CN108306009B - Silicon oxide-carbon composite negative electrode material, preparation method thereof and lithium ion battery - Google Patents

Silicon oxide-carbon composite negative electrode material, preparation method thereof and lithium ion battery Download PDF

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CN108306009B
CN108306009B CN201810199857.9A CN201810199857A CN108306009B CN 108306009 B CN108306009 B CN 108306009B CN 201810199857 A CN201810199857 A CN 201810199857A CN 108306009 B CN108306009 B CN 108306009B
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silicon oxide
negative electrode
silicon
carbon composite
electrode material
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CN108306009A (en
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沈成绪
傅儒生
夏永高
刘兆平
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Ningbo Institute of Material Technology and Engineering of CAS
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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
    • 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
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    • 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
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
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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
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
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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 provides a silicon oxide carbon composite negative electrode material, a preparation method thereof and a lithium ion battery, wherein the preparation method comprises the following steps: a) heating the silicon oxide to a first temperature in an inert atmosphere, adjusting the flow rate of inert gas, and carrying out heat preservation to obtain a silicon oxide composite material connected with the silicon nanowires; the first temperature is 800-1300 ℃; the flow rate of the inert gas is 0sccm to 800 sccm; b) adjusting the silicon oxide composite material connected with the silicon nanowires obtained in the step a) to a second temperature, introducing a carbon source gas for chemical vapor deposition under the condition of introducing an inert gas, and cooling to obtain a silicon oxide carbon composite negative electrode material; the second temperature is 600-1000 ℃. The invention adopts the preparation process of combining in-situ growth of silicon nanowires with carbon coating to obtain the silicon oxide carbon composite cathode material connected with the silicon nanowires; by constructing the three-dimensional conductive network, the electronic island effect of the silicon oxide-based material in the charge-discharge cycle process is effectively relieved, and the electrochemical performance is excellent.

Description

Silicon oxide-carbon composite negative electrode material, preparation method thereof and lithium ion battery
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a silicon oxide carbon composite negative electrode material, a preparation method thereof and a lithium ion battery.
Background
With the wide use of various mobile electronic devices, such as smart phones, notebook computers, and the like, lithium ion batteries have attracted much attention. However, the energy density and power density of the current commercial lithium ion battery are difficult to meet the requirements of technological development on energy storage devices. Therefore, the development of high capacity electrode materials is urgently needed.
Compared with the carbon-based anode material which is commercially used at present, the silicon oxide-based anode material has obvious advantages, such as high specific capacity, low lithium intercalation potential, stable cycle, rich content and the like, so the silicon oxide-based anode material is considered to be a high-capacity anode material with great development potential. However, there are some problems associated with the use of pure silicon oxide material as the negative electrode material of lithium ion batteries, among them: on one hand, the inherent poor conductivity of the conductive material limits the use of the conductive material in large quantity; on the other hand, its loss of contact due to the volume expansion of the electrons also causes its capacity to decay during cycling, in particular: the volume expansion effect (200%) of the silicon oxide-based negative electrode material in the charging and discharging process can easily cause capacity attenuation, wherein the important point is that the volume expansion-shrinkage causes the active material island effect caused by the loss of electronic contact among active material particles, once the active material loses the electronic contact, lithium can not be removed/inserted, and finally the capacity attenuation of the material is caused.
