CN113871587A - Preparation method of silicon @ carbon nanotube @ carbon composite negative electrode material of lithium ion battery - Google Patents

Preparation method of silicon @ carbon nanotube @ carbon composite negative electrode material of lithium ion battery Download PDF

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CN113871587A
CN113871587A CN202111050658.XA CN202111050658A CN113871587A CN 113871587 A CN113871587 A CN 113871587A CN 202111050658 A CN202111050658 A CN 202111050658A CN 113871587 A CN113871587 A CN 113871587A
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CN113871587B (en
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闫小琴
王成登
顾有松
张文远
王东华
史浩锋
纪箴
王贯勇
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Guizhou Zhongshui Material Technology Co ltd
University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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Abstract

A preparation method of a silicon @ carbon nanotube @ carbon composite negative electrode material of a lithium ion battery is disclosed. Firstly, cutting polysilicon into silicon mud serving as a silicon source, obtaining high-purity micron-level flaky silicon powder by means of acid washing and the like, and then refining a micron silicon wafer to a nanometer size by dry ball milling; coating nano silicon by using starch and carbon nano tubes as carbon sources through a two-step ball milling method; and then carrying out high-temperature heat treatment to obtain the silicon @ carbon nanotube @ carbon composite anode material (QSi @ CNTs @ C). In the composite material, carbon nanotubes are mutually connected among nano-silicon to form a conductive network, so that a channel is provided for ion transmission, the conductive effect is achieved, and meanwhile sufficient vacancies can relieve the volume expansion of silicon; the carbon wraps the nano silicon and the carbon nano tubes in the microspheres, so that the nano silicon can be prevented from contacting with electrolyte, the consumption of the electrolyte is reduced, and the volume expansion of the silicon is inhibited. The composite material prepared by the invention has excellent rate capability and cycle performance, the preparation method is simple, the cost is low, and industrialization can be realized.

Description

Preparation method of silicon @ carbon nanotube @ carbon composite negative electrode material of lithium ion battery
Technical Field
The invention belongs to the field of lithium ion battery cathode materials, and particularly relates to a preparation method for constructing a silicon @ carbon nanotube @ carbon composite cathode material of a lithium ion battery. The method adopts low-cost polysilicon cutting silicon mud as a silicon source, prepares nano silicon by ball-milling the polysilicon cutting silicon mud by a dry method, then prepares the silicon @ carbon nano tube @ starch composite material by two-step ball-milling, and finally carries out high-temperature carbonization on the silicon @ carbon nano tube @ carbon lithium ion battery cathode material to obtain the silicon @ carbon nano tube @ carbon lithium ion battery cathode material.
Background
With the continuous progress and rapid development of electronic technology, the demand of human beings for portable battery systems is increasing. Graphite is a poor choice for the current commercial lithium ion battery cathode material due to the advantages of good stability, low working voltage and the like. However, the theoretical specific capacity is lower and is only 372mAh g-1The energy density of the lithium ion battery can not meet the requirement of human society on high energy density of the lithium ion battery. Therefore, an ideal cathode material is foundReplacing graphite is the current focus of research. Silicon has very high theoretical specific capacity, up to 4200mAh g-1About ten times as much as graphite; and the working voltage is low, and the reserves in the crust are extremely abundant, so the lithium ion battery anode is the first choice material of the next generation of high energy density lithium ion battery. However, silicon alone as a negative electrode material has poor conductivity, and generates huge volume change during charging and discharging, so that the electrolyte is continuously consumed, and the capacity of the lithium ion battery is rapidly attenuated, and the coulombic efficiency is low. In response to these problems, reducing the size of silicon to the nanometer level can effectively reduce the volume expansion effect of silicon, and then further compounding with a carbon material having excellent conductivity can improve the conductivity and cycle performance thereof. However, the current silicon-carbon cathode material has poor conductivity, unstable cycle performance, high material cost and complex process. The key point for solving the problems is to develop the silicon-carbon negative electrode material with excellent performance.
Disclosure of Invention
The invention aims to provide a preparation method of a silicon @ carbon nanotube @ carbon negative electrode material, which has economic benefits, is simple to prepare and can realize industrialization. The carbon nano tubes are mutually connected between the nano silicon to form a three-dimensional conductive network which is electron and Li+The ion transmission provides a channel, on one hand, the channel plays a role in conducting electricity, and on the other hand, the sufficient vacancies can relieve the volume expansion of silicon; the carbon wraps the nano silicon and the carbon nano tubes in the microspheres, so that the nano silicon can be prevented from contacting with electrolyte, the consumption of the electrolyte is reduced, and the volume expansion of the silicon is inhibited. The prepared composite material shows good rate performance and excellent cycling stability, and is considered to be an ideal lithium ion battery cathode material.
The preparation method of the lithium ion battery silicon @ carbon nanotube @ carbon negative electrode material is shown in figure 1.
The preparation steps are as follows:
step one, preparing nano silicon: putting the pickled polycrystalline silicon cutting silicon mud into a zirconia ball milling tank, wherein the ratio of ball milling beads to materials (polycrystalline silicon cutting silicon mud) is 50:1, and then putting the ball milling tank on a planetary ball mill. And performing dry ball milling for 10-12h at the rotating speed of 500-600r/min, and sieving the ball-milled silicon powder to obtain the nano-silicon powder.
