CN108807861B - Silicon-carbon composite material for lithium ion battery and preparation method thereof - Google Patents
Silicon-carbon composite material for lithium ion battery and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a silicon-carbon composite material, which is characterized in that: the silicon-carbon composite material is secondary particles with irregular shapes; the secondary particles are formed by compounding a silicon material, a conductive additive and amorphous carbon; the conductive additive is uniformly dispersed in the secondary particles; the conductive additive and the silicon material are tightly bonded together by the amorphous carbon; the outer surface of the secondary particle is provided with a continuous amorphous carbon protective layer. When used as a negative electrode of a lithium ion battery, the silicon-carbon composite material has the electrochemical characteristics of high capacity and high coulombic efficiency. The lithium ion battery prepared from the silicon-carbon composite material has the characteristic of high volume energy density.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a silicon-carbon composite material and a preparation method thereof.
Background
Due to rapid development and wide application of various portable electronic devices and electric vehicles in recent years, demand for lithium ion batteries having high energy density and long cycle life is increasingly urgent. The negative electrode material of the lithium ion battery which is commercialized at present is mainly graphite, but due to low theoretical capacity (372mAh/g), the further improvement of the energy density of the lithium ion battery is limited. Among many novel lithium ion battery cathode materials, silicon cathode materials have the advantage of high capacity (Li) that other cathode materials cannot match22Si5Theoretical lithium storage capacity of 4200mAh/g) which is more than 11 times of the theoretical capacity of the current commercial carbon negative electrode material. However, the silicon material is conductiveThe electrical property is poor, and meanwhile, the volume effect is serious in the lithium intercalation and deintercalation process, the volume change rate is about 400%, and the electrode material pulverization and the separation of the electrode material and a current collector can be caused. In addition, due to the volume effect during charge and discharge, the silicon negative electrode material exposed to the electrolyte continuously forms a fresh surface, and thus the electrolyte is continuously consumed to generate an SEI film, reducing the cycle performance of the electrode material. The above-mentioned drawbacks of silicon-based materials severely limit their commercial applications.
In order to solve the above problems of silicon negative electrodes, the current domestic and foreign research on silicon negative electrode materials mainly focuses on the following aspects: (1) the size of the silicon particles is simply reduced, for example, by using silicon nanoparticles, so as to reduce the volume effect of the silicon particles. However, the nano silicon particles have a large specific surface area, so that the coulombic efficiency of the battery is very low, and the nano silicon powder is reunited into large particles in the subsequent circulation process to generate a new volume effect. (2) The silicon material with special nano structure, such as silicon nano tube, silicon nano wire, porous silicon, etc. is prepared, but the method has higher cost and lower yield, and is only suitable for laboratory research at present. (3) Compounding silicon with carbon materials such as conductive additives, amorphous carbon, graphite and the like to prepare the silicon-carbon composite material. The composite material has attracted the attention of many researchers due to the combination of the high capacity of silicon and the cycle performance of graphite materials. However, when the content of graphite and amorphous carbon is too high and the content of silicon is low, the practical use capacity of the material is low. (4) The surface of the silicon material or the silicon-carbon composite material is coated, so that the material keeps stable SEI in the circulation of the lithium ion battery, and the occurrence of side reactions is reduced to improve the coulombic efficiency.
Chinese patent publication No. CN105161695A discloses spherical active material particles for a negative electrode of a lithium ion battery, and a preparation method and application thereof. The spherical active substance particles are spherical composite particles prepared by spray drying active substance particles such as fibrous carbon, silicon with a micro-nano scale and the like. The spherical active material particles are not secondarily coated and have a porous structure having a larger specific surface area. Therefore, the first coulombic efficiency of the lithium ion battery made of the material is low, and the first round efficiency is only 60% as shown in the embodiment. In addition, the porous structure means that the material has a low density, which results in a low energy density of the lithium ion battery made of the material. Furthermore, the spherical active material particles contain up to 16.7% or more of fibrous carbon, which, in addition to a high specific surface area and a low density, also leads to a low content of active material in the material and thus to a low capacity of the composite material.
Chinese patent publication No. CN106207142A discloses a method for preparing a silicon-carbon composite negative electrode material for a power lithium ion battery. The preparation method of the silicon-carbon composite negative electrode material comprises the following steps: preparing polyimide coated nano silicon particle slurry; spray drying and granulating the slurry to prepare polyimide coated nano silicon particle powder; calcining the polyimide-coated nano silicon particle powder at high temperature, and then crushing and granulating the polyimide-coated nano silicon particle powder without damaging the coating structure; and mixing the crushed powder with graphite material powder to prepare the silicon-carbon composite negative electrode material. The polyimide in-situ polymerization coated nano-silicon has the advantages of complex process, high technical difficulty and difficulty in industrial production, and the polyimide is subjected to spray drying by using an organic solvent, so that explosion prevention and solvent recovery are involved, and the production risk and the cost are high. The silicon-carbon composite negative electrode material is a mixture of a silicon-carbon material and graphite, the proportion of the silicon-carbon material in the mixture is only 20 wt% at most, namely the actual silicon content of the silicon-carbon composite negative electrode material is lower than 20 wt%, so that the capacity of the silicon-carbon composite negative electrode material is far lower than the theoretical capacity of a silicon material.
Chinese patent publication No. CN104868107A discloses a spherical silicon-carbon composite material for lithium ion batteries, and a preparation method and application thereof. The spherical silicon-carbon composite material comprises a porous silicon-carbon composite material and an organic or inorganic carbon source filled in the porous silicon-carbon composite material. Chinese patent publication No. CN104716312B discloses a silicon-carbon composite material for lithium ion batteries, and a preparation method and an application thereof, and the patent is the same applicant and inventor as the patent with application publication No. CN 104868107A. The carbon-silicon composite materials described in the two patents are very similar in structure and preparation method, and the main difference is that in the patent with the publication number of CN104716312B, a step of coating aluminum-containing material on silicon powder by adopting a reduced pressure distillation method is added to the silicon-carbon composite material. The reduced pressure distillation method is only suitable for small-scale experiments in laboratories and cannot be used for industrial production. The silicon-carbon composite material described in both patents is spherical secondary particles prepared by spray drying equipment. After rolling, if the compaction density of a negative pole piece prepared by homogenizing and coating the spherical secondary particles is too high, the spherical secondary particles can be crushed, so that the internal conductive contact of the secondary particles is deteriorated, and the cycle performance of the battery can be deteriorated under the condition that silicon at a newly-broken interface is in direct contact with electrolyte; and if the pole piece compaction density is too low, poor conductive contact between secondary particles is caused, and the energy density of the battery is also low.