At present, in order to solve the problems of poor conductivity of a silicon oxide-based negative electrode material and capacity attenuation caused by loss of electron contact between active material particles due to volume change, researchers have proposed that a three-dimensional conductive network is constructed by using a one-dimensional nanomaterial, such as a Carbon nanotube and a silicon oxide material are physically mixed [ factor Synthesis and High Anode Performance of Carbon fiber Interwolfen atmospheric Nano-SiO ]x/Graphene for Rechargeable Lithium Batteries,ACS Appl.Mater.Interfaces 2013,5,11234](ii) a However, this simple physical mixing method cannot combine silica particles with one-dimensional nanomaterials, and after several charge-discharge cycles, electrons of the active material are still easily lost. And synthesizing a Silicon-based anode material with a sea urchin-like structure in the high-temperature heat treatment process by utilizing the catalysis of platinum metal, such as Yoo et al, wherein the nanowires with a Silicon/Silicon Oxide Core-Shell structure grow on the Surface of the Silicon particles with micron scale and protrude, and form a three-dimensional network [ simple Silicon/Silicon Oxide Core shells antibodies grow on to the Surface of the bulk Silicon, Nano Letters,2011,11,4324](ii) a However, the method has complex preparation process, needs to be catalyzed by noble metals such as platinum and the like, has high preparation cost and is difficult to realizeAnd 4, actual production application. The prior art also discloses that one-dimensional silicon nano-materials are directly prepared to be used as cathode materials (Self-crystallized synthesis of carbon-coated SiO)xnanowires for high capacity lithiumion battery anodes,J.Mater.Chem.A,2017,5,4183](ii) a However, the method mainly utilizes noble metal catalysis, the preparation process is complex, the cost is high, the practical industrial application cannot be realized, and the volume energy density of the electrode prepared by the silicon nanowire is seriously influenced due to low tap density.
Disclosure of Invention
In view of the above, the present invention provides a silicon oxide carbon composite negative electrode material, a preparation method thereof, and a lithium ion battery, and the silicon oxide carbon composite negative electrode material connected with a silicon nanowire can be obtained by the preparation method provided by the present invention, and has excellent electrochemical properties.
The invention provides a preparation method of a silicon oxide carbon composite negative electrode material, which comprises the following steps:
a) heating the silicon oxide to a first temperature in an inert atmosphere, adjusting the flow rate of inert gas, and carrying out heat preservation to obtain a silicon oxide composite material connected with the silicon nanowires; the first temperature is 800-1300 ℃; the flow rate of the inert gas is 0sccm to 800 sccm;
b) adjusting the silicon oxide composite material connected with the silicon nanowires obtained in the step a) to a second temperature, introducing a carbon source gas for chemical vapor deposition under the condition of introducing an inert gas, and cooling to obtain a silicon oxide carbon composite negative electrode material; the second temperature is 600-1000 ℃.
Preferably, the inert atmosphere in step a) is carried out by repeatedly pumping out an inert gas.
Preferably, the heat preservation time in the step a) is 10 min-40 h.
Preferably, the first temperature in step a) is 950 ℃ to 1100 ℃;
the second temperature in the step b) is 700-900 ℃;
the cooling speed adjusted to the second temperature is 5-20 ℃/min.
Preferably, the flow rate of the inert gas introduced in the step b) is 100sccm to 600 sccm.
Preferably, the carbon source gas in step b) includes one or more of ethylene gas, acetylene gas, methane gas and ethanol gas.
Preferably, the carbon source gas is introduced into the step b) at a flow rate of 10sccm to 400 sccm.
Preferably, the time of the chemical vapor deposition in the step b) is 10min to 3 h.
The invention also provides a silicon oxide carbon composite negative electrode material which is prepared by the preparation method of the technical scheme.
The invention also provides a lithium ion battery, which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte;
the negative electrode comprises the silicon oxide carbon composite negative electrode material or the silicon oxide carbon composite negative electrode material prepared by the preparation method in the technical scheme.
The invention provides a silicon oxide carbon composite negative electrode material, a preparation method thereof and a lithium ion battery, wherein the preparation method of the silicon oxide carbon composite negative electrode material comprises the following steps: a) heating the silicon oxide to a first temperature in an inert atmosphere, adjusting the flow rate of inert gas, and carrying out heat preservation to obtain a silicon oxide composite material connected with the silicon nanowires; the first temperature is 800-1300 ℃; the flow rate of the inert gas is 0sccm to 800 sccm; b) adjusting the silicon oxide composite material connected with the silicon nanowires obtained in the step a) to a second temperature, introducing a carbon source gas for chemical vapor deposition under the condition of introducing an inert gas, and cooling to obtain a silicon oxide carbon composite negative electrode material; the second temperature is 600-1000 ℃. Compared with the prior art, the silicon oxide carbon composite negative electrode material connected with the silicon nanowires is obtained by adopting the preparation process of in-situ growth of the silicon nanowires and carbon coating; by constructing the three-dimensional conductive network, the electronic island effect of the silicon oxide-based material caused by volume change in the charge-discharge cycle process can be effectively relieved, so that the silicon oxide-based material has excellent electrochemical performance. Experimental results show that the silicon oxide carbon composite negative electrode material provided by the invention has stable cycle performance in a lithium ion battery, the discharge specific capacity of the silicon oxide carbon composite negative electrode material is stable to be more than 800mAh/g, and the capacity retention rate of the silicon oxide carbon composite negative electrode material is still more than 80% after 200 cycles.