Step two, preparing the silicon @ carbon nanotube composite material: sequentially adding nano silicon, carbon nano tubes and polyvinylpyrrolidone into deionized water, and carrying out ultrasonic treatment for 1-2h to obtain a mixed solution; dividing the mixed solution into N equal parts, respectively placing the N equal parts into zirconia ball milling tanks, and then placing the ball milling tanks on a planetary ball mill. Regulating the rotating speed to 500-600r/min, carrying out wet ball milling for 2-4h, centrifuging and cleaning the obtained solution, and finally placing the solution in a drying box for treatment at 60 ℃ for 10-12h to obtain the silicon @ carbon nanotube composite material which is marked as QSi @ CNTs.
Step three, preparing the silicon @ carbon nanotube @ starch composite material: and (3) weighing a proper amount of starch and the QSi @ CNTs prepared in the second step, adding into a zirconia ball milling tank, and then placing the ball milling tank on a planetary ball mill. The rotating speed is adjusted to 500-600r/min, the composite material is ball milled for 10-12h by a dry method, and the ball milled composite material is sieved to obtain silicon @ carbon nano tube @ Starch composite material powder which is marked as QSi @ CNTs @ Starch.
Step four, preparing the silicon @ carbon nanotube @ carbon composite material: grinding the QSi @ CNTs @ Starch composite material prepared in the third step, placing the ground composite material in a quartz boat, and adding N2And (2) carrying out high-temperature carbonization in the atmosphere, and then naturally cooling to room temperature to obtain the silicon @ carbon nanotube @ carbon composite material which is marked as QSi @ CNTs @ C.
Further, in the first step, the number of the N equal parts of the mixed solution is 2 parts or 4 parts, and the corresponding number of the zirconia ball milling tanks is 2 or 4.
Further, in the step one, the diameters of the zirconia ball grinding beads are respectively 5mm, 8 mm, 10 mm and 15mm, the mass ratio of the correspondingly added grinding beads is 2:2:2:1, the ratio of the grinding beads to the material (polysilicon cutting silica mud) is 50:1, the rotation speed of the ball mill is 500-600r/min, the ball milling time is 10-12h, and a space which is not less than 1/3 needs to be reserved in a ball milling tank.
Further, in the second step, the content of the nano-silicon in the mixed solution prepared by every 100ml of deionized water is 0.5-1 g; the content of the carbon nano tube is 0.25-0.5 g; the content of polyvinylpyrrolidone is 0.25-0.5g, and the total mass of substances added in per 100ml of deionized water is 1-2 g.
Further, the centrifugation and washing processes in the second step are repeated for 2-4 times.
Furthermore, the addition amount of QSi/CNTs in the zirconia ball milling tank in the third step is 0.6-1g, and the corresponding addition amount of starch is 1.6-10 g.
Further, the heat treatment in the fourth step is a step heating, which is heating to 300-.
The technical key points of the preparation process of the silicon @ carbon nanotube @ carbon anode material are as follows: the dosage of nano silicon, carbon nano tube and starch, ball milling time, annealing temperature, heat preservation time and the like.
The mass ratio range of the nano silicon to the carbon nano tube to the starch is 1: 0.25: 4-1:0.5:10, the time of wet ball milling is 2-4h, the time of dry ball milling is 10-12h, the annealing temperature is 700-900 ℃, because the nano silicon and the carbon nano tube can be coated in the carbon ball in the parameter range.
The lithium ion battery silicon @ carbon nanotube @ carbon anode material and the preparation method thereof have the following specific preparation steps:
step one, preparing nano silicon: putting equal parts of the pickled polycrystalline silicon cutting silicon mud into 2 or 4 100ml zirconia ball milling tanks, adding zirconia ball milling beads into the ball milling tanks, wherein the diameters of the ball milling beads are respectively 5mm, 8 mm, 10 mm and 15mm, the corresponding addition mass ratio is 2:2:2:1, and the ratio of the ball milling beads to the materials (polycrystalline silicon cutting silicon mud) is 50:1, and then placing the ball milling tanks on a planetary ball mill. And performing dry ball milling for 10-12h at the rotating speed of 500-600r/min, and sieving the ball-milled silicon powder to obtain the nano-silicon powder.
Step two, preparing the silicon @ carbon nanotube composite material: sequentially adding nano-silicon, a carbon nano-tube and polyvinylpyrrolidone into 100-200ml of deionized water, wherein the content of the added nano-silicon is 0.5-1 g; the content of the carbon nano tube is 0.25-0.5 g. Performing ultrasonic treatment for 1-2h to obtain a mixed solution, wherein the content of polyvinylpyrrolidone is 0.25-0.5 g; dividing the mixed solution into 2 equal parts or 4 equal parts, putting the 2 equal parts or 4 equal parts into 2 zirconia ball milling tanks with the volume of 100ml, adding ball milling beads into the ball milling tanks, wherein the diameters of the ball milling beads are respectively 5mm, 8 mm, 10 mm and 15mm, the corresponding mass ratio of the ball milling beads to the materials (the mixed solution) is 2:2:2:1, and then putting the ball milling tanks on a planet ball mill. And carrying out wet ball milling for 2-4h at the rotation speed of 500-600r/min, centrifuging and cleaning the obtained solution for 2-4 times, and finally treating the solution for 10-12h in a drying box at the temperature of 60 ℃ to obtain silicon @ carbon nanotube composite powder which is marked as QSi @ CNTs.
