CN111816855B - Preparation method of magnesium-containing silicon monoxide/silicon @ resin carbon/CVD carbon material - Google Patents

Preparation method of magnesium-containing silicon monoxide/silicon @ resin carbon/CVD carbon material Download PDF

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CN111816855B
CN111816855B CN202010696593.5A CN202010696593A CN111816855B CN 111816855 B CN111816855 B CN 111816855B CN 202010696593 A CN202010696593 A CN 202010696593A CN 111816855 B CN111816855 B CN 111816855B
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易旭
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Hunan Jinsi Technology Co ltd
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Abstract

The preparation method of the magnesium-containing silicon monoxide/silicon @ resin carbon/CVD carbon material comprises the following steps: adding silicon oxide particles and silicon particles into absolute ethyl alcohol, mixing, and performing ultrasonic dispersion; adding resin, heating to dissolve the resin, stirring, grinding, and spray drying; heat treatment, so that the resin is foamed and then carbonized; placing a magnesium sheet on the surface, and carrying out heat treatment under a vacuum condition; and (4) placing the mixture into a chemical vapor deposition furnace for surface carbon deposition, and thus obtaining the carbon-containing carbon material. The magnesium-containing silicon monoxide/silicon @ resin carbon/CVD carbon material has a unique double-layer coating structure, silicon monoxide with small particle size and magnesium silicide are uniformly dispersed in the carbon material and used for manufacturing a lithium ion battery cathode, and the lithiation rate is increased by 3 to 4.5 times; the preparation method has the advantages of simple operation, low cost and easy industrial production; the obtained battery cathode material can greatly improve the first coulombic efficiency of the lithium ion battery and prolong the service life of the lithium ion battery.

Description

Preparation method of magnesium-containing silicon monoxide/silicon @ resin carbon/CVD carbon material
Technical Field
The invention relates to a preparation method of a magnesium-containing silicon/carbon material, in particular to a preparation method of a magnesium-containing silicon monoxide/silicon carbon material.
Background
Lithium ion batteries are widely used because of their advantages of high voltage, high specific energy and long cycle life; meanwhile, the theoretical capacity of the lithium ion battery taking graphite and other materials as the negative electrode is only 375 mAh g -1 . As portable electronic devices become more and more powerful, increasing the energy density and cycle life of lithium ion batteries is becoming an increasingly urgent need.
Compared with the traditional graphite cathode, the silicon has ultrahigh theoretical specific capacity (4200 mAh g) -1 ) The method is one of the potential choices for upgrading and updating the lithium ion battery. However, there are other problems in using silicon-based materials as the negative electrode of lithium ion batteriesTitle:
silicon is a semiconductor material and inherently has a low electrical conductivity. In the process of charging and discharging, the insertion and the extraction of lithium ions can cause the volume of the material to expand and contract by more than 300%, so that the material is pulverized and cracked, the structure is collapsed, finally, the electrode active substance is separated from the current collector, the internal resistance of the battery is increased, and the cycle performance of the battery is greatly reduced.
In order to improve the cycle performance of the silicon-based negative electrode and improve the structural stability of the material in the cycle process, the silicon material is usually subjected to nanocrystallization and compounding, such as forming a porous material, a silicon thin film material, a silicon nanowire, a silicon composite material and a silicon oxide. The prepared silicon-based composite material is an effective method for relieving volume expansion in the charge and discharge processes, and the method is widely applied to modification research of lithium ion battery cathode materials.
In addition, the silicon-based material has a problem of low first coulombic efficiency (charge-discharge efficiency), which means that when a battery is prepared by matching a positive electrode material and a silicon-based negative electrode material, more lithium ions become negative electrode SEI film components after the first charge-discharge is completed or are consumed in other aspects, and cannot return to the positive electrode, so that the specific capacity is reduced.
CN110176601A discloses a carbon-coated silicon monoxide negative electrode material and a preparation method and application thereof, and the obtained carbon-coated silicon monoxide negative electrode material has a core-shell structure and comprises a core body, a buffer layer and an outer layer which are sequentially distributed from inside to outside; the core body is low-oxygen-value silicon monoxide, the buffer layer is a carbon nano tube, and the outer layer is a carbon coating layer; according to the method, the carbon nano tube is used as a flexible buffer layer to inhibit the volume change of the whole negative electrode material particles, but the volume change of a silicon monoxide core body cannot be inhibited, and the silicon monoxide still undergoes pulverization after multiple charge-discharge cycles; the modification method has no obvious effect on improving the first coulombic efficiency of the material.
CN110311120A discloses a magnesium-containing silicon oxide negative electrode material for a lithium ion battery and a preparation method thereof. The preparation method mainly comprises the steps of raw material preparation, magnesium silicide preparation and preparation of a magnesium-containing silicon oxide cathode material. Magnesium metal and silicon metal in the material are heated and compounded in a rotary heating furnace to generate magnesium silicide, but the amount of the formed magnesium silicide is limited due to uneven mixing degree, so that the effect of improving the first coulombic efficiency of the material cannot be well achieved.
CN103219504A discloses a silicon monoxide composite negative electrode material for lithium ion batteries and a preparation method thereof, wherein the pulverization of silicon particles is prevented by coating a carbon nanotube and an amorphous carbon coating layer on the outer layer of silicon monoxide; however, in each particle of the obtained negative electrode material, the silicon monoxide is gathered together to form a larger inner core, the silicon monoxide still undergoes pulverization after multiple charge-discharge cycles, and meanwhile, the silicon content of the negative electrode material is too low and the specific capacity is small; the modification method has no obvious effect on improving the first coulombic efficiency of the material.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and providing a preparation method of a magnesium-containing silicon monoxide/silicon @ resin carbon/CVD carbon material with sufficient reaction between magnesium and silicon; the magnesium-containing silicon monoxide/silicon @ resin carbon/CVD carbon material prepared by the preparation method has the advantages of high initial coulombic efficiency, large specific capacity and good cycle stability.