In addition, the preparation method provided by the invention is simple and easy to realize, does not need to add a metal catalyst, has low cost and is suitable for commercial application.
Drawings
Fig. 1 is a scanning electron microscope image of a silicon nanowire-connected silicon oxide carbon composite anode material provided in embodiment 1 of the present invention;
fig. 2 is a scanning electron microscope image of the silicon nanowire-connected silicon oxide carbon composite anode material provided in embodiment 2 of the present invention;
fig. 3 is a scanning electron microscope image of the silicon nanowire-connected silicon oxide carbon composite anode material provided in embodiment 3 of the present invention;
fig. 4 is a scanning electron microscope image of the silicon nanowire-connected silicon oxide carbon composite anode material provided in embodiment 4 of the present invention;
fig. 5 is a scanning electron microscope image of the silicon nanowire-connected silicon oxide carbon composite anode material provided in embodiment 5 of the present invention;
FIG. 6 is a scanning electron microscope image of the silicon oxide carbon composite negative electrode material provided in comparative example 1;
fig. 7 is a cycle performance curve of the silicon nanowire-connected silicon oxide carbon composite anode material provided in embodiment 1 of the present invention;
fig. 8 is a cycle performance curve of the silicon nanowire-connected silicon oxide carbon composite anode material provided in embodiment 2 of the present invention;
fig. 9 is a cycle performance curve of the silicon oxide carbon composite anode material provided in comparative example 1.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood 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.
The invention provides a preparation method of a silicon oxide carbon composite negative electrode material, which comprises the following steps:
a) heating the silicon oxide to a first temperature in an inert atmosphere, adjusting the flow rate of inert gas, and carrying out heat preservation to obtain a silicon oxide composite material connected with the silicon nanowires; the first temperature is 800-1300 ℃; the flow rate of the inert gas is 0sccm to 800 sccm;
b) adjusting the silicon oxide composite material connected with the silicon nanowires obtained in the step a) to a second temperature, introducing a carbon source gas for chemical vapor deposition under the condition of introducing an inert gas, and cooling to obtain a silicon oxide carbon composite negative electrode material; the second temperature is 600-1000 ℃.
According to the invention, firstly, the silicon oxide is heated to a first temperature under the inert atmosphere, the flow rate of the inert gas is adjusted, and heat preservation is carried out, so that the silicon oxide composite material connected with the silicon nanowires is obtained. In the present invention, the silica has a general formula represented by formula (I):
SiOx(I)；
wherein x is more than 0 and less than or equal to 2. In a preferred embodiment of the invention, the silicon oxide is selected from silicon monoxide. The source of the silica is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the present invention, the particle size of the silicon oxide is preferably 1 μm to 10 μm, and more preferably 5 μm.
In the present invention, the inert atmosphere is preferably selected from an argon atmosphere or a nitrogen atmosphere, and more preferably an argon atmosphere. In the present invention, the inert gas atmosphere is preferably performed by repeatedly pumping out the inert gas.
In the present invention, the first temperature is 800 to 1300 ℃, preferably 950 to 1100 ℃.
In the invention, the adjustment of the flow rate of the inert gas plays an important role in obtaining the silicon oxide composite material connected with the silicon nanowires. In the present invention, the inert gas flow rate is preferably 0sccm to 800sccm, and more preferably 200sccm to 600 sccm.
In the present invention, the time for the heat-retention is preferably 10min to 40 hours, and more preferably 1 hour to 10 hours.