Step three, preparing the silicon @ carbon nanotube @ starch composite material: weighing 1.6-10g of starch and 0.6-1g of QSi @ CNTs prepared in the second step (namely, controlling the ratio of silicon to carbon nanotubes to starch to be 1:0.5:4-1:0.5:10), adding the starch and 0.6-1g of QSi @ CNTs prepared in the second step into two zirconia ball milling tanks with the volume of 100ml, adding ball milling beads into the ball milling tanks, wherein the diameters of the ball milling beads are 5mm, 8 mm, 10 mm and 15mm respectively, the mass ratio of the corresponding addition amounts is 2:2:2:1, and the ratio of the ball milling beads to materials is 50:1, and then placing the ball milling tanks on a planet ball mill. And (3) performing dry ball milling for 10-12h at the rotating speed of 500-600r/min, and sieving the ball-milled composite material to obtain silicon @ carbon nano tube @ Starch composite material powder which is marked as QSi @ CNTs @ Starch.
Step four, preparing the silicon @ carbon nanotube @ carbon composite material: grinding the QSi @ CNTs @ Starch composite material powder prepared in the third step, placing the ground powder into a quartz boat, and placing the quartz boat in the N2Under the atmosphere, the gas flow rate is 90sccm, the silicon @ carbon nanotube @ carbon composite material is firstly heated to 300 ℃ at the heating rate of 5 ℃/min and is kept for 1-2h, then is heated to 800 ℃ at the same heating rate and is kept for 2-3h, and then is naturally cooled to room temperature along with a furnace, so that the silicon @ carbon nanotube @ carbon composite material is obtained, and is marked as QSi @ CNTs @ C.
Has the advantages that:
(1) the method takes the polysilicon cutting silicon mud as a silicon source, reduces the size of silicon particles by a dry ball milling method, and has the advantages of low cost, simple operation, environmental protection and realization of large-scale industrial production.
(2) The ball milling method is used for coating carbon on the prepared nano silicon, and the carbon nano tubes are mutually connected among the nano silicon to form a three-dimensional conductive network, so that the conductive effect is achieved on one hand, and the sufficient vacant sites can effectively relieve the volume expansion of the silicon on the other hand; the carbon wraps the nano silicon and the carbon nano tubes in the microspheres, so that the nano silicon can be prevented from contacting with the electrolyte, the consumption of the electrolyte is reduced, and the volume expansion of the silicon is inhibited; part of the carbon nano tube extends out of the micro-sphere to provide a channel for ion transmission, thereby playing a good role in electric conduction. The conductivity in the negative electrode material is enhanced, and the transmission rate of lithium ions in the material is accelerated, so that the cycle stability and the rate capability of the lithium ion battery are improved.
(3) The silicon @ carbon nanotube @ carbon anode material prepared by the method has the advantages of simplicity in operation, low cost, capability of realizing industrial production and the like.
Drawings
Fig. 1 is a preparation flow chart of a silicon @ carbon nanotube @ carbon composite anode material.
Fig. 2a and b are scanning electron microscope images of the silicon @ carbon nanotube @ carbon composite anode material.
Fig. 3a and b are an X-ray diffraction pattern and a Raman spectrum of the silicon @ carbon nanotube @ carbon composite anode material respectively.
FIG. 4a is 0.1mV s-1And b is a constant current charging and discharging curve chart of the silicon @ carbon nano tube @ carbon composite negative electrode material at 0.05 ℃.
FIG. 5 is a graph of the cyclic stability of the first 300 cycles of Si, QSi @ C-4, QSi @ C-10, QSi @ CNTs @ C at 0.2C.
FIG. 6 is a graph of the cyclic stability at QSi @ C-10, QSi @ CNTs @ C at 0.2C for the first 300 cycles.
Detailed Description
The technical solutions in the comparative examples and examples of the present invention will be described in detail and completely with reference to the comparative examples and examples of the present invention, but are not limited thereto.
Comparative example 1
Step one, putting the pickled polycrystalline silicon cutting silicon mud into 2 or 4 100ml zirconia ball milling tanks in equal parts, adding zirconia ball milling beads into the ball milling tanks, wherein the diameters of the ball milling beads are respectively 5mm, 8 mm, 10 mm and 15mm, the corresponding mass ratio of the ball milling beads to the materials (polycrystalline silicon cutting silicon mud) is 2:2:2:1, and then placing the ball milling tanks on a planetary ball mill. The dry ball milling is carried out for 10-12h at the rotating speed of 500-600 r/min.
And step two, screening the ball-milled silicon powder through a sieve to obtain the nano silicon powder electrode material marked as Si.