Chinese patent publication No. CN105720258A discloses a lithium ion battery negative electrode material, a preparation method and application thereof, and a lithium ion battery. The preparation method of the cathode material comprises the following steps: 1) uniformly mixing the silicon powder slurry and the binder, and performing spray drying to obtain primary particles A; 2) adding the primary particles A in the synthesis process of the asphalt resin to obtain the asphalt resin containing silicon powder, and sintering and crushing to obtain secondary particles B; 3) and uniformly mixing the secondary particles B with graphite, performing surface modification by using asphalt, and roasting to obtain tertiary finished product particles C. The silicon powder slurry is obtained by water-based wet grinding. Experiments show that silicon powder can react with water violently in the wet grinding process, and the products are silicon dioxide and hydrogen, so that the oxygen content in the ground product is increased by dozens of times compared with the raw material, and finally the problem of low coulombic efficiency of the material in a lithium ion battery is caused. And the smaller the particle size of the ground product, the more severe the oxidation. The negative electrode material is a mixture of a silicon-carbon material and graphite, and the actual silicon content of the silicon-carbon composite negative electrode material is calculated to be lower than 20 wt% according to the claims and the embodiment of the negative electrode material, so that the capacity of the silicon-carbon composite negative electrode material is far lower than the theoretical capacity of a silicon material.
Chinese patent publication No. CN105633387A discloses a method for preparing a silicon-based negative electrode material. The preparation method of the negative electrode material comprises the following steps: performing ball milling on the silicon monoxide, the carbon material and the binder in a solution, and performing spray drying on the mixture to form a precursor of the silicon-based negative electrode material; and sintering and cooling the silicon-based anode material precursor in an inert atmosphere to obtain the silicon-based anode material. The silicon-based negative electrode material is a porous structure with a larger specific surface without secondary coating, and the silicon monoxide primary particles are directly exposed to electrolyte. Therefore, the lithium ion battery made of the material has low initial coulombic efficiency, and the initial efficiency is only 65% as shown in the embodiment. In addition, the porous structure and spherical structure of the silicon-based negative electrode material mean that the packing density of the material is low, which results in low compaction density of the prepared pole piece and thus low energy density of the prepared lithium ion battery.
Chinese patent publication No. CN104362311B discloses a silicon-carbon composite microsphere negative electrode material and a preparation method thereof. The preparation method of the material comprises the steps of firstly mixing nano silicon particles and polyvinyl alcohol solution, and forming first composite microspheres after spray drying; then mixing the first composite microspheres with a polyacrylonitrile solution, coating the surfaces of the first composite microspheres, and volatilizing a solvent to form second composite microspheres with core-shell structures; and finally, carrying out oxidation and carbonization treatment on the second composite microspheres to form the silicon-carbon composite microsphere negative electrode material. The shell of the silicon-carbon composite microsphere negative electrode material is amorphous carbon obtained by carbonizing polyacrylonitrile, and the coulomb efficiency is low. The highest first coulombic efficiency in the six examples shown in this patent is only 65%. In addition, the negative pole piece made of the spherical particles can cause the crushing of the spherical secondary particles if the compaction density is too high after rolling; and if the pole piece compaction density is too low, poor conductive contact between secondary particles is caused, and the energy density of the battery is also low.
Chinese patent publication No. CN103346324B discloses a negative electrode material for lithium ion batteries and a preparation method thereof. The negative electrode material comprises an inner core and a shell wrapped outside the inner core, a hollow layer is arranged between the shell and the inner core, the inner core is a silicon-carbon composite material, the shell is a carbon composite material, and the carbon composite material is formed by a carbon material and a first amorphous carbon precursor. The preparation method of the negative electrode material comprises the following steps: A) mixing the silicon particles, the second amorphous carbon precursor and the first ball-milling medium, and then carrying out spray drying and granulation to obtain a first compound; B) mixing the first compound, the carbon material, the first amorphous carbon precursor and a second ball milling medium, performing ball milling in a protective atmosphere, and performing spray drying granulation to obtain a second compound; C) and roasting the second compound in a protective atmosphere to obtain the lithium ion battery cathode material. However, experiments show that in the step B, the first composite is damaged by the ball milling process, and is uniformly mixed with the carbon material and the first amorphous carbon precursor, so that the core-shell structure cannot be formed, and the hollow layer between the outer shell and the inner core cannot be formed.
Chinese patent publication No. CN102891297B discloses a silicon-carbon composite material for lithium ion batteries and a preparation method thereof. The preparation method of the cathode material is characterized in that silicon and graphite are mixed in a sodium carboxymethyl cellulose solution by ball milling, and are carbonized after being dried and granulated by a spray drying technology. Experiments show that silicon powder can react with water violently in the wet grinding process, and the products are silicon dioxide and hydrogen, so that the oxygen content in the ground product is increased by dozens of times compared with the raw material, and finally the problem of low coulombic efficiency of the material in a lithium ion battery is caused. And the smaller the particle size of the ground product, the more severe the oxidation. The silicon-carbon composite material is not subjected to secondary coating and has a porous structure with a larger specific surface, and primary particles of silicon and graphite are directly exposed to electrolyte. Therefore, the lithium ion battery made of the material has low coulombic efficiency for the first time. In addition, the porous structure and the spherical structure of the silicon-carbon composite material mean that the packing density of the material is low, so that the compaction density of the prepared pole piece is low, and the energy density of the prepared lithium ion battery is low.
Therefore, the existing silicon negative electrode material has low capacity, low coulombic efficiency, large polarization, complex preparation process and difficult realization of commercial application in the lithium ion battery, and is a technical problem in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a silicon-carbon composite material which is used for a lithium ion battery and has high capacity, high coulombic efficiency and long cycle life and a preparation method thereof.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a silicon-carbon composite material is a secondary particle with an irregular shape; the secondary particles are formed by compounding a silicon material, a conductive additive and amorphous carbon; the conductive additive is uniformly dispersed in the secondary particles; the conductive additive and the silicon material are tightly bonded together by the amorphous carbon; the outer surface of the secondary particle is provided with a continuous amorphous carbon protective layer.
The median diameter of the secondary particles is between 1 and 30 mu m; the median diameter of the primary silicon material particles is 0.01-5 μm; the thickness of the amorphous carbon protective layer outside the secondary particles is between 0.01 and 5 mu m; in the silicon-carbon composite material, the content of the silicon material is 1-99 wt%, the content of the conductive additive is 0.05-30 wt%, and the content of the amorphous carbon is 99-1 wt%.