The technical scheme adopted by the invention for solving the technical problems is as follows: the preparation method of the magnesium-containing silicon monoxide/silicon @ resin carbon/CVD carbon material comprises the following steps:
(1) Adding silicon oxide particles and silicon particles into absolute ethyl alcohol, mixing, and performing ultrasonic dispersion to obtain dispersion liquid;
(2) Adding resin into the dispersion liquid, heating to dissolve the resin, stirring and grinding, and spray drying to obtain a dried product;
(3) Carrying out heat treatment on the dried product to enable the resin to foam and then carbonize to obtain a silicon monoxide/silicon @ resin carbon material;
(4) Placing a magnesium sheet on the surface of the SiO/Si @ resin carbon material, and carrying out heat treatment under a vacuum condition to obtain a Mg-containing SiO/Si @ resin carbon material;
(5) And (3) putting the magnesium-containing silicon monoxide/silicon @ resin carbon material into a chemical vapor deposition furnace, and performing surface carbon deposition by using a chemical vapor deposition method (CVD) to obtain the carbon material.
Preferably, in the step (1), the particle size of the silica particles is 1 to 30 μm (more preferably 5 to 15 μm).
Preferably, in the step (1), the particle diameter of the silicon particles is 10 nm to 300 nm (more preferably 50 nm to 150 nm).
Preferably, in the step (1), the mass ratio of the silicon oxide particles to the silicon particles is 1 to 10 (more preferably 3 to 5.
Preferably, in the step (1), the total concentration of the silicon oxide particles and the silicon particles in the dispersion is 400 to 1200 mg/L.
Preferably, in the step (2), the resin is one or more of polyethylene glycol, tween 80, furan resin and polyphenyl resin.
Preferably, in the step (2), the mass of the resin is 0.05 to 5 times (more preferably 0.5 to 2.5 times) the total mass of the silicon oxide particles and the silicon particles in the dispersion.
Preferably, in the step (2), the heating temperature is 30 to 100 ℃; the heating helps to dissolve the resin in the ethanol, so that the resin is uniformly coated on the surfaces of the silicon oxide particles and the silicon particles in the subsequent stirring and grinding process.
Preferably, in the step (2), the stirring and grinding are performed by using a ball mill, and the rotation speed of the ball mill is 1000 to 4500 r/min (more preferably 2000 to 3500 r/min).
Preferably, in the step (2), mixed particles with the median particle diameter of 100 to 800 nm are obtained after stirring and grinding; through grinding, the particle size of the larger silicon monoxide and silicon particles is reduced, and nanocrystallization is realized; several nano-particles are aggregated to form mixed particles, and the surface of the mixed particles is wrapped with resin dissolved in ethanol.
Preferably, in the step (2), the spray pressure of the spray drying is 0.1 to 5 MPa, the inlet temperature is 80 to 300 ℃, and the flow rate is 200 to 800 mL h -1 (ii) a Spray drying was used to remove ethanol and to granulate.
The heat treatment is carried out in two stages, the first stage is set at a low temperature to foam the resin, and the second stage is set at a higher temperature than the first stage to carbonize the resin.
Preferably, in the step (3), the foaming temperature is 100 to 400 ℃, the heating rate is 0.1 to 5 ℃/min, and the foaming time is 1 to 10 hours.
Preferably, in the step (3), the carbonization temperature is 300 to 600 ℃, the heating rate is 0.1 to 5 ℃/min, and the carbonization time is 1 to 10 h.
Preferably, in the step (4), the mass of the magnesium sheet is 1 to 2 times of that of the silicon particles; if the amount of magnesium used is too small, the amount of magnesium silicide to be formed is limited, and if the amount of magnesium is too large, side reactions are likely to occur.
Preferably, in the step (4), the heat treatment is carried out in a tube furnace under a vacuum condition of a gas pressure of 10 -1 ~10 -3 Pa, the temperature of the heat treatment is 400-600 ℃, the heating rate is 5-10 ℃/min, and the heat preservation time is 2-5 hours.
The heat treatment in the tube furnace needs to be carried out under the vacuum condition, so that the melting point of magnesium can be reduced, and side reactions can be avoided; during the heat treatment, the magnesium metal is molten and reacts with silicon to generate magnesium silicide after permeating into the silicon monoxide/silicon @ resin carbon material.
The resin carbon formed by carbonizing after resin foaming is coated on the surfaces of the silicon particles and the silicon oxide particles, and has a bridging effect among the particles, so that a three-dimensional porous framework structure is formed and becomes a magnesium diffusion channel when reacting in a tubular furnace, and the full reaction between metal magnesium and the silicon particles is facilitated.
Preferably, in the step (5), the temperature of the chemical vapor deposition is 600-1300 ℃ (more preferably 900-1200 ℃), the heating rate is 0.1-5 ℃/min (more preferably 1-3 ℃/min), the air pressure is 1-12kPa (more preferably 2-6 kPa), the reaction gas is one or more than two of methane, propylene or acetylene, and the gas flow is 0.5-10L min -1 (more preferably 1 to 5L min) -1 ) The treatment time is from 0.5 to 48h (more preferably from 1 to 5h). Pyrolytic carbon can be uniformly generated in situ on the surface of the silicon monoxide/magnesium silicide and in the gaps of the silicon monoxide/magnesium silicide @ resin carbon composite material by CVD, so that a fully-closed carbon coating layer is formed on the surface of the silicon monoxide/magnesium silicide particles.
After the resin wrapping the silicon monoxide and the silicon surface is foamed and carbonized, a uniform three-dimensional porous carbon skeleton is formed; when the magnesium and the porous carbon skeleton are subjected to heat treatment simultaneously, the three-dimensional porous carbon skeleton plays a role of a magnesium diffusion channel, so that the magnesium and silicon particles fully react to form a large amount of magnesium silicide; after the battery is manufactured, magnesium oxide can be preferentially formed when lithium ions are embedded into a negative electrode material, so that the formation of lithium oxide is reduced, and the first coulombic efficiency of the battery is increased; according to the invention, CVD pyrolytic carbon is deposited in situ on the basis of the three-dimensional porous framework, and a uniform and totally-enclosed carbon coating layer is formed on the surfaces of silicon monoxide and magnesium silicide together with the three-dimensional porous framework, so that the lithiation rate of an electrode material is increased by 3 to 4.5 times in the charging and discharging process of a lithium ion battery, and the charging and discharging efficiency is improved; the resin carbon/CVD carbon double-layer structure coated on the surfaces of the silicon monoxide and the magnesium silicide has better mechanical property relative to a single carbon layer or graphite layer, the resin carbon can ensure that the silicon monoxide and the magnesium silicide are uniformly dispersed in the carbon material, and the silicon monoxide and the magnesium silicide are not aggregated into large particles, so that the possibility of pulverization caused by volume expansion is reduced; compared with a single resin carbon coating layer, the coating effect and the conductive lithium-conducting performance of the method are better, and the charging and discharging efficiency is improved.
