode.
In order to solve the problems, the invention adopts the following technical scheme:
the utility model provides a silicon nanotube composite negative pole material for lithium cell, a silicon nanotube composite negative pole material for lithium cell comprises basement and the compound nanotube of vertical arrangement on the basement, compound nanotube is by inside to outside, by silicon nanotube, titanium dioxide film and amorphous carbon layer in proper order.
According to the invention, the silicon nanotube is used as the negative electrode material, the TiO2 is deposited on the surface of the silicon nanotube by using a sputtering deposition method, the volume change caused by Li deintercalation can be reduced in the charging and discharging process of the negative electrode material, the Li deintercalation can be faster and more thorough, the reversible specific capacity is higher, and a more stable SEI film can be formed, so that the coulombic efficiency of the material is improved, the service life of the lithium battery is prolonged, meanwhile, the amorphous carbon is continuously coated on the outer surface of the silicon dioxide, the internal resistance of the negative electrode material can be reduced, the lithium dendrite can be prevented from puncturing the diaphragm, the internal thermal diffusion of the battery can be improved, and the gram capacity and the conductivity of.
According to the invention, under the preferable conditions, the inner diameter of the silicon dioxide nanotube is 50-300 nanometers, and the outer diameter is 70-400 nanometers.
According to the invention, the appropriate film thickness can not only allow the lithium ions to pass and diffuse, keep higher ion transmission efficiency, but also effectively prevent the formation of an unstable SEI layer and improve the cycling stability of the electrode, but the film thickness is too large, which can cause the film to fall off from the silicon substrate and affect the stability of the cathode. Under the preferable condition, the thickness of the titanium dioxide film is 50-200 nanometers.
According to the invention, under the preferable condition, the thickness of the carbon layer is 5-20 nm.
The invention also provides a preparation method of the silicon oxide nanotube composite negative electrode material for the lithium battery, which comprises the following steps:
(1) preparing a silicon nanotube on a silicon substrate to obtain a silicon substrate A1 loaded with the silicon nanotube:
(2) placing A1 in a vacuum deposition chamber, introducing mixed gas of oxygen and argon into the deposition chamber, and depositing a titanium dioxide film on a silicon nanotube by taking a titanium target as a target material to obtain A2;
(3) uniformly mixing A2 and a carbon source in water, then carrying out a closed reaction for 2-6 hours at 100-160 ℃, carrying out high-temperature heat treatment on the reaction product for 0.5-1.5 hours at 650-750 ℃ under the protection of inert gas, and cooling to obtain the silicon nanotube composite anode material for the lithium battery.
According to the invention, under the preferable conditions, in the step (1), the preparation method of the silicon nanometer is as follows:
(1a) cleaning and drying a monocrystalline silicon wafer substrate, and sputtering a layer of gold film with the thickness of 2-6 nm on the surface of the silicon wafer by using an ion sputtering instrument as a catalyst to provide nucleation points for the growth of silicon dioxide nanotubes;
(1b) putting the corundum boat bearing the zinc sulfide powder and the silicon substrate into a horizontal tube furnace, enabling the zinc sulfide to be positioned in the center of a high-temperature area of the horizontal tube furnace, enabling the silicon substrate to be positioned at a position 10 cm-30 cm downstream of the zinc sulfide, sealing the tube furnace, introducing high-purity inert gas serving as carrier gas, and washing out residual air in a growth chamber;
(1c) controlling the flow rate of the inert gas at 30sccm-300sccm, keeping the pressure in the growth chamber at 80 Pa-1000 Pa, heating the tubular furnace to the synthesis temperature of 1100-1200 ℃, keeping the constant temperature for 0.2-1 hour, naturally cooling the tubular furnace to the room temperature after the reaction is finished, and taking out the synthesized product, namely the silicon dioxide nanotube.
According to the invention, the sputtering deposition process is an important factor influencing the performance of the titanium dioxide film, and under the preferable conditions, in the step (2), the deposition process is as follows: the pressure of the deposition chamber is 2-10 Pa. Further preferably, the negative bias applied to the substrate A1 is-120V to-80V, and the bias duty ratio is 40-80%. According to the invention, under the preferable condition, the target current of the titanium target is 1-3A; and/or
According to the invention, under the preferable condition, the distance between the titanium target and the substrate A1 is 3-15 cm; and/or
According to the invention, the deposition time is an important factor influencing the thickness of the titanium dioxide film, and under the preferable condition, the deposition time is 5-30 min, preferably 5-15 min.