After the silicon oxide composite material connected with the silicon nanowires is obtained, the obtained silicon oxide composite material connected with the silicon nanowires is adjusted to a second temperature, carbon source gas is introduced to carry out chemical vapor deposition under the condition of introducing inert gas, and the silicon oxide carbon composite negative electrode material is obtained after cooling. In the present invention, the second temperature is 600 to 1000 ℃, preferably 700 to 900 ℃.
In the present invention, the first temperature is preferably 950 to 1100 ℃, and the second temperature is preferably 700 to 900 ℃; in this case, the process of adjusting from the first temperature to the second temperature is a cooling process; the cooling rate adjusted to the second temperature is preferably 5 ℃/min to 20 ℃/min, and more preferably 10 ℃/min.
In the invention, inert gas is needed to be introduced while carbon source gas is introduced for chemical vapor deposition; the kind of the inert gas is the same as that described in the above technical scheme, and is not described again here. In the present invention, the flow rate of the inert gas is preferably 100sccm to 600sccm, and more preferably 200 sccm.
In the present invention, the carbon source gas preferably includes one or more of ethylene gas, acetylene gas, methane gas, and ethanol gas, and more preferably ethylene gas. The source of the carbon source gas is not particularly limited in the present invention.
In the present invention, the flow rate of the carbon source gas is preferably 10sccm to 400sccm, and more preferably 100 sccm.
In the present invention, the time of the chemical vapor deposition is preferably 10min to 3 hours, and more preferably 30min to 2 hours.
The preparation method provided by the invention realizes in-situ growth of the silicon nanowires by carrying out heat treatment on the raw material silicon oxide and controlling factors such as temperature, time, carrier gas flow rate and the like in the heat treatment process; and then carbon coating is carried out through chemical vapor deposition under specific conditions, so as to obtain the silicon oxide carbon composite cathode material connected with the silicon nanowire. On one hand, the silicon nanowire is an excellent cathode active material, and on the other hand, the silicon nanowire grown on the surface of the micron silicon oxide in situ is coated by carbon to construct a three-dimensional conductive network, so that the electronic island effect of the silicon oxide-based material caused by volume change in the charge-discharge cycle process is effectively relieved, and the electrochemical performance of the silicon oxide-based material is improved.
In addition, the preparation method provided by the invention is simple and can be carried out through a one-step method; meanwhile, the temperature, the time and the flow rate of the carrier gas can be controlled; and no metal catalyst is needed, so that the cost is low, and the method is suitable for commercial application.
The invention also provides a silicon oxide carbon composite negative electrode material which is prepared by the preparation method of the technical scheme. The silicon oxide carbon composite negative electrode material provided by the invention is a silicon oxide carbon composite negative electrode material connected with silicon nanowires, has excellent electrochemical performance, has stable cycle performance when being applied to a lithium ion battery, has stable discharge specific capacity of more than 800mAh/g, and has capacity retention rate of more than 80% after 200 cycles.
The invention also provides a lithium ion battery, which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte;
the negative electrode comprises the silicon oxide carbon composite negative electrode material or the silicon oxide carbon composite negative electrode material prepared by the preparation method in the technical scheme.
The positive electrode of the lithium ion battery is not particularly limited, and is preferably a lithium sheet; the source of the lithium sheet is not particularly limited, and a commercially available product can be adopted.
In the invention, the negative electrode includes the silicon oxide carbon composite negative electrode material described in the above technical scheme or the silicon oxide carbon composite negative electrode material prepared by the preparation method described in the above technical scheme, and details are not repeated herein.
The separator of the lithium ion battery according to the present invention is not particularly limited, and for example, a polypropylene microporous membrane (Celgard 2400) well known to those skilled in the art may be used.
The electrolyte of the lithium ion battery is not particularly limited in the present invention, and for example, a mixed solution of Ethylene Carbonate (EC) and dimethyl carbonate (DMC) of 1mol/L lithium hexafluorophosphate (EC/DMC volume ratio is 1: 1) known to those skilled in the art may be used.