Step three, QSi @ CNTs @ C is mixed with conductive carbon black (super P) and polyacrylic acid (PAA) according to the ratio of 8:1:1, and 2-2.5ml of deionized water is added into each gram of mixture. Stirring and mixing to form the electrode slurry. The electrode slurry was uniformly coated on a copper foil and vacuum dried, the electrolyte was 90% (1M LiPF6 ED/DEC (volume ratio 1:1)) + 10% FEC, and button cells were made.
Testing the electrochemical performance of Si, wherein the discharge specific capacity of the first ring is 3983.8mAh/g, the charge specific capacity of the first ring is 2931.4mAh/g, and the coulomb efficiency of the first ring is 73.5%; after 300 cycles, the capacity remained 2.916 mAh/g.
Comparative example 2
Step one, weighing 2-4g of starch, equally dividing the starch into 2 or 4 zirconia ball milling tanks of 100ml, adding zirconia ball milling beads into the ball milling tanks, wherein the diameters of the ball milling beads are 5mm, 8 mm, 10 mm and 15mm respectively, the mass ratio of the corresponding addition amounts is 2:2:2:1, and the ratio of the ball milling beads to the material (starch) is 50:1, and then placing the ball milling tanks on a planet ball mill. Ball milling is carried out for 10-12h by a dry method at the rotating speed of 500-600r/min, and the ball milled starch is sieved.
Step two, taking 1-2g of the starch after ball milling, grinding and placing in a quartz boat, and adding N2Under the atmosphere, the gas flow rate is 80-100sccm, the material is heated to 400 ℃ for heat preservation for 1-2h at the heating rate of 3-5 ℃/min, then heated to 900 ℃ for heat preservation for 2-3h at the same heating rate, and then naturally cooled to room temperature along with the furnace to obtain the carbon sheet electrode material marked as C.
Step three, mixing the C with conductive carbon black (super P) and polyacrylic acid (PAA) according to a ratio of 8:1:1, and adding 2-2.5ml of deionized water per gram of the mixture. Stirring and mixing to form the electrode slurry. The electrode slurry was uniformly coated on a copper foil and vacuum dried, the electrolyte was 90% (1M LiPF6 ED/DEC (volume ratio 1:1)) + 10% FEC, and button cells were made.
Testing the electrochemical performance of C, wherein the discharge specific capacity of the first ring is 415mAh/g, the charge specific capacity of the first ring is 178.4mAh/g, and the coulomb efficiency of the first ring is 42%; after 300 cycles, the capacity remained at 127.7 mAh/g.
Example 1
Step one, putting the pickled polycrystalline silicon cutting silicon mud into 2 or 4 100ml zirconia ball milling tanks in equal parts, adding zirconia ball milling beads into the ball milling tanks, wherein the diameters of the ball milling beads are respectively 5mm, 8 mm, 10 mm and 15mm, the corresponding mass ratio of the ball milling beads to the materials (polycrystalline silicon cutting silicon mud) is 2:2:2:1, and then placing the ball milling tanks on a planetary ball mill. And performing dry ball milling for 10-12h at the rotating speed of 500-600r/min, and sieving the ball-milled silicon powder to obtain the nano-silicon powder.
Step two, sequentially adding the nano-silicon, the carbon nano-tube and the polyvinylpyrrolidone into 100-200ml of deionized water, wherein the content of the added nano-silicon is 0.5-1 g; the content of the carbon nano tube is 0.25-0.5 g. Performing ultrasonic treatment for 1-2h to obtain a mixed solution, wherein the content of polyvinylpyrrolidone is 0.25-0.5 g; dividing the mixed solution into 2 equal parts and 4 equal parts, putting the mixed solution into 2 or 4 zirconia ball milling tanks with the volume of 100ml, adding ball milling beads into the ball milling tanks, wherein the diameters of the ball milling beads are respectively 5mm, 8 mm, 10 mm and 15mm, the corresponding mass ratio of the ball milling beads to the materials (the mixed solution) is 2:2:2:1, and the ratio of the ball milling beads to the materials (the mixed solution) is 50:1, and then placing the ball milling tanks on a planetary ball mill. And (3) carrying out wet ball milling for 2-4h at the rotating speed of 500-600r/min, centrifuging and cleaning the obtained solution for 2-4 times, and finally treating the solution for 10-12h in a drying box at the temperature of 60 ℃ to obtain the silicon @ carbon nanotube composite material powder.
Step three, taking the composite material powder prepared in the step three, grinding the composite material powder, placing the ground composite material powder in a quartz boat, and adding N2Under the atmosphere, the gas flow rate is 80-100sccm, the material is heated to 400 ℃ at the heating rate of 3-5 ℃/min and is kept for 1-2h, then the material is heated to 900 ℃ at the same heating rate and is kept for 2-3h, and then the material is naturally cooled to room temperature along with the furnace to obtain the silicon @ carbon nanotube composite electrode material which is marked as QSi @ CNTs.
Step four, QSi @ CNTs are mixed with conductive carbon black (super P) and polyacrylic acid (PAA) according to the ratio of 8:1:1, and 2-2.5ml of deionized water is added into each gram of mixture. Stirring and mixing to form the electrode slurry. The electrode slurry was uniformly coated on a copper foil and vacuum dried, the electrolyte was 90% (1M LiPF6 ED/DEC (volume ratio 1:1)) + 10% FEC, and button cells were made.