The invention provides a preparation method of the silicon-carbon composite material, which comprises the following steps:
(1) dispersing or grinding or dissolving the silicon material, the conductive additive and the first carbon precursor with a solvent respectively, and mixing the three slurries or solutions to obtain silicon/conductive additive/first carbon precursor mixed slurry; or dispersing or grinding or dissolving the silicon material, the conductive additive and the first carbon precursor with a solvent simultaneously to obtain silicon/conductive additive/first carbon precursor mixed slurry; a dispersant can be used in the dispersing or grinding process to improve the efficiency;
(2) drying the mixed slurry, and then performing high-temperature carbonization in a non-oxidizing atmosphere;
(3) and (3) crushing the product obtained in the step (2) to obtain irregularly-shaped secondary particles with the median particle diameter of 1-30 mu m.
(4) Coating the product obtained in the step (3) with a second carbon precursor, and then performing high-temperature carbonization in a non-oxidizing atmosphere;
(5) and (4) crushing and sieving the product obtained in the step (4) to obtain the silicon-carbon composite material.
Wherein in step (1):
the silicon material can be crystalline silicon or amorphous silicon;
the conductive additive can be one or a mixture of more of Super P, Ketjen black, vapor-phase-grown carbon fiber, acetylene black, conductive graphite, carbon nanotubes and graphene;
the first carbon precursor is one or a combination of more of glucose, sucrose, chitosan, starch, citric acid, gelatin, alginic acid, carboxymethyl cellulose, sodium carboxymethyl cellulose, coal pitch, petroleum pitch, phenolic resin, tar, naphthalene oil, anthracene oil, polyvinyl chloride, polystyrene, polyvinylidene fluoride, polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol, epoxy resin, polyacrylonitrile and polymethyl methacrylate;
the dispersing method can adopt any one of a high-speed dispersing machine, a high-speed stirring mill, a ball mill or a sand mill;
the grinding method can adopt any one of a high-speed stirring mill, a ball mill, a tube mill, a cone mill, a rod mill or a sand mill;
the solvent used for dispersing, grinding or dissolving is one or a combination of more of water, methanol, ethanol, isopropanol, N-butanol, ethylene glycol, diethyl ether, acetone, N-methylpyrrolidone, methyl butanone, tetrahydrofuran, benzene, toluene, xylene, N-dimethylformamide, N-dimethylacetamide and trichloromethane.
The dispersing agent used for dispersing or grinding can be one or a combination of more of sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate, cetyl trimethyl ammonium bromide, polyacrylate, polyvinylpyrrolidone, and polyoxyethylene sorbitan monooleate.
Wherein in step (2):
the drying treatment can be any one of spray drying, mechanical drying, vacuum drying, hot air drying and freeze drying;
the high-temperature carbonization can adopt any one of a rotary furnace, a roller kiln, a pushed slab kiln, an atmosphere box furnace or a tubular furnace;
the temperature of the high-temperature carbonization reaction is 500-1400 ℃, and the heat preservation time is 0.5-24 hours;
the non-oxidizing atmosphere is provided by at least one of the following gases: nitrogen, argon, hydrogen or helium.
Wherein in step (3):
the pulverization treatment can adopt any one of an airflow pulverizer, a ball mill, a turbine type pulverizer and a Raymond mill.
Wherein in step (4):
the coating method of the second carbon precursor can adopt any one of a mechanical fusion machine, a VC mixer or a high-speed dispersion machine;
the second carbon precursor is one or a combination of more of coal pitch, petroleum pitch, polyvinyl alcohol, epoxy resin, polyacrylonitrile and polymethyl methacrylate;
the solvent which can be selected by the coating method adopting the VC mixer or the high-speed dispersion machine can be one or the combination of more of water, methanol, ethanol, isopropanol, N-butanol, glycol, diethyl ether, acetone, N-methylpyrrolidone, methyl butanone, tetrahydrofuran, benzene, toluene, xylene, N-dimethylformamide, N-dimethylacetamide and trichloromethane.
The equipment used for high-temperature carbonization can be any one of a rotary furnace, a roller kiln, a pushed slab kiln, an atmosphere box furnace or a tubular furnace;
the temperature of the high-temperature carbonization reaction is 500-1400 ℃, and the heat preservation time is 0.5-24 hours;
the non-oxidizing atmosphere is provided by at least one of the following gases: nitrogen, argon, hydrogen or helium.
The invention also protects the lithium ion battery cathode material prepared by the silicon-carbon composite material, the lithium ion battery cathode prepared by the lithium ion battery cathode material, and the lithium ion battery prepared by the lithium ion battery cathode.
Has the advantages that:
when used as a negative electrode of a lithium ion battery, the silicon-carbon composite material has the electrochemical characteristics of high capacity, high coulombic efficiency and good cycle performance. The lithium ion battery prepared from the silicon-carbon composite material has the characteristics of high volume energy density and good cycle performance. The preparation method of the silicon-carbon composite material is simple, low in cost, good in repeatability, simple in required equipment and capable of realizing large-scale industrial production. The silicon-carbon composite material has wide raw material source and low cost. The invention can really realize the large-scale production of the silicon-containing cathode in the field of lithium ion batteries.
The silicon-carbon composite material is secondary particles with irregular shapes; the secondary particles are formed by compounding a silicon material, a conductive additive and amorphous carbon; the conductive additive is uniformly dispersed in the secondary particles; the conductive additive and the silicon material are tightly bonded together by the amorphous carbon; the outer surface of the secondary particle is provided with a continuous amorphous carbon protective layer. Compared with the prior art, the invention has the following advantages:
1. the irregularly shaped secondary particles have a lower porosity than the spherical secondary particles when stacked, and are effective in improving the porosity
The compaction density of the pole piece is high, so that the energy density of the lithium ion battery is improved; battery pole piece rolling process
The contained secondary particles of irregular shapes are not easily crushed; irregular particle shape also increases between secondary particles
The contact point effectively improves the conductivity of the pole piece and reduces the polarization of the lithium ion battery using the material.
2. The conductive additive is uniformly dispersed in the secondary particles, so that the conductivity in the secondary particles can be effectively improved, and the process is simple and convenient
The polarization of the lithium ion battery using the material is reduced in one step.
3. Each silicon particle is connected by amorphous carbon, which provides excellent electron and lithium ion transport channels, and then
The polarization of the lithium ion battery using the material is reduced in one step.