The preparation method of the lithium ion battery is not particularly limited, and the method for preparing the lithium ion battery, which is well known to those skilled in the art, can be adopted. The specific steps are preferably as follows:
the silicon oxide carbon composite negative electrode material connected with the silicon nanowires in the technical scheme, the adhesive and the conductive agent are mixed according to the ratio of 80: 10: 10, adding a proper amount of water as a dispersing agent to prepare slurry, then uniformly coating the slurry on a copper foil current collector, and preparing a negative plate through vacuum drying and rolling; then using a metal lithium sheet as a counter electrode, 1mol/L LiPF6The mixed solvent (ethylene carbonate (EC) and dimethyl carbonate (DMC) in a volume ratio of 1: 1) as an electrolyte, and a polypropylene microporous membrane (Celgard 2400) as a separator were assembled in a glove box protected by argon gas to obtain a lithium ion battery.
The invention provides a silicon oxide carbon composite negative electrode material, a preparation method thereof and a lithium ion battery, wherein the preparation method of the silicon oxide carbon composite negative electrode material comprises the following steps: a) heating the silicon oxide to a first temperature in an inert atmosphere, adjusting the flow rate of inert gas, and carrying out heat preservation to obtain a silicon oxide composite material connected with the silicon nanowires; the first temperature is 800-1300 ℃; the flow rate of the inert gas is 0sccm to 800 sccm; b) adjusting the silicon oxide composite material connected with the silicon nanowires obtained in the step a) to a second temperature, introducing a carbon source gas for chemical vapor deposition under the condition of introducing an inert gas, and cooling to obtain a silicon oxide carbon composite negative electrode material; the second temperature is 600-1000 ℃. Compared with the prior art, the silicon oxide carbon composite negative electrode material connected with the silicon nanowires is obtained by adopting the preparation process of in-situ growth of the silicon nanowires and carbon coating; by constructing the three-dimensional conductive network, the electronic island effect of the silicon oxide-based material caused by volume change in the charge-discharge cycle process can be effectively relieved, so that the silicon oxide-based material has excellent electrochemical performance. Experimental results show that the silicon oxide carbon composite negative electrode material provided by the invention has stable cycle performance in a lithium ion battery, the discharge specific capacity of the silicon oxide carbon composite negative electrode material is stable to be more than 800mAh/g, and the capacity retention rate of the silicon oxide carbon composite negative electrode material is still more than 80% after 200 cycles.
In addition, the preparation method provided by the invention is simple and easy to realize, does not need to add a metal catalyst, has low cost and is suitable for commercial application.
To further illustrate the present invention, the following examples are provided for illustration.
Example 1
Placing 1.5g of commercial silicon monoxide (SiO) with the particle size of 5 μm in an atmosphere furnace, repeatedly exhausting gas under the argon atmosphere to ensure that the inert atmosphere is ensured in the furnace chamber, then heating to 1000 ℃, adjusting the argon flow rate to 200sccm, and preserving the heat for 5 hours; and then cooling to 900 ℃ at the speed of 10 ℃/min, introducing ethylene gas with the flow rate of 100sccm on the basis of the argon flow rate of 200sccm, keeping for 1h for carrying out chemical vapor deposition carbon coating, and finally naturally cooling to obtain the silicon oxide carbon composite negative electrode material (SiO/SNWs @ C) connected with the silicon nanowire.
A scanning electron microscope image of the silicon oxide carbon composite anode material connected with the silicon nanowire provided in embodiment 1 of the present invention is shown in fig. 1.
Example 2
Placing 1.5g of commercial silicon monoxide (SiO) with the particle size of 5 μm in an atmosphere furnace, repeatedly exhausting gas under the argon atmosphere to ensure that the inert atmosphere is ensured in the furnace chamber, then heating to 1000 ℃, adjusting the argon flow rate to 600sccm, and preserving the heat for 5 hours; and then cooling to 900 ℃ at the speed of 10 ℃/min, adjusting the flow rate of argon gas to be 200sccm, introducing ethylene gas with the flow rate of 100sccm, keeping for 1h for carrying out chemical vapor deposition carbon coating, and finally naturally cooling to obtain the silicon oxide carbon composite anode material (SiO/SNWs @ C) connected with the silicon nanowire.
A scanning electron microscope image of the silicon oxide carbon composite anode material connected with the silicon nanowire provided in embodiment 2 of the present invention is shown in fig. 2.