The invention has the beneficial effects that:
(1) According to the magnesium-containing silicon monoxide/silicon @ resin carbon/CVD carbon material, magnesium and silicon react fully, and more magnesium silicide is contained;
(2) The magnesium-containing SiO/Si @ resin carbon/CVD carbon material has a unique double-layer coating structure, siO and Mg silicide with small particle sizes are uniformly dispersed in the carbon material, the volume change of the silicon material in the charging and discharging processes is reduced, and pulverization is avoided; a totally-enclosed carbon coating layer is formed on the surfaces of the silicon monoxide and the magnesium silicide, the carbon coating layer is uniformly coated, the mechanical strength of the carbon coating layer is high, and the carbon coating layer is used for manufacturing a lithium ion battery cathode, and the lithiation rate is increased by 3 to 4.5 times;
(3) The preparation method has the advantages of simple operation, low cost and easy industrial production;
(4) The battery cathode material obtained by the invention can greatly improve the first coulombic efficiency of the lithium ion battery and prolong the service life of the lithium ion batteryA life; the obtained lithium ion battery has a capacity of 1 ag -1 The first coulombic efficiency at the circulating current of (1) was 91% at 1 ag -1 The capacity (specific capacity 953 mAh g) of 95% can be still maintained after 200 cycles under the current density of (1) -1 ) The coulombic efficiency is kept above 98%.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a negative electrode plate made of a magnesium-containing SiO/Si @ resin C/CVD carbon material prepared in example 1 of the present invention;
FIG. 2 shows that the concentration of the negative electrode of the lithium ion battery assembled by using the Mg-containing SiO/Si @ resin C/CVD carbon material prepared in example 1 is 0.1A g -1 A first charging and discharging curve chart under current density;
FIG. 3 shows that the amount of lithium ion battery assembled by using the negative electrode made of the Mg-containing SiO/Si @ resin C/CVD carbon material prepared in example 1 of the present invention is 1 Ag -1 Graph of cycling performance at current density.
Detailed Description
The present invention will be further described with reference to the following examples and the accompanying drawings.
While the following is a description of the preferred embodiments of the present invention, it should be noted that those skilled in the art can make various modifications and adaptations without departing from the principle of the present invention, and such modifications and adaptations are intended to be within the scope of the present invention as set forth in the following claims.
In each example, the raw materials used were all common commercial products.
Example 1
Preparation of magnesium-containing silicon monoxide/silicon @ resin carbon/CVD carbon material:
1) Adding silicon monoxide particles with the D50 particle size of 8 mu m and silicon particles with the D50 particle size of 100 nm into absolute ethyl alcohol for mixing, wherein the mass ratio of the silicon monoxide particles to the silicon particles is 5;
2) Adding polyethylene glycol resin into the dispersion, and heating to make the resinDissolving in ethanol, and grinding in a ball mill under stirring to obtain mixed particles with D50 particle diameter of 500 nm; the mass of the polyethylene glycol resin is 0.5 times of the total mass of silicon oxide particles and silicon particles in the dispersion liquid, the heating and dissolving temperature is 70 ℃, and the rotating speed of the ball mill is 2700 r/min; spray-drying the mixed granules at a spray pressure of 1 MPa, an inlet temperature of 200 deg.C and a flow rate of 500 mL h -1 Obtaining a dry product;
3) Foaming and carbonizing the dried product; wherein the foaming temperature is 240 ℃, the heating rate is 2 ℃/min, and the processing time is 5h; the carbonization temperature is 450 ℃, the heating rate is 2 ℃/min, and the carbonization time is 5h, so that the silicon monoxide/silicon @ resin carbon material is obtained;
4) Placing a magnesium sheet on the surface of the SiO/Si @ resin carbon material, and carrying out heat treatment in a tube furnace to obtain a Mg-containing SiO/Si @ resin carbon material; wherein the mass of the magnesium sheet is 1.5 times of that of the silicon particles, and the pressure in the tube furnace is 10 during heating -3 Pa, the heat treatment temperature is 720 ℃, the heating rate is 7 ℃/min, and the heat preservation time is 3 h;
5) Putting the magnesium-containing silicon monoxide/silicon @ resin carbon material into a Chemical Vapor Deposition (CVD) furnace for surface carbon deposition to obtain the carbon material; wherein the CVD treatment temperature is 900 ℃, the temperature rise rate of the CVD furnace is 2 ℃/min, and the treatment time is 20 h; the gas pressure is 6kPa, and the gas flow is 5L min -1 The carbon source is acetylene.
Preparing an electrode: mixing 90mg of magnesium-containing silicon monoxide/silicon @ resin carbon/CVD carbon material and 10mg of sodium carboxymethylcellulose (CMC) in an agate mortar, fully grinding, adding 600 mu l of ultrapure water, and stirring for 12 hours by using a magnetic stirrer; coating on a current collector to form a composite coating of 40 μm, and drying in a vacuum drying oven at 85 ℃; and cutting the current collector with the mixed material into a wafer with the diameter of 12mm to obtain the lithium ion battery cathode prepared from the magnesium-containing silicon monoxide/silicon @ resin carbon/CVD carbon material.
Assembling the battery: drying the prepared cathode in a vacuum drying oven, and putting the dried cathode in an argon-filled sealed glove box with metal lithium as a counter electrode, a microporous polypropylene film as a diaphragm and 1.0M LiPF 6 Is dissolved inThe volume ratio is 1:1:1, a CR2025 button cell is assembled by using a mixed solvent of ethylene carbonate (EG), dimethyl carbonate (DMC) and dimethyl carbonate (DMC) as an electrolyte and metal lithium as a counter electrode.
And (3) testing electrical properties: and testing the charge and discharge performance of the button cell in a voltage range of 0.02V to 1V.