4. The amorphous carbon in the secondary particles coats and connects the silicon particles with higher specific surface area and the conductive additive into a whole, so that the method is effective
The specific surface area of the composite material is reduced, the formation of SEI is reduced, and the coulomb efficiency of the material is improved.
5. The silicon particles are immobilized within a network or matrix of amorphous carbon that is effectively inhibited and
buffer the expansion of silicon particles and prevent the silicon particles from gradually fusing into larger-sized particles during charging and discharging, resulting in
Greater expansion and failure of a portion of the silicon material.
6. The continuous amorphous carbon protective layer on the outer surface of the secondary particles further reduces the specific surface area of the composite material and SEI
The formation of (2) is beneficial to improving the coulombic efficiency of the material.
Drawings
Fig. 1 is a schematic structural view of a silicon carbon composite material of the present invention.
Fig. 2 is a 500-fold scanning electron micrograph of the silicon carbon composite prepared in example 1.
FIG. 3 is a scanning electron micrograph of the silicon carbon composite material prepared in example 1 at 50000 times before secondary coating.
Fig. 4 is a scanning electron micrograph of the silicon carbon composite material prepared in example 1 magnified 20000 times after secondary coating.
Fig. 5 is a graph of cycle performance of a silicon-containing negative electrode full cell prepared in example 1.
Detailed Description
The present invention will be further described with reference to the following specific examples.
As shown in fig. 1, the silicon-carbon composite material provided by the invention is a secondary particle with an irregular shape; the secondary particles are formed by compounding a silicon material 1, a conductive additive 2 and amorphous carbon 3; the conductive additive 2 is uniformly dispersed in the secondary particles; the conductive additive 2 and the silicon material 1 are tightly bonded together by amorphous carbon 3; the outer surface of the secondary particle has a continuous amorphous carbon protective layer 4.
Example 1
Taking 1000g of micron crystal silicon powder with the median particle size of 4 mu m, 1500g of ethanol and 50g of polyvinylpyrrolidone, and sanding the micron crystal silicon powder with the median particle size of 4 mu m and the ethanol in a sand mill by using zirconia beads with the diameter of 0.3mm to obtain nano silicon particle slurry with the median particle size of 0.4 mu m. To the slurry were added 20g of multiwall carbon nanotube-containing slurry and 20g of ketjen black powder, and sanding was continued for 30 minutes. An aqueous glucose solution was prepared by dissolving 250g of glucose in 2250g of deionized water. The aqueous glucose solution was poured into a sand mill and thoroughly mixed with the silicon nanoparticle slurry for 30 minutes. The uniformly mixed anhydrous ethanol/water slurry of silicon particles/multi-walled carbon nanotubes/ketjen black/glucose was further diluted with deionized water to a solid content of 10%, followed by spray drying. The resulting spherical secondary particles had a median particle diameter of about 15 μm. And heating the spray-dried dry powder in an argon inert atmosphere at 600 ℃ for 2 hours to carbonize glucose, thereby obtaining amorphous carbon bonded and coated silicon particles/multi-walled carbon nanotubes/Ketjen black composite particles. And (3) carrying out jet milling treatment on all the spherical composite particles to obtain irregular composite particles with the median diameter of 10 mu m.
536g of the composite particles and 429g of 2000-mesh petroleum asphalt are mechanically mixed by a VC mixer for 10 minutes, then the temperature of the equipment is raised to 300 ℃ while stirring under the nitrogen protection atmosphere, and then the equipment is kept for 30 minutes, and then the equipment is slowly cooled to the room temperature. And (2) preserving the heat of the asphalt-coated material at 400 ℃ for 2 hours in an argon inert atmosphere, then heating to 900 ℃ for carbonization for 2 hours, naturally cooling to room temperature, crushing and sieving to obtain the silicon particle/multi-wall carbon nanotube/Ketjen black/amorphous carbon composite particle with the amorphous carbon coating.
Fig. 2 shows a scanning electron micrograph of the final silicon carbon composite product of example 1 at 500 x magnification. The product was seen to be irregularly shaped secondary particles. FIG. 3 shows a scanning electron micrograph of the silicon-carbon composite material prepared in example 1 at 50000 times before secondary coating. It is obvious that the multi-wall carbon nano-tube and the Ketjen black are uniformly dispersed among and on the surface of the silicon particles, and the electrical contact among the silicon particles is ensured. Fig. 4 shows 20000 times scanning electron micrograph of the silicon-carbon composite material prepared in example 1 after secondary coating. It can be seen that the surface of the secondary particles is tightly coated with a layer of amorphous carbon to form a dense protective layer.
And (3) homogenizing, coating, drying and rolling 80 parts of the silicon-carbon composite material, 10 parts of the conductive additive and 10 parts of the binder in a water-based system to obtain the silicon-containing negative pole piece.
Half-cell evaluation: and (3) sequentially stacking the prepared silicon-containing negative pole piece, the diaphragm, the lithium piece and the stainless steel gasket, dripping 200 mu L of electrolyte, and sealing to prepare the 2016 type lithium ion half-cell. The capacity and discharge efficiency were tested using a small (micro) current range device from blue-electron, inc. The first reversible lithium removal specific capacity of the half-cell of the silicon-containing cathode is measured to be 1306mAh/g, and the first charge-discharge efficiency is 81.2%.
Full cell evaluation: the prepared silicon-containing negative pole piece is cut, vacuum-baked, wound together with a matched positive pole piece and a diaphragm, filled into an aluminum plastic shell with a corresponding size, injected with a certain amount of electrolyte, sealed and formed to obtain a complete silicon-containing negative pole lithium ion full battery. The capacity and the average voltage of the full battery at 0.2C and the capacity retention rate data of the full battery which is cycled for 200 times at the charge and discharge rate of 0.5C are tested by a battery tester of New Wille electronics Limited of Shenzhen. The volumetric energy density of the full cell thus obtained was 782Wh/L, and the capacity retention rate after 200 charge-discharge cycles was 83.8%. Fig. 5 is a graph of cycle performance of a silicon-containing negative electrode full cell prepared in example 1.