According to the invention, under the preferable conditions, in the step (2), the flow rate of the oxygen is 50-120 sccm;
according to the invention, under the preferable condition, the flow rate of the argon is 100-200 sccm.
According to the present invention, the carbon source is not particularly limited, and may be a carbon source commonly used for preparing amorphous carbon, and preferably, in the step (3), the carbon source is at least one selected from glucose, sucrose, ascorbic acid and citric acid.
According to the invention, under the preferable conditions, in the step (3), the concentration of the carbon source is 0.05-0.2 mol/L.
Compared with the prior art, the silicon nanotube composite negative electrode material for the lithium battery and the preparation method thereof have the outstanding characteristics and excellent effects that:
the invention uses the silicon nanotube as the cathode material, and uses the sputtering deposition method to deposit TiO on the surface of the silicon nanotube2The lithium ion battery cathode material has the advantages that the volume change caused by Li deintercalation can be reduced in the charge and discharge process of the cathode material, Li deintercalation can be quicker and more thorough, the reversible specific capacity is higher, a more stable SEI film can be formed, the coulombic efficiency of the material is improved, the service life of the lithium battery is prolonged, meanwhile, the amorphous carbon is continuously coated on the outer surface of silicon dioxide, the internal resistance of the cathode material can be reduced, lithium dendrites can be prevented from puncturing a diaphragm, the internal thermal diffusion of the battery is improved, and the gram capacity and the conductivity of the material can be improved.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
A preparation method of a silicon nanotube composite negative electrode material for a lithium battery comprises the following steps:
(1) cleaning and drying a monocrystalline silicon wafer substrate, and sputtering a layer of gold film with the thickness of 3nm on the surface of the silicon wafer by using an ion sputtering instrument as a catalyst to provide nucleation points for the growth of silicon dioxide nanotubes; putting the corundum boat bearing the zinc sulfide powder and the silicon substrate into a horizontal tube furnace, enabling the zinc sulfide to be located in the center of a high-temperature area of the horizontal tube furnace, enabling the silicon substrate to be located 15cm downstream of the zinc sulfide, sealing the tube furnace, introducing high-purity inert gas serving as carrier gas, and washing away residual air in a growth chamber; controlling the flow rate of the inert gas at 150sccm, keeping the pressure in the growth chamber at 500Pa, heating the tubular furnace to the synthesis temperature of 1200 ℃, keeping the constant temperature for 0.5 hour, naturally cooling the tubular furnace to the room temperature after the reaction is finished, and taking out the synthesized product, namely the silicon dioxide nanotube.
(2) Placing A1 in a vacuum deposition chamber, introducing argon gas into the deposition chamber until the pressure is 5 Pa, then introducing a mixed gas of oxygen gas and argon gas (the oxygen gas flow is 60 sccm; the argon gas flow is 150 sccm), starting a bias power supply, and depositing a titanium dioxide film on the silicon nanotube by taking a titanium target as a target material to obtain A2; the sputtering conditions were: for the metal substrate A1The applied negative bias is-100V, the bias duty ratio is 50%, the target current is 1-3A, and the target material and the metal substrate A1The distance is 10m, and the deposition time is 10 min;
(3) uniformly mixing A2 with ascorbic acid in water, wherein the concentration of the ascorbic acid is 0.1 mol/L; and then carrying out closed reaction for 4 hours at the temperature of 140 ℃, carrying out high-temperature heat treatment on the reaction product for 1 hour at the temperature of 650 ℃ under the protection of inert gas, and cooling to obtain the silicon nanotube composite negative electrode material for the lithium battery.
The silicon nanotube composite negative electrode material for the lithium battery in the embodiment comprises a substrate and composite nanotubes vertically arranged on the substrate, wherein the composite nanotubes sequentially comprise a silicon nanotube, a titanium dioxide film and an amorphous carbon layer from inside to outside, the inner diameter of the silicon nanotube is 100 nanometers, and the outer diameter of the silicon nanotube is 150 nanometers; the thickness of the titanium dioxide film is 150 nanometers; the amorphous carbon layer has a thickness of 10 nm.