FIG. 1 is an SEM image of a negative electrode sheet made from a Mg-containing SiO/Si @ resin carbon/CVD carbon material prepared in this example, in which it can be seen that fine particles are wrapped in carbon and bridged with other surrounding small particles by carbon; the resin carbon/CVD carbon layer was shown to coat the SiO and MgSi particles well, with the SiO and MgSi particles being uniformly dispersed in the carbon.
As can be seen from FIG. 2, the lithium ion battery assembled by using the negative electrode sheet made of the Mg-containing SiO/Si @ resin C/CVD carbon material prepared in this example was 0.1A g -1 The first coulombic efficiency is 91% under the current density of the current, and the first coulombic efficiency is obviously improved.
As can be seen from FIG. 3, the lithium ion battery assembled by using the negative electrode sheet made of the Mg-containing SiO/Si @ resin C/CVD carbon material prepared in this example was 1 Ag -1 After 200 cycles under the current density of (1), the capacity (specific capacity 953 mAh g) can still be kept at 95 percent -1 ) The coulombic efficiency can be kept above 98%, and the circulation stability is good.
Example 2
Preparation of magnesium-containing silicon monoxide/silicon @ resin carbon/CVD carbon material:
1) Adding silicon monoxide particles with the D50 particle size of 5 mu m and silicon particles with the D50 particle size of 50 nm into absolute ethyl alcohol, wherein the mass ratio of the silicon monoxide particles to the silicon particles is 1;
2) Adding Tween 80 resin into the dispersion, heating to dissolve the resin in ethanol, and placing in a ball mill for fully stirring and grinding to obtain mixed particles with D50 particle diameter of 100 nm; the mass of the Tween 80 resin is the total mass of silicon oxide particles and silicon particles in the dispersion liquid0.1 time of the total amount of the raw materials, the heating and dissolving temperature is 30 ℃, and the rotating speed of the ball mill is 2000 r/min; spray drying the mixed granules at a spray pressure of 0.1 MPa, an inlet temperature of 80 ℃ and a flow rate of 200 mL h -1 To obtain a dry product;
3) Foaming and carbonizing the dried product; wherein the foaming temperature is 100 ℃, and the heating rate is as follows: 0.1 The temperature is controlled to be lower than the boiling point of the water, and the treatment time is 1 h; the carbonization temperature is 300 ℃, the heating rate is 0.1 ℃/min, and the carbonization time is 1 h, so that the silicon monoxide/silicon @ resin carbon material is obtained;
4) Placing a magnesium sheet on the surface of the SiO/Si @ resin carbon material, and carrying out heat treatment in a tube furnace to obtain a Mg-containing SiO/Si @ resin carbon material; wherein the mass of the magnesium sheet is 1 time of that of the silicon particles, and the pressure in the tube furnace is 10 during heating -3 Pa, the heat treatment temperature is 650 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 2 h
5) Putting the magnesium-containing silicon monoxide/silicon @ resin carbon material into a Chemical Vapor Deposition (CVD) furnace for surface carbon deposition to obtain the carbon material; wherein the CVD treatment temperature is 600 ℃, the temperature rise rate of the CVD furnace is 0.1 ℃/min, and the treatment time is 1 h; the gas pressure is 2kPa, and the gas flow is 1L min -1 The carbon source is methane.
Preparing an electrode: mixing 90mg of magnesium-containing silicon monoxide/silicon @ resin carbon/CVD carbon material and 10mg of sodium carboxymethylcellulose (CMC) in an agate mortar, fully grinding, adding 600 mu l of ultrapure water, and stirring for 12 hours by using a magnetic stirrer; coating on a current collector to form a composite coating of 40 μm, and drying in a vacuum drying oven at 85 ℃; and cutting the current collector attached with the mixed material into a circular sheet with the diameter of 12mm to obtain the lithium ion battery cathode prepared by using the magnesium-containing silicon monoxide/silicon @ resin carbon/CVD carbon material.
Assembling the battery: drying the prepared cathode in a vacuum drying box, using metal lithium as a counter electrode in an argon-filled sealed glove box, using a microporous polypropylene film as a diaphragm and using 1.0M LiPF 6 Has a dissolution volume ratio of 1:1: 1a mixed solvent of ethylene carbonate (EG), dimethyl carbonate (DMC) and dimethyl carbonate (DMC) as an electrolyte, and metallic lithium as a counter electrode, to assemble CR2025A button cell.
And (3) testing electrical properties: and testing the charge and discharge performance of the button cell in a voltage range of 0.02V to 1V.
Through detection, in the cathode electrode plate prepared in the embodiment, fine particles of silicon monoxide and magnesium silicide are wrapped in carbon and bridged with other surrounding small particles through the carbon; the resin carbon/CVD carbon layer was shown to coat the SiO and MgSi particles well, with the SiO and MgSi particles being uniformly dispersed in the carbon.
The cell prepared in this example was tested at 0.1 ag -1 The first coulombic efficiency was 84% at current density of (1); at 1A g -1 The specific capacity of 921 mAh g can be still kept after 200 times of circulation under the current density of -1 And the obtained battery has good cycle performance.
Example 3
Preparation of magnesium-containing silicon monoxide/silicon @ resin carbon/CVD carbon material:
1) Adding silicon monoxide particles with the D50 particle size of 15 mu m and silicon particles with the D50 particle size of 150 nm into absolute ethyl alcohol for mixing, wherein the mass ratio of the silicon monoxide particles to the silicon particles is 3;
2) Adding furan resin into the dispersion liquid, heating to dissolve the resin in ethanol, and placing the solution in a ball mill for fully stirring and grinding to obtain mixed particles with the D50 particle size of 300 nm; the mass of the furan resin is 0.2 times of the total mass of silicon oxide particles and silicon particles in the dispersion liquid, the heating and dissolving temperature is 50 ℃, and the rotating speed of the ball mill is 2200 r/min; spray-drying the mixed granules at a spray pressure of 0.5 MPa, an inlet temperature of 150 ℃ and a flow rate of 400 mL h -1 Obtaining a dry product;
3) Foaming and carbonizing the dried product; wherein the foaming temperature is 180 ℃, the heating rate is 1 ℃/min, and the processing time is 3 h; the carbonization temperature is 400 ℃, the heating rate is 1 ℃/min, and the carbonization time is 3 h, so that the silicon monoxide/silicon @ resin carbon material is obtained;
4) Placing magnesium on the surface of the SiO/Si @ resin carbon materialCarrying out heat treatment on the sheet in a tube furnace to obtain a magnesium-containing silicon monoxide/silicon @ resin carbon material; wherein the mass of the magnesium sheet is 1.7 times of that of the silicon particles, and the pressure in the tubular furnace is 10 during heating -2 Pa, heat treatment temperature of 740 ℃, heating rate of 8 ℃/min, and heat preservation time of 4 h;
5) Putting the magnesium-containing silicon monoxide/silicon @ resin carbon material into a Chemical Vapor Deposition (CVD) furnace for surface carbon deposition to obtain the carbon material; the CVD treatment temperature is 800 ℃, the temperature rise rate of the CVD furnace is 1 ℃/min, and the treatment time is 10 h; the gas pressure is 4 kPa, and the gas flow is 2L min -1 The carbon source is acetylene.