Example 2
Taking 1000g of amorphous silicon nano-powder with the median particle size of 0.1 mu m, 1500g of ethanol and 10g of hexadecyl trimethyl ammonium bromide, and sanding and dispersing the amorphous silicon nano-powder with the median particle size of 0.1 mu m in a sand mill by using zirconia beads with the diameter of 0.3mm until silicon nano-particle slurry with the median particle size of 0.1 mu m is obtained. To the slurry was added 20g of ketjen black powder, and sanding was continued for 30 minutes. 250g of sucrose was dissolved in 2250g of deionized water to prepare an aqueous sucrose solution. The sucrose aqueous solution was poured into a sand mill and thoroughly mixed with the silicon nanoparticle slurry for 30 minutes. The uniformly mixed anhydrous ethanol/water slurry of silicon particles/ketjen black/sucrose was further diluted with deionized water to a solid content of 10%, followed by spray drying treatment. The resulting spherical secondary particles had a median particle diameter of about 28 μm. And heating the spray-dried dry powder at 700 ℃ for 2 hours in an inert atmosphere of argon gas to carbonize the sucrose, thereby obtaining amorphous carbon bonded and coated silicon particles/ketjen black composite particles. And (3) carrying out jet milling treatment on all the spherical composite particles to obtain irregular composite particles with the median diameter of 11 mu m. And (3) mixing 530g of the composite particles and 424g of 2000-mesh petroleum asphalt at a high speed for 10 minutes by using a VC mixer, adding a mechanical fusion machine, and performing high-speed fusion treatment at 1500rpm for 30 minutes to obtain the petroleum asphalt-coated silicon particle/Ketjen black/amorphous carbon composite particles. And (2) preserving the heat of the materials at 300 ℃ for 2 hours in an argon inert atmosphere, then heating to 900 ℃ for carbonization for 2 hours, naturally cooling to room temperature, crushing and sieving to obtain the silicon particles/Ketjen black/amorphous carbon composite particles with the amorphous carbon coating.
The evaluation methods of the half cell and the full cell are the same as example 1, and the first reversible lithium removal specific capacity of the half cell with the silicon-containing cathode is measured to be 1332mAh/g, and the first charge-discharge efficiency is 81.8%. The volume energy density of the full battery is measured to reach 771Wh/L, and the capacity retention rate after 200 charge-discharge cycles is 84.2%.
Example 3
Taking 1000g of amorphous silicon nano-particles with the median particle size of the secondary particle agglomerate of 2 mu m and the median particle size of the primary particle of 0.2 mu m, 1000g of ethanol and 10g of hexadecyl trimethyl ammonium bromide, and sanding and dispersing the amorphous silicon nano-particles with the median particle size of 0.2 mu m in a sand mill by using zirconia beads with the diameter of 0.3mm until silicon nano-particle slurry with the median particle size of 0.2 mu m is obtained. 50g of vapor grown carbon fiber powder was added to the slurry and sanding was continued for 30 minutes. 240g of phenolic resin is dissolved in 2160g of absolute ethyl alcohol to prepare phenolic resin solution. The phenolic resin solution was poured into a sand mill and mixed thoroughly with the silicon nanoparticle slurry for 30 minutes. The uniformly mixed anhydrous ethanol slurry of silicon particles/vapor-phase grown carbon fibers/phenolic resin was further diluted with anhydrous ethanol to a solid content of 10%, followed by spray drying treatment. The resulting spherical secondary particles had a median particle diameter of about 12 μm. And heating the spray-dried dry powder in an argon inert atmosphere at 800 ℃ for 2 hours to carbonize the phenolic resin, thereby obtaining amorphous carbon bonded and coated silicon particles/vapor-grown carbon fiber composite particles. And (3) carrying out jet milling treatment on all the spherical composite particles to obtain irregular composite particles with the median diameter of 6 mu m. 561g of the composite particles were taken, 449g of petroleum asphalt sieved with a 200-mesh sieve was taken, mechanically mixed for 10 minutes by a VC mixer, and then 300g of dimethylcaproamide was added by spraying while stirring. The apparatus was then warmed to 300 ℃ with nitrogen and stirred for a further 30 minutes, and then cooled to room temperature. And (2) preserving the heat of the asphalt-coated material at 400 ℃ for 2 hours in an argon inert atmosphere, then heating to 1000 ℃ for carbonization for 2 hours, naturally cooling to room temperature, crushing and sieving to obtain the silicon particle/vapor-grown carbon fiber composite particle with the amorphous carbon coating.
The evaluation methods of the half cell and the full cell are the same as example 1, and the first reversible lithium removal specific capacity of the half cell containing the silicon negative electrode is measured to be 1289mAh/g, and the first charge-discharge efficiency is 80.6%. The volume energy density of the full battery is measured to be 764Wh/L, and the capacity retention rate after 200 charge-discharge cycles is 84.0%.
Example 4
1000g of silicon micron wire, 900g of deionized water and 20g of sodium hexametaphosphate were sanded with 0.8mm zirconia beads in a sand mill until a slurry of silicon particles having a median particle size of 2 μm was obtained. Slurry containing 10g of graphene was added to the slurry and sanding was continued for 30 minutes. 250g of sucrose is dissolved in 1000g of deionized water to prepare a sucrose aqueous solution. The sucrose aqueous solution was poured into a sand mill and sufficiently mixed with the silicon particle mixed slurry for 30 minutes. The uniformly mixed aqueous slurry of silicon particles/graphene/sucrose was further diluted with deionized water to a solid content of 15%, followed by spray drying to obtain spherical secondary particles having a median particle diameter of about 30 μm. And heating the spray-dried dry powder in an inert atmosphere of argon at 800 ℃ for 2 hours to carbonize sucrose, thereby obtaining amorphous carbon bonded and coated silicon particle/graphene composite particles. And (3) carrying out jet milling treatment on all the spherical composite particles to obtain irregular composite particles with the median diameter of 15 mu m. 530g of the composite particles and 424g of coal tar pitch powder passing through a 100-mesh sieve were mechanically mixed in a VC mixer for 10 minutes, the temperature of the apparatus was raised to 200 ℃ while introducing nitrogen gas, and the mixture was stirred for 30 minutes and then cooled to room temperature. And (2) preserving the heat of the asphalt-coated material at 300 ℃ for 2 hours in an argon inert atmosphere, then heating to 900 ℃ for carbonization for 2 hours, naturally cooling to room temperature, crushing and sieving to obtain the silicon particle/graphene/amorphous carbon composite particle with the amorphous carbon coating.
The evaluation methods of the half cell and the full cell are the same as example 1, and the first reversible lithium removal specific capacity of the half cell containing the silicon negative electrode is measured to be 1249mAh/g, and the first charge-discharge efficiency is 78.2%. The volume energy density of the full cell is determined to reach 755Wh/L, and the capacity retention rate after 200 charge-discharge cycles is 80.3%.