Testing QSi @ CNTs electrochemical performance, wherein the first circle discharge specific capacity is 2107.4mAh/g, the first circle charge specific capacity is 1635.3mAh/g, and the first circle coulombic efficiency is 77.6%; after 300 cycles, the capacity remained at 341.5 mAh/g.
Example 2
Step one, putting the pickled polycrystalline silicon cutting silicon mud into 2 or 4 100ml zirconia ball milling tanks in equal parts, adding zirconia ball milling beads into the ball milling tanks, wherein the diameters of the ball milling beads are respectively 5mm, 8 mm, 10 mm and 15mm, the corresponding mass ratio of the ball milling beads to the materials (polycrystalline silicon cutting silicon mud) is 2:2:2:1, and then placing the ball milling tanks on a planetary ball mill. And performing dry ball milling for 10-12h at the rotating speed of 500-600r/min, and sieving the ball-milled silicon powder to obtain the nano-silicon powder.
And step two, weighing 0.2-0.5g of starch and 0.8-2g of nano silicon powder prepared in the step one (namely, controlling the ratio of silicon to starch to be 1:4), adding the starch and the nano silicon powder into two zirconia ball milling tanks with the volume of 100ml, adding zirconia ball milling beads into the ball milling tanks, wherein the diameters of the ball milling beads are respectively 5mm, 8 mm, 10 mm and 15mm, the corresponding addition mass ratio is 2:2:2:1, and the ratio of the ball milling beads to materials is 50:1, and then placing the ball milling tanks on a planetary ball mill. And performing dry ball milling for 10-12h at the rotation speed of 500-600r/min, and sieving the ball-milled composite material to obtain silicon @ Starch composite material powder which is marked as QSi @ Starch-4.
Step three, taking the QSi @ Starch composite material powder prepared in the step two, grinding the powder, placing the powder in a quartz boat, and putting the quartz boat in the quartz boat2Under the atmosphere, the gas flow rate is 80-100sccm, the material is heated to 400 ℃ for heat preservation for 1-2h at the heating rate of 3-5 ℃/min, then heated to 900 ℃ for heat preservation for 2-3h at the same heating rate, and then naturally cooled to room temperature along with the furnace to obtain the silicon @ carbon composite electrode material, which is marked as QSi @ C-4.
Step four, QSi @ C-4 was mixed with conductive carbon black (super P) and polyacrylic acid (PAA) in a ratio of 8:1:1, and 2-2.5ml of deionized water was added per gram of the mixture. Stirring and mixing to form the electrode slurry. The electrode slurry was uniformly coated on a copper foil and vacuum dried, the electrolyte was 90% (1M LiPF6 ED/DEC (volume ratio 1:1)) + 10% FEC, and button cells were made.
QSi @ C-4 electrochemical performance is tested, the first circle discharge specific capacity is 1697.9mAh/g, the first circle charge specific capacity is 1301.5mAh/g, and the first circle coulombic efficiency is 76.65%; after 300 cycles, the capacity remained at 229.6 mAh/g.
Example 3
Step one, putting the pickled polycrystalline silicon cutting silicon mud into 2 or 4 100ml zirconia ball milling tanks in equal parts, adding zirconia ball milling beads into the ball milling tanks, wherein the diameters of the ball milling beads are respectively 5mm, 8 mm, 10 mm and 15mm, the corresponding mass ratio of the ball milling beads to the materials (polycrystalline silicon cutting silicon mud) is 2:2:2:1, and then placing the ball milling tanks on a planetary ball mill. And performing dry ball milling for 10-12h at the rotating speed of 500-600r/min, and sieving the ball-milled silicon powder to obtain the nano-silicon powder.
And step two, weighing 0.2-0.5g of starch and 1.2-3g of nano silicon powder prepared in the step one (namely, controlling the ratio of silicon to starch to be 1:6), adding the starch and the nano silicon powder into two zirconia ball milling tanks with the volume of 100ml, adding zirconia ball milling beads into the ball milling tanks, wherein the diameters of the ball milling beads are respectively 5mm, 8 mm, 10 mm and 15mm, the corresponding addition mass ratio is 2:2:2:1, and the ratio of the ball milling beads to materials is 50:1, and then placing the ball milling tanks on a planetary ball mill. And performing dry ball milling for 10-12h at the rotation speed of 500-600r/min, and sieving the ball-milled composite material to obtain silicon @ Starch composite material powder, wherein the mark is QSi @ Starch-6.
Step three, taking the QSi @ Starch composite material powder prepared in the step two, grinding the powder, placing the powder in a quartz boat, and putting the quartz boat in the quartz boat2Under the atmosphere, the gas flow rate is 80-100sccm, the material is heated to 400 ℃ at the heating rate of 3-5 ℃/min and is kept for 1-2h, then the material is heated to 900 ℃ at the same heating rate and is kept for 2-3h, and then the material is naturally cooled to room temperature along with the furnace to obtain the silicon @ carbon composite electrode material which is marked as QSi @ C-6.