Preparing an electrode: mixing 90mg of magnesium-containing silicon monoxide/silicon @ resin carbon/CVD carbon material and 10mg of sodium carboxymethylcellulose (CMC) in an agate mortar, fully grinding, adding 600 mu l of ultrapure water, and stirring for 12 hours by using a magnetic stirrer; coating on a current collector to form a composite coating of 40 μm, and drying in a vacuum drying oven at 85 ℃; and cutting the current collector attached with the mixed material into a circular sheet with the diameter of 12mm to obtain the lithium ion battery cathode prepared by using the magnesium-containing silicon monoxide/silicon @ resin carbon/CVD carbon material.
Assembling the battery: drying the prepared cathode in a vacuum drying oven, and putting the dried cathode in an argon-filled sealed glove box with metal lithium as a counter electrode, a microporous polypropylene film as a diaphragm and 1.0M LiPF 6 Has a dissolution volume ratio of 1:1:1, a CR2025 button cell is assembled by using a mixed solvent of ethylene carbonate (EG), dimethyl carbonate (DMC) and dimethyl carbonate (DMC) as an electrolyte and metal lithium as a counter electrode.
And (3) testing electrical properties: and testing the charge and discharge performance of the button cell in a voltage range of 0.02V to 1V.
Through detection, in the cathode electrode plate prepared in the embodiment, fine particles of silicon monoxide and magnesium silicide are wrapped in carbon and are bridged with other surrounding small particles through the carbon; the resin carbon/CVD carbon layer was shown to coat the silicon monoxide and magnesium silicide particles well, with the silicon monoxide and magnesium silicide particles uniformly dispersed in the carbon.
Upon detection, the cell prepared in this example was at 0.1 ag -1 The first coulombic efficiency was 83% at the current density of (1); at 1A g -1 The specific capacity of the alloy can be maintained at 912 mAh g after 200 cycles under the current density of the alloy -1 And the obtained battery has good cycle performance.
Example 4
Preparation of magnesium-containing silicon monoxide/silicon @ resin carbon/CVD carbon material:
1) Adding silicon monoxide particles with the D50 particle size of 23 mu m and silicon particles with the D50 particle size of 250 nm into absolute ethyl alcohol for mixing, wherein the mass ratio of the silicon monoxide particles to the silicon particles is 7;
2) Adding polyphenyl resin into the dispersion, heating to dissolve the resin into ethanol, and placing the mixture into a ball mill for fully stirring; grinding to obtain mixed particles with D50 particle size of 700 nm; the mass of the polyphenyl resin is 0.7 times of the total mass of silicon oxide particles and silicon particles in the dispersion liquid, the heating and dissolving temperature is 90 ℃, and the rotating speed of a ball mill is 3000 r/min; spray-drying the mixed granules at a spray pressure of 2 MPa, an inlet temperature of 250 ℃ and a flow rate of 600 mL h -1 To obtain a dry product;
3) Foaming and carbonizing the dried product; wherein the foaming temperature is 360 ℃, the heating rate is 3 ℃/min, and the processing time is 7 h; the carbonization temperature is 500 ℃, the heating rate is 3 ℃/min, and the carbonization time is 7 h, so that the silicon monoxide/silicon @ resin carbon material is obtained;
4) Placing a magnesium sheet on the surface of the SiO/Si @ resin carbon material, and carrying out heat treatment in a tube furnace to obtain a Mg-containing SiO/Si @ resin carbon material; wherein the mass of the magnesium sheet is 2 times of that of the silicon particles, and the pressure in the tubular furnace is 10 during heating -1 Pa, the heat treatment temperature is 750 ℃, the heating rate is 10 ℃/min, and the heat preservation time is 5h;
5) Putting the magnesium-containing silicon monoxide/silicon @ resin carbon material into a Chemical Vapor Deposition (CVD) furnace for surface carbon deposition to obtain the carbon material; wherein the CVD treatment temperature is 1100 ℃, the temperature rise rate of the CVD furnace is 3 ℃/min, and the treatment time is 30 h; the gas pressure is 9 kPa, and the gas flow is 8L min -1 The carbon source is methane.
Preparing an electrode: mixing 90mg of magnesium-containing silicon monoxide/silicon @ resin carbon/CVD carbon material and 10mg of sodium carboxymethylcellulose (CMC) in an agate mortar, fully grinding, adding 600 mu l of ultrapure water, and stirring for 12 hours by using a magnetic stirrer; coating on a current collector to form a composite coating of 40 μm, and drying in a vacuum drying oven at 85 ℃; and cutting the current collector attached with the mixed material into a circular sheet with the diameter of 12mm to obtain the lithium ion battery cathode prepared by using the magnesium-containing silicon monoxide/silicon @ resin carbon/CVD carbon material.
Assembling the battery: drying the prepared cathode in a vacuum drying box, using metal lithium as a counter electrode in an argon-filled sealed glove box, using a microporous polypropylene film as a diaphragm and using 1.0M LiPF 6 Has a dissolution volume ratio of 1:1:1, a CR2025 button cell is assembled by using a mixed solvent of ethylene carbonate (EG), dimethyl carbonate (DMC) and dimethyl carbonate (DMC) as an electrolyte and metal lithium as a counter electrode.