Example 3
Placing 1.5g of commercial silicon monoxide (SiO) with the particle size of 5 μm in an atmosphere furnace, repeatedly exhausting gas under the argon atmosphere to ensure that the inert atmosphere is ensured in the furnace chamber, then heating to 1000 ℃, adjusting the argon flow rate to 0sccm, and preserving the heat for 5 hours; and then cooling to 900 ℃ at the speed of 10 ℃/min, adjusting the flow rate of argon gas to be 200sccm, introducing ethylene gas with the flow rate of 100sccm, keeping for 1h for carrying out chemical vapor deposition carbon coating, and finally naturally cooling to obtain the silicon oxide carbon composite anode material (SiO/SNWs @ C) connected with the silicon nanowire.
A scanning electron microscope image of the silicon oxide carbon composite anode material connected with the silicon nanowire provided in embodiment 3 of the present invention is shown in fig. 3.
Example 4
Placing 1.5g of commercial silicon monoxide (SiO) with the particle size of 5 mu m in an atmosphere furnace, repeatedly exhausting gas under the argon atmosphere to ensure that the inert atmosphere is ensured in the furnace chamber, then heating to 950 ℃, adjusting the argon flow rate to 200sccm, and preserving the heat for 5 hours; and then cooling to 900 ℃ at the speed of 10 ℃/min, adjusting the flow rate of argon gas to be 200sccm, introducing ethylene gas with the flow rate of 100sccm, keeping for 1h for carrying out chemical vapor deposition carbon coating, and finally naturally cooling to obtain the silicon oxide carbon composite anode material (SiO/SNWs @ C) connected with the silicon nanowire.
A scanning electron microscope image of the silicon oxide carbon composite anode material connected with the silicon nanowire provided in embodiment 4 of the present invention is shown in fig. 4.
Example 5
Placing 1.5g of commercial silicon monoxide (SiO) with the particle size of 5 μm in an atmosphere furnace, repeatedly exhausting gas under the argon atmosphere to ensure that the inert atmosphere is ensured in the furnace chamber, then heating to 1100 ℃, adjusting the argon flow rate to 200sccm, and preserving the heat for 5 hours; and then cooling to 900 ℃ at the speed of 10 ℃/min, introducing ethylene gas with the flow rate of 100sccm on the basis of the argon flow rate of 200sccm, keeping for 1h for carrying out chemical vapor deposition carbon coating, and finally naturally cooling to obtain the silicon oxide carbon composite negative electrode material (SiO/SNWs @ C) connected with the silicon nanowire.
A scanning electron microscope image of the silicon oxide carbon composite anode material connected with the silicon nanowire provided in embodiment 5 of the present invention is shown in fig. 5.
Comparative example 1
Placing 1.5g of commercial silicon monoxide (SiO) with the particle size of 5 mu m in an atmosphere furnace, repeatedly exhausting gas under the argon atmosphere to ensure the inert atmosphere in the furnace chamber, then adjusting the argon flow rate to 200sccm, heating to 900 ℃, introducing ethylene gas with the flow rate of 100sccm, keeping for 1h for carrying out chemical vapor deposition carbon coating, and finally naturally cooling to obtain the silicon oxide carbon composite negative electrode material.
The scanning electron microscope image of the silicon oxide carbon composite negative electrode material provided by the comparative example 1 is shown in fig. 6.
Example 6
The silicon oxide carbon composite negative electrode material connected with the silicon nanowire provided in example 1, a binder (styrene butadiene rubber (SBR) and sodium carboxymethylcellulose in a mass ratio of 3: 7), and a conductive agent Super P were mixed according to a ratio of 80: 10: 10, adding a proper amount of water as a dispersing agent to prepare slurry, then uniformly coating the slurry on a copper foil current collector, and preparing a negative plate through vacuum drying and rolling; 1mol/L LiPF with metallic lithium sheet as counter electrode6The mixed solvent (ethylene carbonate (EC) and dimethyl carbonate (DMC) in a volume ratio of 1: 1) as an electrolyte, and a polypropylene microporous membrane (Celgard 2400) as a separator were assembled in a glove box protected by argon gas to obtain a lithium ion battery.