Example 2
A preparation method of a silicon nanotube composite negative electrode material for a lithium battery comprises the following steps:
(1) cleaning and drying a monocrystalline silicon wafer substrate, and sputtering a layer of gold film with the thickness of 5nm on the surface of the silicon wafer by using an ion sputtering instrument as a catalyst to provide nucleation points for the growth of silicon dioxide nanotubes; putting the corundum boat bearing the zinc sulfide powder and the silicon substrate into a horizontal tube furnace, enabling the zinc sulfide to be located in the center of a high-temperature area of the horizontal tube furnace, enabling the silicon substrate to be located 20cm downstream of the zinc sulfide, sealing the tube furnace, introducing high-purity inert gas serving as carrier gas, and washing away residual air in a growth chamber; controlling the flow rate of the inert gas at 200sccm, keeping the pressure in the growth chamber at 800Pa, heating the tubular furnace to the synthesis temperature of 1200 ℃, keeping the temperature constant for 1 hour, naturally cooling the tubular furnace to the room temperature after the reaction is finished, and taking out the synthesized product, namely the silicon dioxide nanotube.
(2) Placing A1 in a vacuum deposition chamber, introducing argon gas into the deposition chamber until the pressure is 8 Pa, then introducing a mixed gas of oxygen gas and argon gas (the oxygen gas flow is 100 sccm; the argon gas flow is 150 sccm), starting a bias power supply, and depositing a titanium dioxide film on the silicon nanotube by taking a titanium target as a target material to obtain A2; the sputtering conditions were: for the metal substrate A1The applied negative bias is-100V, the bias duty ratio is 60%, the target current is 2A, the target material and the metal substrate A1The distance is 8cm, and the deposition time is 15 min;
(3) uniformly mixing A2 with glucose in water, wherein the concentration of the glucose is 0.15 mol/L; and then carrying out closed reaction for 3 hours at 120 ℃, carrying out high-temperature heat treatment on the reaction product for 1 hour at 700 ℃ under the protection of inert gas, and cooling to obtain the silicon nanotube composite negative electrode material for the lithium battery.
The silicon nanotube composite negative electrode material for the lithium battery in the embodiment comprises a substrate and composite nanotubes vertically arranged on the substrate, wherein the composite nanotubes sequentially comprise a silicon nanotube, a titanium dioxide film and an amorphous carbon layer from inside to outside, the inner diameter of the silicon nanotube is 250 nanometers, and the outer diameter of the silicon nanotube is 300 nanometers; the thickness of the titanium dioxide film is 100 nanometers; the amorphous carbon layer has a thickness of 15 nm.
Example 3
A preparation method of a silicon nanotube composite negative electrode material for a lithium battery comprises the following steps:
(1) cleaning and drying a monocrystalline silicon wafer substrate, and sputtering a layer of gold film with the thickness of 6nm on the surface of the silicon wafer by using an ion sputtering instrument as a catalyst to provide nucleation points for the growth of a silicon dioxide nanotube; putting the corundum boat bearing the zinc sulfide powder and the silicon substrate into a horizontal tube furnace, enabling the zinc sulfide to be located in the center of a high-temperature area of the horizontal tube furnace, enabling the silicon substrate to be located 10cm downstream of the zinc sulfide, sealing the tube furnace, introducing high-purity inert gas serving as carrier gas, and washing away residual air in a growth chamber; controlling the flow rate of the inert gas at 30sccm, keeping the pressure in the growth chamber at 80Pa, heating the tubular furnace to the synthesis temperature of 1200 ℃, keeping the constant temperature for 0.2 hour, naturally cooling the tubular furnace to the room temperature after the reaction is finished, and taking out the synthesized product, namely the silicon dioxide nanotube.
(2) Placing A1 in a vacuum deposition chamber, introducing argon gas into the deposition chamber until the pressure is 2 Pa, then introducing a mixed gas of oxygen gas and argon gas (the oxygen gas flow is 120 sccm; the argon gas flow is 200 sccm), starting a bias power supply, and depositing a titanium dioxide film on the silicon nanotube by taking a titanium target as a target material to obtain A2; the sputtering conditions were: for the metal substrate A1The applied negative bias is-80V, the bias duty ratio is 80%, the target current is 1A, and the target material and the metal substrate A1The distance is 15cm, and the deposition time is 5 min;
(3) uniformly mixing A2 with ascorbic acid in water, wherein the concentration of the ascorbic acid is 0.2 mol/L; and then carrying out closed reaction for 6 hours at 100 ℃, carrying out high-temperature heat treatment on the reaction product for 1.5 hours at 650 ℃ under the protection of inert gas, and cooling to obtain the silicon nanotube composite negative electrode material for the lithium battery.