Step four, QSi @ C-6 was mixed with conductive carbon black (super P) and polyacrylic acid (PAA) in a ratio of 8:1:1, and 2-2.5ml of deionized water was added per gram of the mixture. Stirring and mixing to form the electrode slurry. The electrode slurry was uniformly coated on a copper foil and vacuum dried, the electrolyte was 90% (1M LiPF6 ED/DEC (volume ratio 1:1)) + 10% FEC, and button cells were made.
Testing QSi @ C-6 electrochemical performance, wherein the first circle discharge specific capacity is 1301.5mAh/g, the first circle charge specific capacity is 929.6mAh/g, and the first circle coulombic efficiency is 71.43%; after 300 cycles, the capacity remained at 313.4 mAh/g.
Example 4
Step one, putting the pickled polycrystalline silicon cutting silicon mud into 2 or 4 100ml zirconia ball milling tanks in equal parts, adding zirconia ball milling beads into the ball milling tanks, wherein the diameters of the ball milling beads are respectively 5mm, 8 mm, 10 mm and 15mm, the corresponding mass ratio of the ball milling beads to the materials (polycrystalline silicon cutting silicon mud) is 2:2:2:1, and then placing the ball milling tanks on a planetary ball mill. And performing dry ball milling for 10-12h at the rotating speed of 500-600r/min, and sieving the ball-milled silicon powder to obtain the nano-silicon powder.
And step two, weighing 0.2-0.5g of starch and 1.6-4g of nano silicon powder prepared in the step one (namely, controlling the ratio of silicon to starch to be 1:8), adding the starch and the nano silicon powder into two zirconia ball milling tanks with the volume of 100ml, adding zirconia ball milling beads into the ball milling tanks, wherein the diameters of the ball milling beads are respectively 5mm, 8 mm, 10 mm and 15mm, the corresponding addition mass ratio is 2:2:2:1, and the ratio of the ball milling beads to materials is 50:1, and then placing the ball milling tanks on a planetary ball mill. And performing dry ball milling for 10-12h at the rotation speed of 500-600r/min, and sieving the ball-milled composite material to obtain silicon @ Starch composite material powder, wherein the mark is QSi @ Starch-8.
Step three, taking the QSi @ Starch-8 composite material powder prepared in the step two, grinding the composite material powder, placing the ground composite material powder into a quartz boat, and placing the quartz boat in a reactor N2Under the atmosphere, the gas flow rate is 80-100sccm, the material is heated to 400 ℃ at the heating rate of 3-5 ℃/min for 1-2h, then heated to 900 ℃ at the same heating rate of 700 ℃ for 2-3h, and then naturally cooled to room temperature along with the furnace to obtain the silicon @ carbon composite electrode material, which is marked as QSi @ C-8.
Step four, QSi @ C-8 was mixed with conductive carbon black (super P) and polyacrylic acid (PAA) in a ratio of 8:1:1, and 2-2.5ml of deionized water was added per gram of the mixture. Stirring and mixing to form the electrode slurry. The electrode slurry was uniformly coated on a copper foil and vacuum dried with 90% electrolyte (1M LiPF)6ED/DEC (volume ratio of 1:1)) + 10% FEC, and making into button cells.
Testing QSi @ C-8 electrochemical performance, wherein the first circle discharge specific capacity is 1014.2mAh/g, the first circle charge specific capacity is 661.3mAh/g, and the first circle coulombic efficiency is 65.2%; after 300 cycles, the capacity remained at 402.6 mAh/g.
Example 5
Step one, putting the pickled polycrystalline silicon cutting silicon mud into 2 or 4 100ml zirconia ball milling tanks in equal parts, adding zirconia ball milling beads into the ball milling tanks, wherein the diameters of the ball milling beads are respectively 5mm, 8 mm, 10 mm and 15mm, the corresponding mass ratio of the ball milling beads to the materials (polycrystalline silicon cutting silicon mud) is 2:2:2:1, and then placing the ball milling tanks on a planetary ball mill. And performing dry ball milling for 10-12h at the rotating speed of 500-600r/min, and sieving the ball-milled silicon powder to obtain the nano-silicon powder.
And step two, weighing 0.2-0.5g of starch and 2-5g of nano silicon powder prepared in the step one (namely, controlling the ratio of silicon to starch to be 1:10), adding the starch and the nano silicon powder into two zirconia ball milling tanks with the volume of 100ml, adding zirconia ball milling beads into the ball milling tanks, wherein the diameters of the ball milling beads are 5mm, 8 mm, 10 mm and 15mm respectively, the corresponding addition mass ratio is 2:2:2:1, and the ratio of the ball milling beads to materials is 50:1, and then placing the ball milling tanks on a planetary ball mill. And performing dry ball milling for 10-12h at the rotation speed of 500-600r/min, and sieving the ball-milled composite material to obtain silicon @ Starch composite material powder which is marked as QSi @ Starch-10.