Example 7
The silicon oxide carbon composite negative electrode material connected with the silicon nanowire provided in example 2, a binder (styrene butadiene rubber (SBR) and sodium carboxymethylcellulose in a mass ratio of 3: 7), and a conductive agent Super P were mixed in the following ratio of 80: 10: 10, adding a proper amount of water as a dispersing agent to prepare slurry, then uniformly coating the slurry on a copper foil current collector, and preparing a negative plate through vacuum drying and rolling; 1mol/L LiPF with metallic lithium sheet as counter electrode6The mixed solvent (ethylene carbonate (EC) and dimethyl carbonate (DMC) in a volume ratio of 1: 1) as an electrolyte, and a polypropylene microporous membrane (Celgard 2400) as a separator were assembled in a glove box protected by argon gas to obtain a lithium ion battery.
Comparative example 2
Mixing the silicon oxide carbon composite negative electrode material provided by the comparative example 1, a binder (styrene butadiene rubber (SBR) and sodium carboxymethyl cellulose in a mass ratio of 3: 7) and a conductive agent Super P according to a ratio of 80: 10: 10, adding a proper amount of water as a dispersing agent to prepare slurry, then uniformly coating the slurry on a copper foil current collector, and preparing a negative plate through vacuum drying and rolling; a metal lithium sheet is used as a counter electrode,1mol/L LiPF6The mixed solvent (ethylene carbonate (EC) and dimethyl carbonate (DMC) in a volume ratio of 1: 1) as an electrolyte, and a polypropylene microporous membrane (Celgard 2400) as a separator were assembled in a glove box protected by argon gas to obtain a lithium ion battery.
The cycle performance of the lithium ion batteries provided in the embodiments 6 to 7 and the comparative example 2 of the invention is respectively tested, and the test is specifically carried out by adopting a constant rate charge and discharge mode: the charge-discharge voltage range is 0.005-1.5V, and the charge-discharge multiplying power is 0.2C; the adopted test instrument is a Land test instrument for testing the electrochemical performance of the battery, and the test condition is room temperature. The test results are shown in FIGS. 7 to 9. Experimental results show that the silicon oxide carbon composite negative electrode material connected with the silicon nanowires prepared by the invention shows stable cycle performance in a lithium ion battery, the specific discharge capacity of the material is stable to be more than 800mAh/g, and the capacity retention rate of the material is still more than 80% after the material is cycled for 200 circles.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (7)

1. A preparation method of a silicon oxide carbon composite negative electrode material comprises the following steps:
a) heating the silicon monoxide to a first temperature under an inert atmosphere, adjusting the flow rate of inert gas, and carrying out heat preservation to obtain a silicon oxide composite material connected with the silicon nanowires; the first temperature is 950 ℃ to 1100 ℃; the flow rate of the inert gas is 200 sccm-600 sccm;
b) adjusting the silicon oxide composite material connected with the silicon nanowires obtained in the step a) to a second temperature, introducing a carbon source gas for chemical vapor deposition under the condition of introducing an inert gas, and cooling to obtain a silicon oxide carbon composite negative electrode material; the second temperature is 700-900 ℃; the cooling speed for adjusting to the second temperature is 5-20 ℃/min;
the flow rate of the inert gas introduced in the step b) is 200 sccm; the flow rate of the carbon source gas is 100 sccm.
2. The method according to claim 1, wherein the inert gas atmosphere in step a) is performed by repeatedly pumping out an inert gas.
3. The method according to claim 1, wherein the holding time in step a) is 10min to 40 h.
4. The method of claim 1, wherein the carbon source gas in step b) comprises one or more of ethylene gas, acetylene gas, methane gas, and ethanol gas.
5. The method according to claim 1, wherein the time of the chemical vapor deposition in the step b) is 10min to 3 h.
6. A silicon oxide carbon composite negative electrode material is characterized by being prepared by the preparation method of any one of claims 1 to 5.
7. A lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte;
the negative electrode comprises the silicon oxide carbon composite negative electrode material of claim 6 or the silicon oxide carbon composite negative electrode material prepared by the preparation method of any one of claims 1 to 5.
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