Example 5
1000g of crystalline silicon powder with the median particle size of 4 mu m, 2000g of absolute ethyl alcohol, 20g of polyvinylpyrrolidone and 200g of conductive graphite are taken and sanded by zirconia beads with the particle size of 0.3mm in a sand mill until the particle size peak value of the obtained mixed slurry of the conductive graphite and the silicon particles is 0.3 mu m. An aqueous glucose solution was prepared by dissolving 160g of glucose in 2000g of deionized water. The aqueous glucose solution was poured into a sand mill and thoroughly mixed with the silicon particle/conductive graphite slurry for 30 minutes. The uniformly mixed silicon particle/conductive graphite/glucose slurry was further diluted with deionized water to a solid content of 10%, followed by spray drying to obtain spherical secondary particles having a median particle diameter of about 20 μm. And heating the spray-dried dry powder at 600 ℃ for 3 hours in a nitrogen inert atmosphere to carbonize glucose, thereby obtaining amorphous carbon bonded and coated silicon particle/conductive graphite composite particles. And (3) carrying out jet milling treatment on all the spherical composite particles to obtain irregular composite particles with the median diameter of 10 mu m. 183g of coal pitch was charged into 800g of tetrahydrofuran, and 613g of the above graphite sheet/silicon particle/amorphous carbon composite powder was added with stirring, and the dispersion pan speed was raised to 1000rpm, and the temperature of the stirring vessel was raised to 150 ℃ under a nitrogen atmosphere. Dispersion was continued for 30 minutes after the temperature reached 150 ℃. Then the temperature is raised to 200 ℃, and the mixture is slowly stirred until the tetrahydrofuran is completely evaporated to dryness. And (2) preserving the temperature of the asphalt-coated material at 300 ℃ for 2 hours in an argon inert atmosphere, then heating to 900 ℃ for carbonization for 2 hours, naturally cooling to room temperature, crushing and sieving to obtain the silicon particle/conductive graphite/amorphous carbon composite particle with the amorphous carbon coating.
The evaluation methods of the half cell and the full cell are the same as example 1, and the first reversible lithium removal specific capacity of the half cell with the silicon negative electrode is measured to be 1338mAh/g, and the first charge-discharge efficiency is 77.9%. The volume energy density of the full cell is found to reach 758Wh/L, and the capacity retention rate after 200 charge-discharge cycles is 83.0%.
Example 6
Taking 1000g of polycrystalline silicon powder with the median particle size of 3 mu m, 1000g of deionized water and 20g of sodium polyacrylate, and dispersing for 30 minutes at high speed in a high-speed dispersion machine to obtain silicon particle slurry. A slurry containing 20g of multi-walled carbon nanotubes was added to the slurry and dispersion was continued for 30 minutes. 80g of glucose is dissolved in 320g of deionized water to prepare a glucose aqueous solution, the glucose aqueous solution is poured into a dispersion machine, and the glucose aqueous solution and the mixed slurry of the silicon particles and the multi-walled carbon nanotubes are fully mixed for 30 minutes. And further diluting the uniformly mixed water slurry of the silicon particles/the multi-walled carbon nano tubes/glucose with deionized water until the solid content is 20%, and then carrying out spray drying treatment to obtain spherical secondary particles with the median particle size of about 50 microns. And heating the spray-dried dry powder at 700 ℃ for 2 hours in an inert atmosphere of argon to carbonize glucose, thereby obtaining the amorphous carbon bonded and coated graphite flake/silicon particle composite particles. And performing ball milling treatment on all the spherical composite particles to obtain irregular composite particles with the median diameter of 20 mu m. 520g of the composite particles and 80g of polyvinyl alcohol were mechanically mixed in a VC mixer for 10 minutes, and then 300g of water was added by spraying while stirring. The apparatus was then warmed to 100 ℃ with nitrogen and stirred for 60 minutes, then stirred and held until the water evaporated and the powder cooled to room temperature. And (2) preserving the heat of the polyvinyl alcohol-coated material at 250 ℃ for 2 hours in a nitrogen inert atmosphere, then heating to 700 ℃ for carbonization for 3 hours, naturally cooling to room temperature, crushing and sieving to obtain the silicon particle/multi-wall carbon nanotube/amorphous carbon composite particle with the amorphous carbon coating.
The evaluation methods of the half cell and the full cell are the same as example 1, and the first reversible lithium removal specific capacity of the half cell containing the silicon negative electrode is 1652mAh/g, and the first charge-discharge efficiency is 75.1%. The volume energy density of the whole battery is up to 739Wh/L, and the capacity retention rate after 200 charge-discharge cycles is 75.1%.
Example 7
1000g of crystalline silicon particles having a median particle size of 3 μm were sanded with 2800g of dimethylformamide in a sand mill with 0.8mm zirconia beads to give a slurry of silicon particles having a median particle size of 0.5. mu.m. 10g of Super P powder was added to the slurry and sanding was continued for 30 minutes. 100g of coal tar pitch was dispersed in 900g of dimethylformamide to prepare a pitch suspension. The bitumen suspension was poured into a sand mill and mixed thoroughly with the silica particles/Super P slurry for 30 minutes. And heating the uniformly mixed silicon particle/Super P/asphalt slurry by using a VC mixer under the condition of stirring and vacuumizing for drying treatment. And heating the dried material in an inert atmosphere of argon at 900 ℃ for 2 hours to carbonize the asphalt, so as to obtain the amorphous carbon bonded and coated silicon particle/Super P composite particle. The carbonized material was crushed by a twin-roll mill and sieved with a 100-mesh sieve, and then crushed by a jet mill to obtain irregularly shaped particles having a median particle diameter of 10 μm. 250g of coal pitch was taken and added to 1000g of dimethylformamide, 511g of the above silicon particle/Super P/amorphous carbon composite powder was added with stirring, the speed of the dispersion plate was raised to 1000rpm, and the temperature of the stirring vessel was raised to 150 ℃ under a nitrogen atmosphere. Dispersion was continued for 30 minutes after the temperature reached 150 ℃. Then the temperature is raised to 200 ℃, and the slow stirring is kept until the dimethylformamide is completely evaporated to dryness. And (2) keeping the asphalt-coated material at 300 ℃ for 2 hours in an argon inert atmosphere, then heating to 900 ℃ for carbonization for 2 hours, naturally cooling to room temperature, crushing and sieving to obtain the silicon particle/Super P/amorphous carbon composite particle with the amorphous carbon coating.
The evaluation methods of the half cell and the full cell are the same as example 1, and the first reversible lithium removal specific capacity of the half cell with the silicon-containing cathode is measured to be 1511mAh/g, and the first charge-discharge efficiency is 79.2%. The volume energy density of the full cell reaches 776Wh/L, and the capacity retention rate after 200 charge-discharge cycles is 79.8%.