Step three, taking the QSi @ Starch-10 composite material powder prepared in the step two, grinding the composite material powder, placing the ground composite material powder into a quartz boat, and placing the quartz boat in a reactor N2Under the atmosphere, the gas flow rate is 80-100sccm, the material is heated to 400 ℃ at the heating rate of 3-5 ℃/min for 1-2h, then heated to 900 ℃ at the same heating rate of 700 ℃ for 2-3h, and then naturally cooled to room temperature along with the furnace to obtain the silicon @ carbon composite electrode material, which is marked as QSi @ C-10.
Step four, QSi @ C-10 was mixed with conductive carbon black (super P) and polyacrylic acid (PAA) in a ratio of 8:1:1, and 2-2.5ml of deionized water was added per gram of the mixture. Stirring and mixing to form the electrode slurry. The electrode slurry was uniformly coated on a copper foil and vacuum dried, the electrolyte was 90% (1M LiPF6 ED/DEC (volume ratio 1:1)) + 10% FEC, and button cells were made.
Testing QSi @ C-10 electrochemical performance, wherein the first circle discharge specific capacity is 810.5mAh/g, the first circle charge specific capacity is 512.8mAh/g, and the first circle coulombic efficiency is 62.3%; after 300 cycles, the capacity remained at 601.4 mAh/g.
Example 6
Step one, putting the pickled polycrystalline silicon cutting silicon mud into 2 or 4 100ml zirconia ball milling tanks in equal parts, adding zirconia ball milling beads into the ball milling tanks, wherein the diameters of the ball milling beads are respectively 5mm, 8 mm, 10 mm and 15mm, the corresponding mass ratio of the ball milling beads to the materials (polycrystalline silicon cutting silicon mud) is 2:2:2:1, and then placing the ball milling tanks on a planetary ball mill. And performing dry ball milling for 10-12h at the rotating speed of 500-600r/min, and sieving the ball-milled silicon powder to obtain the nano-silicon powder.
Step two, sequentially adding the nano-silicon, the carbon nano-tube and the polyvinylpyrrolidone into 100-200ml of deionized water, wherein the content of the added nano-silicon is 0.5-1 g; the content of the carbon nano tube is 0.25-0.5 g. Performing ultrasonic treatment for 1-2h to obtain a mixed solution, wherein the content of polyvinylpyrrolidone is 0.25-0.5 g; dividing the mixed solution into 2 equal parts or 4 equal parts, putting the 2 equal parts or 4 equal parts into 2 or 4 zirconia ball milling tanks with the volume of 100ml, adding zirconia ball milling beads into the ball milling tanks, wherein the diameters of the ball milling beads are respectively 5mm, 8 mm, 10 mm and 15mm, the mass ratio of the corresponding addition amounts is 2:2:2:1, and the ratio of the ball milling beads to the materials (the mixed solution) is 50:1, and then placing the ball milling tanks on a planet ball mill. And (2) carrying out wet ball milling for 2-4h at the rotation speed of 500-600r/min, centrifuging and cleaning the obtained solution for 2-4 times, and finally treating the solution for 10-12h in a drying box at the temperature of 60 ℃ to obtain the silicon @ carbon nanotube composite material which is marked as QSi @ CNTs.
Step three, weighing 1.6-10g of starch and 0.6-1g of QSi @ CNTs prepared in the step two (namely, controlling the ratio of silicon to carbon nanotubes to starch to be 1:0.5:4-1:0.5:10), adding the starch and the QSi @ CNTs into two zirconia ball milling tanks with the volume of 100ml, adding zirconia ball milling beads into the ball milling tanks, wherein the diameters of the ball milling beads are respectively 5mm, 8 mm, 10 mm and 15mm, the corresponding mass ratio of the addition is 2:2:2:1, and the ratio of the ball milling beads to materials is 50:1, and then placing the ball milling tanks on a planet ball mill. And (3) performing dry ball milling for 10-12h at the rotating speed of 500-600r/min, and sieving the ball-milled composite material to obtain silicon @ carbon nano tube @ Starch composite material powder which is marked as QSi @ CNTs @ Starch.
Step four, taking the QSi @ CNTs @ Starch composite material powder prepared in the step three, grinding the composite material powder, placing the ground composite material powder into a quartz boat, and placing the quartz boat in the presence of N2Under the atmosphere, the gas flow rate is 80-100sccm, the material is heated to 300-400 ℃ at the heating rate of 3-5 ℃/min and is insulated for 1-2h, then the material is heated to 700-900 ℃ at the same heating rate and is insulated for 2-3h, and then the material is naturally cooled to room temperature along with the furnace to obtain the silicon @ carbon nanotube @ carbon composite electrode material which is marked as QSi @ CNTs @ C.
Step five, QSi @ CNTs @ C is mixed with conductive carbon black (super P) and polyacrylic acid (PAA) according to the ratio of 8:1:1, and 2-2.5ml of deionized water is added into each gram of mixture. Stirring and mixing to form the electrode slurry. The electrode slurry was uniformly coated on a copper foil and vacuum dried with 90% electrolyte (1M LiPF)6ED/DEC (volume ratio of 1:1)) + 10% FEC, and making into button cells.
Testing QSi @ CNTs @ C electrochemical performance, wherein the first circle discharge specific capacity is 1013.8mAh/g, the first circle charge specific capacity is 809.9mAh/g, and the first circle coulombic efficiency is 79.88%; after 300 cycles, the capacity remained at 720 mAh/g.