The silicon nanotube composite negative electrode material for the lithium battery in the embodiment comprises a substrate and composite nanotubes vertically arranged on the substrate, wherein the composite nanotubes sequentially comprise a silicon nanotube, a titanium dioxide film and an amorphous carbon layer from inside to outside, the inner diameter of the silicon nanotube is 300 nanometers, and the outer diameter of the silicon nanotube is 400 nanometers; the thickness of the titanium dioxide film is 50 nanometers; the amorphous carbon layer has a thickness of 20 nm.
Example 4
A preparation method of a silicon nanotube composite negative electrode material for a lithium battery comprises the following steps:
(1) cleaning and drying a monocrystalline silicon wafer substrate, and sputtering a layer of gold film with the thickness of 2nm on the surface of the silicon wafer by using an ion sputtering instrument as a catalyst to provide nucleation points for the growth of silicon dioxide nanotubes; putting the corundum boat bearing the zinc sulfide powder and the silicon substrate into a horizontal tube furnace, enabling the zinc sulfide to be located in the center of a high-temperature area of the horizontal tube furnace, enabling the silicon substrate to be located 30cm downstream of the zinc sulfide, sealing the tube furnace, introducing high-purity inert gas serving as carrier gas, and washing away residual air in a growth chamber; controlling the flow rate of the inert gas at 300sccm, keeping the pressure in the growth chamber at 1000Pa, heating the tubular furnace to the synthesis temperature of 1100 ℃, keeping the temperature constant for 0.2 hour, naturally cooling the tubular furnace to the room temperature after the reaction is finished, and taking out the synthesized product, namely the silicon dioxide nanotube.
(2) Placing A1 in a vacuum deposition chamber, introducing argon gas into the deposition chamber until the pressure is 10 Pa, then introducing a mixed gas of oxygen gas and argon gas (the oxygen gas flow is 50 sccm; the argon gas flow is 10 sccm), starting a bias power supply, and depositing a titanium dioxide film on the silicon nanotube by taking a titanium target as a target material to obtain A2; the sputtering conditions were: for the metal substrate A1The applied negative bias is-80V, the bias duty ratio is 40%, the target current is 3A, the target material and the metal substrate A1The distance is 3 cm, and the deposition time is 30 min;
(3) uniformly mixing A2 with glucose in water, wherein the concentration of the glucose is 0.05 mol/L; and then carrying out closed reaction for 2 hours at 160 ℃, carrying out high-temperature heat treatment on the reaction product for 0.5 hour at 750 ℃ under the protection of inert gas, and cooling to obtain the silicon nanotube composite negative electrode material for the lithium battery.
The silicon nanotube composite negative electrode material for the lithium battery in the embodiment comprises a substrate and composite nanotubes vertically arranged on the substrate, wherein the composite nanotubes sequentially comprise a silicon nanotube, a titanium dioxide film and an amorphous carbon layer from inside to outside, the inner diameter of the silicon nanotube is 50 nanometers, and the outer diameter of the silicon nanotube is 70 nanometers; the thickness of the titanium dioxide film is 200 nanometers; the amorphous carbon layer has a thickness of 5 nm.
Comparative example 1
A preparation method of a silicon nanotube composite negative electrode material for a lithium battery comprises the following steps:
(1) cleaning and drying a monocrystalline silicon wafer substrate, and sputtering a layer of gold film with the thickness of 3nm on the surface of the silicon wafer by using an ion sputtering instrument as a catalyst to provide nucleation points for the growth of silicon dioxide nanotubes; putting the corundum boat bearing the zinc sulfide powder and the silicon substrate into a horizontal tube furnace, enabling the zinc sulfide to be located in the center of a high-temperature area of the horizontal tube furnace, enabling the silicon substrate to be located 15cm downstream of the zinc sulfide, sealing the tube furnace, introducing high-purity inert gas serving as carrier gas, and washing away residual air in a growth chamber; controlling the flow rate of the inert gas at 150sccm, keeping the pressure in the growth chamber at 500Pa, heating the tubular furnace to the synthesis temperature of 1200 ℃, keeping the constant temperature for 0.5 hour, naturally cooling the tubular furnace to the room temperature after the reaction is finished, and taking out the synthesized product, namely the silicon dioxide nanotube.