Example 8
1000g of polycrystalline silicon powder with a median particle size of 5 μm, 2000g of isopropanol and 20g of polyvinylpyrrolidone were sanded with 0.8mm zirconia beads in a sand mill until silicon nanoparticle slurry with a median particle size of 0.4 μm was obtained. 170g of conductive graphite and a slurry containing 30g of multi-walled carbon nanotubes were added to the slurry and sanding was continued for 30 minutes. 400g of phenolic resin is dissolved in 3600g of isopropanol to prepare a phenolic resin isopropanol solution. The phenolic resin isopropanol solution was poured into a sand mill and mixed thoroughly with the silicon nanoparticle slurry for 30 minutes. And heating and vacuumizing the uniformly mixed isopropanol slurry of the silicon particles/the conductive graphite/the multi-walled carbon nano tubes/the phenolic resin by using a VC mixer under the condition of stirring for drying. And heating the dried material at 800 ℃ for 2 hours in an argon inert atmosphere to carbonize phenolic resin, thereby obtaining amorphous carbon bonded and coated silicon particle/conductive graphite/multi-walled carbon nanotube composite particles. The carbonized material was crushed by a twin-roll mill and sieved with a 100-mesh sieve, and then crushed by a jet mill to obtain irregularly shaped particles having a median particle diameter of 12 μm. 840g of coal pitch is added into 3360g of dimethylformamide, 700g of the silicon particle/conductive graphite/multi-walled carbon nanotube composite particle powder is added while stirring, the speed of a dispersion plate is increased to 1000rpm, and the temperature of a stirring container is increased to 150 ℃ under the nitrogen atmosphere. Dispersion was continued for 30 minutes after the temperature reached 150 ℃. Then the temperature is raised to 200 ℃, and the slow stirring is kept until the dimethylformamide is completely evaporated to dryness. And (2) preserving the heat of the material coated with the asphalt at 300 ℃ for 2 hours in an argon inert atmosphere, then heating to 1000 ℃ for carbonization for 2 hours, naturally cooling to room temperature, crushing and sieving to obtain the silicon particle/conductive graphite/multi-walled carbon nanotube/amorphous carbon composite particle with the amorphous carbon coating.
The evaluation methods of the half cell and the full cell are the same as example 1, and the first reversible lithium removal specific capacity of the half cell containing the silicon negative electrode is 938mAh/g, and the first charge-discharge efficiency is 85.3%. The volume energy density of the full cell is measured to reach 804Wh/L, and the capacity retention rate after 200 charge-discharge cycles is 86.3%.
Example 9
1000g of polycrystalline silicon powder with a median particle size of 2 μm and 2000g of dimethylacetamide were sanded with 0.3mm zirconia beads in a sand mill until silicon nanoparticle slurry with a median particle size of 0.3 μm was obtained. A slurry containing 8g of single-walled carbon nanotubes was added to the slurry and sanding was continued for 30 minutes. 160g of petroleum pitch was dispersed in 1440g of dimethylacetamide. The dimethylacetamide dispersion of petroleum asphalt was poured into a sand mill and mixed with the silicon nanoparticle slurry thoroughly for 30 minutes. And heating and vacuumizing the uniformly mixed dimethylacetamide slurry of the silicon particles/the single-walled carbon nanotubes/the petroleum asphalt under the condition of stirring by using a VC mixer for drying. And (3) drying to obtain a material, heating the material at 700 ℃ for 2 hours in an argon inert atmosphere to carbonize petroleum asphalt, and obtaining amorphous carbon bonded and coated silicon particle/single-walled carbon nanotube composite particles. The carbonized material was crushed by a twin-roll mill and sieved with a 100-mesh sieve, and then crushed by a jet mill to obtain irregularly shaped particles having a median particle diameter of 10 μm. 326g of coal tar pitch was added to 1500g of dimethylformamide, 544g of the above silicon particle/conductive graphite/multiwalled carbon nanotube composite particle powder was added while stirring, the speed of the dispersion plate was increased to 1000rpm, and the temperature of the stirring vessel was increased to 150 ℃ under a nitrogen atmosphere. Dispersion was continued for 30 minutes after the temperature reached 150 ℃. Then the temperature is raised to 200 ℃, and the slow stirring is kept until the dimethylformamide is completely evaporated to dryness. And (2) preserving the asphalt-coated material at 300 ℃ for 2 hours in an argon inert atmosphere, then heating to 900 ℃ for carbonization for 2 hours, naturally cooling to room temperature, crushing and sieving to obtain the silicon particle/single-walled carbon nanotube/amorphous carbon composite particle with the amorphous carbon coating.
The evaluation methods of the half cell and the full cell are the same as example 1, and the first reversible lithium removal specific capacity of the half cell containing the silicon negative electrode is 1353mAh/g, and the first charge-discharge efficiency is 78.4%. The volume energy density of the full battery is measured to reach 771Wh/L, and the capacity retention rate after 200 charge-discharge cycles is 82.6%.
Comparative example 1
The process is similar to example 1 except that no two conductive additives, multiwall carbon nanotubes and ketjen black, were added during the material synthesis. The product is a silicon particle/amorphous carbon composite particle with an amorphous carbon coating layer, not containing any conductive additive.
The evaluation methods of the half cell and the full cell are the same as example 1, and the first reversible lithium removal specific capacity of the half cell containing the silicon negative electrode is measured to be 1003mAh/g, and the first charge-discharge efficiency is 70.1%. The volumetric energy density of the full cell of the silicon-containing negative electrode was 639Wh/L, and the capacity retention rate after 200 charge-discharge cycles was 30.7%.
Comparative example 2
The process is similar to example 2, and differs from example 2 in that the spray-dried spherical secondary particles are not crushed and are directly coated with amorphous carbon for the second time.
The evaluation methods of the half cell and the full cell are the same as example 1, and the first reversible lithium removal specific capacity of the half cell containing the silicon negative electrode is 1150mAh/g, and the first charge-discharge efficiency is 75.1%. The volumetric energy density of the full cell of the silicon-containing negative electrode was found to be 692Wh/L, and the capacity retention rate after 200 charge-discharge cycles was found to be 61.2%.
Comparative example 3
The process is similar to that of example 3, except that the surface of the secondary particles is not coated with amorphous carbon.