The following table summarizes the performance parameters of the silicon-carbon composite anode material
Figure BDA0003252627750000101
As can be seen from the table above, the reversible capacity after 300 cycles is higher for all six examples than for the two comparative examples. Particularly, QSi @ C-10 and QSi @ CNTs @ C still maintain higher capacity after 300 turns, and in addition, QSi @ CNTs @ C also has the first turn coulombic efficiency of 79.88%, which shows that the silicon-carbon composite negative electrode material has better cycle stability and improves the advantages of the silicon-carbon negative electrode material in the preparation of lithium ion batteries. The characteristics of simple preparation process and low cost of the used raw materials are combined, so that QSi @ CNTs @ C has great application prospect as the lithium ion battery cathode material.
The above embodiments are only examples of the present invention, and should not be construed as limiting the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (7)

1. A preparation method of a silicon @ carbon nanotube @ carbon composite anode material of a lithium ion battery is characterized by comprising the following preparation steps:
step one, preparing nano silicon: putting the pickled polycrystalline silicon cutting silicon mud into a zirconia ball milling tank, wherein the ratio of ball milling beads to the polycrystalline silicon cutting silicon mud is 50:1, and then putting the ball milling tank on a planetary ball mill; performing dry ball milling for 10-12h at the rotating speed of 500-600r/min, and sieving the ball-milled silicon powder to obtain nano silicon powder;
step two, preparing the silicon @ carbon nanotube composite material: sequentially adding nano silicon, carbon nano tubes and polyvinylpyrrolidone into deionized water, and carrying out ultrasonic treatment for 1-2h to obtain a mixed solution; dividing the mixed solution into N equal parts, respectively putting the N equal parts into zirconia ball milling tanks, and then putting the ball milling tanks on a planetary ball mill; regulating the rotating speed to 500-600r/min, carrying out wet ball milling for 2-4h, centrifuging and cleaning the obtained solution, and finally placing the solution in a drying box for treatment at 60 ℃ for 10-12h to obtain the silicon @ carbon nanotube composite material which is marked as QSi @ CNTs;
step three, preparing the silicon @ carbon nanotube @ starch composite material: and (3) weighing a proper amount of starch and the QSi @ CNTs prepared in the second step, adding into a zirconia ball milling tank, and then placing the ball milling tank on a planetary ball mill. The rotating speed is adjusted to 500-600r/min, the composite material is ball-milled for 10-12h by a dry method, and the ball-milled composite material is sieved to obtain silicon @ carbon nano tube @ Starch composite material powder which is marked as QSi @ CNTs @ Starch;
step four, preparing the silicon @ carbon nanotube @ carbon composite material: grinding the QSi @ CNTs @ Starch composite material prepared in the third step, placing the ground composite material in a quartz boat, and adding N2And (2) carrying out high-temperature carbonization in the atmosphere, and then naturally cooling to room temperature to obtain the silicon @ carbon nanotube @ carbon composite material which is marked as QSi @ CNTs @ C.
2. The method for preparing the silicon @ carbon nanotube @ carbon composite anode material for the lithium ion battery as claimed in claim 1, wherein the number of the N equal parts of the mixed solution in the step one is 2 or 4, and the number of the corresponding zirconia ball milling pots is 2 or 4.
3. The method for preparing the silicon @ carbon nanotube @ carbon composite anode material of the lithium ion battery as claimed in claim 1, wherein in the step one, the diameters of the zirconia ball milling beads are 5mm, 8 mm, 10 mm and 15mm respectively, the corresponding mass ratio of the zirconia ball milling beads is 2:2:1, the ratio of the ball milling beads to the polysilicon cutting silicon mud is 50:1, the rotation speed of the ball mill is 500-600r/min, the ball milling time is 12h, and a space not less than 1/3 needs to be reserved in the zirconia tank.
4. The method for preparing the silicon @ carbon nanotube @ carbon composite anode material of the lithium ion battery as claimed in claim 1, wherein the content of the nano-silicon in the mixed solution prepared by every 100ml of deionized water in the second step is 0.5-1 g; the content of the carbon nano tube is 0.25-0.5 g; the content of polyvinylpyrrolidone is 0.25-0.5g, and the total mass of substances added in per 100ml of deionized water is 1-2 g.
5. The method for preparing the silicon @ carbon nanotube @ carbon composite anode material for the lithium ion battery as claimed in claim 1, wherein the centrifugation and cleaning processes in the second step are repeated for 2-4 times.
6. The method for preparing the silicon @ carbon nanotube @ carbon composite anode material for the lithium ion battery as claimed in claim 1, wherein the addition amount of QSi/CNTs in the zirconia ball milling pot in the step three is 0.6-1g, and the corresponding addition amount of starch is 1.6-10 g.
7. The method for preparing the silicon @ carbon nanotube @ carbon composite anode material for the lithium ion battery as claimed in claim 1, wherein the heat treatment manner in the fourth step is sectional heating, the heating is performed at a heating rate of 3-5 ℃/min to 300-2The flow rate is 80-100 sccm.
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