(2) Placing A1 in a vacuum deposition chamber, introducing argon gas into the deposition chamber until the pressure is 5 Pa, then introducing a mixed gas of oxygen gas and argon gas (the oxygen gas flow is 60 sccm; the argon gas flow is 150 sccm), starting a bias power supply, and depositing a titanium dioxide film on the silicon nanotube by taking a titanium target as a target material to obtain A2; the sputtering conditions were: for the metal substrate A1The applied negative bias is-100V, the bias duty ratio is 50%, the target current is 1-3A, and the target material and the metal substrate A1The distance was 10m and the deposition time was 10 min.
Comparative example 2
A preparation method of a silicon nanotube composite negative electrode material for a lithium battery comprises the following steps:
(1) cleaning and drying a monocrystalline silicon wafer substrate, and sputtering a layer of gold film with the thickness of 3nm on the surface of the silicon wafer by using an ion sputtering instrument as a catalyst to provide nucleation points for the growth of silicon dioxide nanotubes; putting the corundum boat bearing the zinc sulfide powder and the silicon substrate into a horizontal tube furnace, enabling the zinc sulfide to be located in the center of a high-temperature area of the horizontal tube furnace, enabling the silicon substrate to be located 15cm downstream of the zinc sulfide, sealing the tube furnace, introducing high-purity inert gas serving as carrier gas, and washing away residual air in a growth chamber; controlling the flow rate of the inert gas at 150sccm, keeping the pressure in the growth chamber at 500Pa, heating the tubular furnace to the synthesis temperature of 1200 ℃, keeping the constant temperature for 0.5 hour, naturally cooling the tubular furnace to the room temperature after the reaction is finished, and taking out the synthesized product, namely the silicon dioxide nanotube.
(2) Uniformly mixing A1 with ascorbic acid in water, wherein the concentration of the ascorbic acid is 0.1 mol/L; and then carrying out closed reaction for 4 hours at the temperature of 140 ℃, carrying out high-temperature heat treatment on the reaction product for 1 hour at the temperature of 650 ℃ under the protection of inert gas, and cooling to obtain the silicon nanotube composite negative electrode material for the lithium battery.
The silicon nanotube composite negative electrode material for the lithium battery in the embodiment comprises a substrate and composite nanotubes vertically arranged on the substrate, wherein the composite nanotubes sequentially comprise a silicon nanotube, a titanium dioxide film and an amorphous carbon layer from inside to outside, the inner diameter of the silicon nanotube is 100 nanometers, and the outer diameter of the silicon nanotube is 150 nanometers; the thickness of the titanium dioxide film is 150 nanometers; the amorphous carbon layer has a thickness of 10 nm.
Comparative example 3
A preparation method of a silicon nanotube composite negative electrode material for a lithium battery comprises the following steps:
(1) cleaning and drying a monocrystalline silicon wafer substrate, and sputtering a layer of gold film with the thickness of 3nm on the surface of the silicon wafer by using an ion sputtering instrument as a catalyst to provide nucleation points for the growth of silicon dioxide nanotubes; putting the corundum boat bearing the zinc sulfide powder and the silicon substrate into a horizontal tube furnace, enabling the zinc sulfide to be located in the center of a high-temperature area of the horizontal tube furnace, enabling the silicon substrate to be located 15cm downstream of the zinc sulfide, sealing the tube furnace, introducing high-purity inert gas serving as carrier gas, and washing away residual air in a growth chamber; controlling the flow rate of the inert gas at 150sccm, keeping the pressure in the growth chamber at 500Pa, heating the tubular furnace to the synthesis temperature of 1200 ℃, keeping the constant temperature for 0.5 hour, naturally cooling the tubular furnace to the room temperature after the reaction is finished, and taking out the synthesized product, namely the silicon dioxide nanotube.
The internal resistance, capacity and cycle life of the lithium batteries of examples 1 to 4 and comparative examples 1 to 3 were also tested, and the experimental results are shown in table 1.