And (3) testing electrical properties: and testing the charge and discharge performance of the button cell in a voltage range of 0.02V to 1V.
Through detection, in the cathode electrode plate prepared in the embodiment, fine particles of silicon monoxide and magnesium silicide are wrapped in carbon and are bridged with other surrounding small particles through the carbon; the resin carbon/CVD carbon layer was shown to coat the SiO and MgSi particles well, with the SiO and MgSi particles being uniformly dispersed in the carbon.
The cell prepared in this example was tested at 0.1 ag -1 The first coulombic efficiency was 86% at the current density of (1); at 1A g -1 The specific capacity of 895 mAh g can be still kept after 200 times of circulation under the current density of -1 And the obtained battery has good cycle performance.
Example 5
Preparation of magnesium-containing silicon monoxide/silicon @ resin carbon/CVD carbon material:
1) Adding silicon monoxide particles with the D50 particle size of 18 mu m and silicon particles with the D50 particle size of 20 nm into absolute ethyl alcohol for mixing, wherein the mass ratio of the silicon monoxide particles to the silicon particles is 10;
2) Adding furan resin into the dispersion, heating to dissolve the resin in ethanol, and placing the solution in a ball mill for fully stirring and grinding to obtain mixed particles with the D50 particle size of 800 nm; the mass of the furan resin is 1 time of the total mass of silicon oxide particles and silicon particles in the dispersion liquid, the heating and dissolving temperature is 100 ℃, and the rotating speed of the ball mill is 3500 r/min; spray-drying the mixed granules at a spray pressure of 5 MPa, an inlet temperature of 300 ℃ and a flow rate of 800 mL h -1 To obtain a dry product;
3) Foaming and carbonizing the dried product; wherein the foaming temperature is 400 ℃, the heating rate is 5 ℃/min, and the processing time is 10 h; the carbonization temperature is 600 ℃, the heating rate is 5 ℃/min, and the carbonization time is 10 h, so that the silicon monoxide/silicon @ resin carbon material is obtained;
4) Placing a magnesium sheet on the surface of the SiO/Si @ resin carbon material, and carrying out heat treatment in a tube furnace to obtain a Mg-containing SiO/Si @ resin carbon material; wherein the mass of the magnesium sheet is 1.2 times of that of the silicon particles, and the pressure in the tube furnace is 10 during heating -2 Pa, the heat treatment temperature is 680 ℃, the heating rate is 6 ℃/min, and the heat preservation time is 2.5 hours;
5) Putting the magnesium-containing silicon monoxide/silicon @ resin carbon material into a Chemical Vapor Deposition (CVD) furnace for surface carbon deposition, wherein the CVD treatment temperature is 1300 ℃, the temperature rise rate of the CVD furnace is 5 ℃/min, and the treatment time is 48 h; the gas pressure is 12kPa, and the gas flow is 10L min -1 The carbon source is acetylene.
Preparing an electrode: mixing 90mg of magnesium-containing silicon monoxide/silicon @ resin carbon/CVD carbon material and 10mg of sodium carboxymethylcellulose (CMC) in an agate mortar, fully grinding, adding 600 mu l of ultrapure water, and stirring for 12 hours by using a magnetic stirrer; coating on a current collector to form a composite coating of 40 μm, and drying in a vacuum drying oven at 85 ℃; and cutting the current collector attached with the mixed material into a circular sheet with the diameter of 12mm to obtain the lithium ion battery cathode prepared by using the magnesium-containing silicon monoxide/silicon @ resin carbon/CVD carbon material.
Assembling the battery: the manufactured cathode is in trueDrying in an air drying box, using metal lithium as a counter electrode, using a microporous polypropylene membrane as a diaphragm and 1.0M LiPF in an argon-filled sealed glove box 6 Is dissolved in a solvent at a volume ratio of 1:1:1, a mixed solvent of ethylene carbonate (EG), dimethyl carbonate (DMC) and dimethyl carbonate (DMC) is used as an electrolyte, and metal lithium is used as a counter electrode, so that the CR2025 button cell is assembled.
And (3) testing electrical properties: and testing the charge and discharge performance of the button cell in a voltage range of 0.02V to 1V.
Through detection, in the cathode electrode plate prepared in the embodiment, fine particles of silicon monoxide and magnesium silicide are wrapped in carbon and are bridged with other surrounding small particles through the carbon; the resin carbon/CVD carbon layer was shown to coat the SiO and MgSi particles well, with the SiO and MgSi particles being uniformly dispersed in the carbon.
The cell prepared in this example was tested at 0.1 ag -1 At a current density of (1) the first coulombic efficiency was 88%, at 1 ag -1 The specific capacity of 918 mAh g can be still maintained after 200 cycles under the current density of (1) -1 And the obtained battery has good cycle performance.
Comparative example 1
Preparation of silicon monoxide @ resin carbon material:
1) Adding silicon oxide particles with the D50 particle size of 120 nm into absolute ethyl alcohol, and fully dispersing the silicon oxide particles by using ultrasound to obtain dispersion liquid, wherein the concentration of the silicon oxide particles in the dispersion liquid is 1000 mg/L;
2) Adding polyethylene glycol resin into the dispersion, heating to dissolve the resin in ethanol, and placing the mixture in a ball mill to be fully stirred and ground to obtain a mixture; the mass of the resin is 0.7 times of that of silicon oxide particles, the heating and dissolving temperature is 90 ℃, the rotating speed of a ball mill is 3000 r/min, and the D50 particle size of the obtained mixture is 700 nm;
3) Spray-drying the mixture at a spray pressure of 2 MPa, an inlet temperature of 250 ℃ and a flow rate of 600 mL h -1 Obtaining a dry product;
4) Placing the dried product in a high-temperature furnace for heat treatment foaming and carbonization to obtain the product; wherein the heat treatment foaming temperature is 360 ℃, the heating rate is 3 ℃/min, and the treatment time is 7 h; wherein the carbonization temperature is 1100 ℃, the heating rate is 3 ℃/min, and the processing time is 30 h;
preparing an electrode: mixing 90mg of silicon monoxide @ resin carbon and 10mg of sodium carboxymethylcellulose (CMC) in an agate mortar, fully grinding, adding 600 mu l of ultrapure water, and stirring for 12 hours by using a magnetic stirrer; coating the mixture on a current collector to form a composite coating with the thickness of 40 mu m, and drying the composite coating in a vacuum drying oven at the temperature of 85 ℃; and cutting the current collector with the mixed material into a circular sheet with the diameter of 12mm to obtain the silicon monoxide @ resin carbon material battery cathode.
Assembling the battery: drying the obtained negative electrode in a vacuum drying box, taking metal lithium as a counter electrode in an argon-filled sealed glove box, taking a microporous polypropylene membrane as a diaphragm and 1.0M LiPF 6 Has a dissolution volume ratio of 1:1:1, a mixed solvent of ethylene carbonate (EG), dimethyl carbonate (DMC) and dimethyl carbonate (DMC) is used as an electrolyte, and metal lithium is used as a counter electrode, so that the CR2025 button cell is assembled.
And (3) testing electrical properties: and testing the charge and discharge performance of the button cell in a voltage range of 0.02V to 1V. At 0.1A g -1 At a current density of (1) the first coulombic efficiency was 75%, at 1 ag -1 The specific capacity is 754 mAh g after 200 cycles under the current density of (1) -1 。
Comparative example 2
Preparation of silicon monoxide @ CVD carbon material:
1) Depositing silicon oxide particles with the D50 particle size of 120 nm in a CVD furnace to obtain the silicon oxide particles; wherein the CVD treatment temperature is 1100 ℃, the temperature rise rate of the CVD furnace is 3 ℃/min, and the treatment time is 30 h; the gas pressure is 9 kPa, and the gas flow is 8L min -1 The carbon source is methane.
Preparing an electrode: mixing 90mg of silicon monoxide @ CVD carbon and 10mg of sodium carboxymethylcellulose (CMC) in an agate mortar, fully grinding, adding 600 mu l of ultrapure water, and stirring for 12 hours by using a magnetic stirrer; coating the mixture on a current collector to form a composite coating with the thickness of 40 mu m, and drying the composite coating in a vacuum drying oven at the temperature of 85 ℃; and cutting the current collector attached with the mixed material into a circular sheet with the diameter of 12mm to obtain the silicon monoxide @ CVD carbon material battery cathode.
Assembling the battery: drying the obtained negative electrode in a vacuum drying box, taking metal lithium as a counter electrode in an argon-filled sealed glove box, taking a microporous polypropylene membrane as a diaphragm and 1.0M LiPF 6 Has a dissolution volume ratio of 1:1:1, a CR2025 button cell is assembled by using a mixed solvent of ethylene carbonate (EG), dimethyl carbonate (DMC) and dimethyl carbonate (DMC) as an electrolyte and metal lithium as a counter electrode.
And (3) testing electrical properties: and testing the charge and discharge performance of the button cell in a voltage range of 0.02V to 1V. At 0.1A g -1 The first coulombic efficiency at a current density of 73% was at 1 ag -1 After 200 cycles, the specific capacity is 732 mAh g -1 。
Comparative example 3
The preparation method of the carbon material of silicon monoxide/silicon @ resin/CVD comprises the following steps:
1) Adding silicon monoxide particles with the D50 particle size of 10 microns and silicon particles with the D50 particle size of 120 nm into absolute ethyl alcohol for mixing, wherein the mass ratio of the silicon monoxide particles to the silicon particles is 5;
2) Adding polyethylene glycol resin into the dispersion, heating to dissolve the resin in ethanol, and placing in a ball mill for fully stirring and grinding to obtain mixed particles with D50 particle size of 500 nm; the mass of the polyethylene glycol resin is 0.5 times of the total mass of silicon oxide particles and silicon particles in the dispersion liquid, the heating and dissolving temperature is 70 ℃, and the rotating speed of the ball mill is 2700 r/min; spray-drying the mixed granules at a spray pressure of 1 MPa, an inlet temperature of 200 deg.C and a flow rate of 500 mL h -1 To obtain a dry product;
3) Placing the dried product in a CVD furnace for heat treatment foaming, carbonization and CVD to obtain the product; wherein the heat treatment foaming temperature is 240 ℃, and the heating rate is as follows: 2. the temperature is controlled to be lower than the boiling point of the water, and the treatment time is 5 hours; the carbonization temperature is 450 ℃, the heating rate is 2 ℃/min, and the carbonization time is 5h; the CVD treatment temperature is 900 ℃, and the temperature rising rate of the CVD furnace isThe temperature is 2 ℃/min, and the treatment time is 20 h; the gas pressure is 6kPa, and the gas flow is 5L min -1 The carbon source is acetylene.
Preparing an electrode: mixing 90mg of silicon monoxide/silicon @ resin carbon/CVD carbon material and 10mg of sodium carboxymethylcellulose (CMC) in an agate mortar, fully grinding, adding 600 mu l of ultrapure water, and stirring for 12 hours by using a magnetic stirrer; coating on a current collector to form a composite coating of 40 μm, and drying in a vacuum drying oven at 85 ℃; and cutting the current collector with the mixed material into a circular piece with the diameter of 12mm to obtain the battery cathode made of the silicon monoxide/silicon @ resin carbon/CVD carbon material.
Assembling the battery: drying the obtained negative electrode in a vacuum drying box, and putting the negative electrode in an argon-filled sealed glove box, wherein the metal lithium is used as a counter electrode, a microporous polypropylene film is used as a diaphragm, and 1.0M LiPF is added 6 Has a dissolution volume ratio of 1:1:1, a mixed solvent of ethylene carbonate (EG), dimethyl carbonate (DMC) and dimethyl carbonate (DMC) is used as an electrolyte, and metal lithium is used as a counter electrode, so that the CR2025 button cell is assembled.