The method for measuring the cycle life comprises the following steps: charging the lithium ion batteries to 3.65V at a current of 1C respectively at 23 ℃, charging the lithium ion batteries at a constant voltage after the voltage rises to 3.65V, limiting the voltage to 3.8V, stopping the current to 0.1C, and standing for 10 minutes; the cell was discharged to 2.0V at 1C current and left for 10 minutes. Repeating the above steps 200 times to obtain the capacity of the battery after 200 cycles of discharging at 1C to 2.0V, recording the first discharge capacity of the battery at 23 ℃, and calculating the capacity maintenance rate before and after the cycles according to the following formula:
capacity retention rate (200 th cycle discharge capacity/first cycle discharge capacity) × 100%
Wherein, the internal resistance of the battery is measured by a BVIR battery voltage internal resistance tester.
TABLE 1 tables of Performance of lithium Battery anodes in examples 1 to 4 and comparative examples 1 to 3
Figure DEST_PATH_IMAGE001
The comparison of data shows that the silicon nanotube composite negative electrode material for the lithium battery can obviously reduce the internal resistance and prolong the cycle life.

Claims (6)

1. The preparation method of the silicon oxide nanotube composite negative electrode material for the lithium battery is characterized by comprising the following steps of:
(1) preparing a silicon nanotube on a silicon substrate to obtain a silicon substrate A1 loaded with the silicon nanotube:
(2) placing A1 in a vacuum deposition chamber, introducing mixed gas of oxygen and argon into the deposition chamber, and depositing a titanium dioxide film on a silicon nanotube by taking a titanium target as a target material to obtain A2;
(3) uniformly mixing A2 and a carbon source in water, then carrying out a closed reaction for 2-6 hours at 100-160 ℃, carrying out high-temperature heat treatment on the reaction product for 0.5-1.5 hours at 650-750 ℃ under the protection of inert gas, and cooling to obtain the silicon nanotube composite anode material for the lithium battery.
2. The method for preparing a silicon oxide nanotube composite anode material for a lithium battery as claimed in claim 1, wherein in the step (2), the deposition process comprises: the pressure of the deposition chamber is 2-10 Pa; and/or
The negative bias voltage applied to the substrate A1 is-120 to-80V, and the bias duty ratio is 40 to 80 percent; and/or
The target current of the titanium target is 1-3A; and/or
The distance between the titanium target and the substrate A1 is 3-15 cm; and/or
The deposition time is 5-30 min.
3. The method for preparing the silicon oxide nanotube composite anode material for a lithium battery as claimed in claim 1 or 2, wherein in the step (2), the flow rate of the oxygen is 50 to 120 sccm;
the flow rate of the argon is 100-200 sccm.
4. The method for preparing a silicon oxide nanotube composite anode material for a lithium battery according to claim 1, wherein in the step (3), the carbon source is at least one selected from glucose, sucrose, ascorbic acid and citric acid.
5. The method for preparing the silicon oxide nanotube composite anode material for a lithium battery as claimed in claim 1, wherein in the step (3), the concentration of the carbon source is 0.05 to 0.2 mol/L.
6. The method for preparing a silicon oxide nanotube composite anode material for a lithium battery as claimed in claim 1, wherein in the step (1), the method for preparing silicon nano-particles comprises:
(1a) cleaning and drying a monocrystalline silicon wafer substrate, and sputtering a layer of gold film with the thickness of 2-6 nm on the surface of the silicon wafer by using an ion sputtering instrument as a catalyst to provide nucleation points for the growth of silicon dioxide nanotubes;
(1b) putting the corundum boat bearing the zinc sulfide powder and the silicon substrate into a horizontal tube furnace, enabling the zinc sulfide to be positioned in the center of a high-temperature area of the horizontal tube furnace, enabling the silicon substrate to be positioned at a position 10 cm-30 cm downstream of the zinc sulfide, sealing the tube furnace, introducing high-purity inert gas serving as carrier gas, and washing out residual air in a growth chamber;
(1c) controlling the flow rate of the inert gas at 30sccm-300sccm, keeping the pressure in the growth chamber at 80 Pa-1000 Pa, heating the tubular furnace to the synthesis temperature of 1100-1200 ℃, keeping the constant temperature for 0.2-1 hour, naturally cooling the tubular furnace to the room temperature after the reaction is finished, and taking out the synthesized product, namely the silicon dioxide nanotube.
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