And (3) testing electrical properties: and testing the charge and discharge performance of the button cell in a voltage range of 0.02V to 1V. At 0.1A g -1 At a current density of (1) the first coulombic efficiency was 76%, at 1 ag -1 After 200 cycles, the specific capacity is 704 mAh g -1 。

Claims (15)

1. The preparation method of the magnesium-containing silicon monoxide/silicon @ resin carbon/CVD carbon material is characterized by comprising the following steps of:
(1) Adding silicon oxide particles and silicon particles into absolute ethyl alcohol, mixing, and performing ultrasonic dispersion to obtain dispersion liquid;
(2) Adding resin into the dispersion liquid, heating to dissolve the resin, stirring and grinding, and performing spray drying to obtain a dried product;
(3) Carrying out heat treatment on the dried product to enable the resin to foam and then carbonize to obtain a silicon monoxide/silicon @ resin carbon material;
(4) Placing a magnesium sheet on the surface of the SiO/Si @ resin carbon material, and carrying out heat treatment under a vacuum condition to obtain a Mg-containing SiO/Si @ resin carbon material;
(5) Putting the magnesium-containing silicon monoxide/silicon @ resin carbon material into a chemical vapor deposition furnace, and performing surface carbon deposition by using a chemical vapor deposition method to obtain the magnesium-containing silicon monoxide/silicon @ resin carbon material;
in the step (1), the particle size of the silicon oxide particles is 1-30 mu m; the particle size of the silicon particles is 10 nm to 300 nm; the mass ratio of the silicon oxide particles to the silicon particles is 1 to 10;
in the step (2), the resin is one or more than two of polyethylene glycol, tween 80, furan resin and polyphenyl resin; the mass of the resin is 0.05 to 5 times of the total mass of the silicon oxide particles and the silicon particles in the dispersion liquid.
2. The process of claim 1 wherein in step (1); the total concentration of silicon oxide particles and silicon particles in the dispersion is 400 to 1200 mg/L.
3. The method for preparing a magnesium-containing silicon monoxide/silicon @ resin carbon/CVD carbon material as claimed in claim 1, wherein the heating temperature in step (2) is 30 to 100 ℃.
4. The method for preparing the magnesium-containing silicon monoxide/silicon @ resin carbon/CVD carbon material according to claim 1, wherein in the step (2), the stirring and grinding are carried out by using a ball mill, and the rotation speed of the ball mill is 1000 to 4500 r/min; stirring and grinding to obtain mixed particles with the median particle size of 100 to 800 nm.
5. The method for preparing a magnesium-containing silicon monoxide/silicon @ resin carbon/CVD carbon material as claimed in claim 1, wherein in the step (2), the spray drying is carried out at a spray pressure of 0.1 to 5 MPa, an inlet temperature of 80 to 300 ℃ and a flow rate of 200 to 800 mL h -1 。
6. The method for preparing the magnesium-containing silicon monoxide/silicon @ resin carbon/CVD carbon material according to any one of claims 1 to 5, wherein in the step (3), the foaming temperature is 100 to 400 ℃, the heating rate is 0.1 to 5 ℃/min, and the foaming time is 1 to 10 hours; the carbonization temperature is 300 to 600 ℃, the heating rate is 0.1 to 5 ℃/min, and the carbonization time is 1 to 10 h.
7. The preparation method of the magnesium-containing silicon monoxide/silicon @ resin carbon/CVD carbon material as claimed in any one of claims 1 to 5, wherein in the step (4), the mass of the magnesium sheet is 1 to 2 times of that of the silicon particles.
8. The method for preparing the magnesium-containing SiO/Si @ resin carbon/CVD carbon material as defined in claim 6, wherein in the step (4), the mass of the magnesium sheet is 1 to 2 times that of the silicon particles.
9. The method for preparing a magnesium-containing SiO/Si @ resin C/CVD carbon material as claimed in any one of claims 1 to 5, wherein the heat treatment is performed in step (4) in a tube furnace under a vacuum condition of 10 atm -1 ~10 -3 Pa, the temperature of the heat treatment is 400 to 600 ℃, the heating rate is 5 to 10 ℃/min, and the heat preservation time is 2 to 5 hours.
10. The method for preparing a Mg-containing SiO/Si @ resin C/CVD carbon material as claimed in claim 6, wherein in the step (4), the heat treatment is carried out in a tube furnace under a vacuum condition at a gas pressure of 10 atm -1 ~10 -3 Pa, the temperature of the heat treatment is 400 to 600 ℃, the heating rate is 5 to 10 ℃/min, and the heat preservation time is 2 to 5 hours.
11. The method for preparing a magnesium-containing SiO/Si @ resin carbon/CVD carbon material as defined in claim 7, wherein in the step (4), the heat treatment is carried out in a tube furnace under a vacuum condition at a pressure of 10 atm -1 ~10 -3 Pa, the temperature of the heat treatment is 400 to 600 ℃, the heating rate is 5 to 10 ℃/min, and the heat preservation time is 2 to 5 hours.
12. The preparation method of the magnesium-containing SiO/Si @ resin carbon/CVD carbon material as claimed in any one of claims 1 to 5, wherein in the step (5), the temperature of chemical vapor deposition is 600 ℃ to 1300 ℃, the temperature rise rate is 0.1 to 5 ℃/min, the air pressure is 1 to 12kPa, the reaction gas is one or more of methane, propylene or acetylene, and the gas flow is 0.5 to 10L min -1 The treatment time is 0.5 to 48h.
13. The preparation method of the magnesium-containing silicon monoxide/silicon @ resin carbon/CVD carbon material as claimed in claim 6, wherein in the step (5), the temperature of chemical vapor deposition is 600-1300 ℃, the temperature rise rate is 0.1-5 ℃/min, the air pressure is 1-12kPa, the reaction gas is one or more of methane, propylene or acetylene, and the gas flow is 0.5-10L min -1 The treatment time is 0.5 to 48h.
14. The preparation method of the Mg-containing SiO/Si @ resin C/CVD carbon material as claimed in claim 7, wherein in the step (5), the temperature of chemical vapor deposition is 600 ℃ to 1300 ℃, the temperature rise rate is 0.1 to 5 ℃/min, the air pressure is 1 to 12kPa, the reaction gas is one or more of methane, propylene or acetylene, and the gas flow is 0.5 to 10L min -1 The treatment time is 0.5 to 48h.
15. The preparation method of the magnesium-containing silicon monoxide/silicon @ resin carbon/CVD carbon material as claimed in claim 9, wherein in the step (5), the temperature of chemical vapor deposition is 600-1300 ℃, the temperature rise rate is 0.1-5 ℃/min, the air pressure is 1-12kPa, the reaction gas is one or more of methane, propylene or acetylene, and the gas flow is 0.5-10L min -1 The processing time is 0.5 to 48h.
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