The evaluation methods of the half cell and the full cell are the same as example 1, and the first reversible lithium removal specific capacity of the half cell with the silicon-containing cathode is measured to be 1334mAh/g, and the first charge-discharge efficiency is measured to be 62.1%. The volumetric energy density of the full cell of the silicon-containing negative electrode was 621Wh/L, and the capacity retention rate after 200 charge-discharge cycles was 15.3%.
Examples summary of electrochemical data:
the above description is only a preferred embodiment of the present invention, and should not be taken as limiting the invention in any way, and any person skilled in the art can make any simple modification, equivalent replacement, and improvement on the above embodiment without departing from the technical spirit of the present invention, and still fall within the protection scope of the technical solution of the present invention.
Claims (5)
1. A preparation method of a silicon-carbon composite material for a lithium ion battery is characterized by comprising the following steps:
the preparation method comprises the following steps: taking 1000g of microcrystalline silicon powder with the median particle size of 4 mu m, 1500g of ethanol and 50g of polyvinylpyrrolidone, sanding the mixture in a sand mill to obtain nano silicon particle slurry with the median particle size of 0.4 mu m, adding slurry containing 20g of multi-walled carbon nanotubes and 20g of Ketjen black powder into the nano silicon particle slurry, continuing sanding the mixture for 30 minutes, dissolving 250g of glucose in 2250g of deionized water to prepare a glucose aqueous solution, pouring the glucose aqueous solution into the sand mill, fully mixing the glucose aqueous solution with the silicon nanoparticle slurry for 30 minutes, diluting the mixture with deionized water to reach the solid content of 10 percent, then carrying out spray drying treatment to obtain spherical secondary particles with the median particle size of 15 mu m, then heating the spherical secondary particles in an argon inert atmosphere at 600 ℃ for 2 hours to carbonize the glucose to obtain amorphous carbon bonded and coated silicon particles/multi-walled carbon nanotubes/Ketjen black spherical composite particles, carrying out airflow crushing treatment on all the spherical composite particles, obtaining irregular-shaped composite particles with the median particle size of 10 microns, taking 536g of the irregular-shaped composite particles, taking 429g of 2000-mesh petroleum asphalt, mechanically mixing for 10 minutes by using a VC mixer, heating the equipment to 300 ℃ while stirring in a nitrogen protection atmosphere, keeping the temperature for 30 minutes, then slowly cooling to room temperature, keeping the temperature of the petroleum asphalt-coated material at 400 ℃ for 2 hours in an argon inert atmosphere, then heating to 900 ℃ for carbonization for 2 hours, naturally cooling to room temperature, crushing and sieving to obtain silicon particles/multi-walled carbon nanotubes/ketjenblack/amorphous carbon composite particles with amorphous carbon coatings;
alternatively, the preparation method comprises the following steps: taking 1000g of amorphous silicon nano-powder with the median particle size of secondary particle agglomerate of 2 mu m and the median particle size of primary particles of 0.2 mu m, 1000g of ethanol and 10g of hexadecyl trimethyl ammonium bromide, carrying out sand grinding and dispersion in a sand mill until silicon nano-particle slurry with the median particle size of 0.2 mu m is obtained, adding 50g of vapor phase growth carbon fiber powder into the silicon nano-particle slurry, continuing sand grinding for 30 minutes, dissolving 240g of phenolic resin in 2160g of absolute ethanol to prepare phenolic resin solution, pouring the phenolic resin solution into the sand mill, fully mixing the phenolic resin solution with the silicon nano-particle slurry for 30 minutes, diluting the solution with absolute ethanol until the solid content is 10 percent, then carrying out spray drying treatment to obtain spherical secondary particles with the median particle size of 12 mu m, heating the spray dried dry powder in argon inert atmosphere at 800 ℃ for 2 hours to carbonize the phenolic resin to obtain amorphous carbon particle/vapor phase growth carbon fiber composite particles bonded and coated with amorphous carbon, carrying out jet milling treatment on all the spherical composite particles to obtain irregular composite particles with the median diameter of 6 mu m; collecting 561g of the irregular-shaped composite particles, collecting 449g of petroleum asphalt which is sieved by a 200-mesh sieve, mechanically mixing for 10 minutes by a VC mixer, spraying and adding 300g of dimethyl caproamide while stirring, heating the equipment to 300 ℃ while introducing nitrogen, continuously stirring for 30 minutes, cooling to room temperature, keeping the petroleum asphalt-coated material at 400 ℃ for 2 hours in an argon inert atmosphere, heating to 1000 ℃ for carbonization for 2 hours, naturally cooling to room temperature, crushing and sieving to obtain silicon particles/vapor-grown carbon fiber/amorphous carbon composite particles with amorphous carbon coatings;
alternatively, the preparation method comprises the following steps: taking 1000g of polycrystalline silicon powder with the median particle size of 3 mu m, 1000g of deionized water and 20g of sodium polyacrylate, dispersing for 30 minutes at a high speed in a high-speed dispersion machine to obtain silicon particle slurry, adding the slurry containing 20g of multi-walled carbon nanotubes into the silicon particle slurry, continuing to disperse for 30 minutes, dissolving 80g of glucose in 320g of deionized water to prepare a glucose aqueous solution, pouring the glucose aqueous solution into the dispersion machine, fully mixing the glucose aqueous solution with the mixed slurry of silicon particles/multi-walled carbon nanotubes for 30 minutes, diluting the mixture with the deionized water until the solid content is 20%, then carrying out spray drying treatment to obtain spherical secondary particles with the median particle size of 50 mu m, heating the spray dried dry powder in an argon inert atmosphere at 700 ℃ for 2 hours to carbonize the glucose to obtain amorphous carbon bonded and multi-walled carbon nanotube/silicon particle spherical composite particles, carrying out ball milling treatment on all the spherical composite particles, obtaining irregular-shaped composite particles with the median particle size of 20 microns, taking 520g of the irregular-shaped composite particles, taking 80g of polyvinyl alcohol, mechanically mixing for 10 minutes by using a VC mixer, spraying and adding 300g of water while stirring, heating the equipment to 100 ℃ while introducing nitrogen, continuously stirring for 60 minutes, continuously stirring and keeping the temperature until the water is evaporated to dryness, cooling the powder to room temperature, keeping the temperature of the polyvinyl alcohol-coated material at 250 ℃ for 2 hours in a nitrogen inert atmosphere, heating to 700 ℃ for carbonization for 3 hours, naturally cooling to room temperature, crushing and sieving to obtain silicon particles/multi-walled carbon nanotubes/amorphous carbon composite particles with amorphous carbon coatings;
alternatively, the preparation method comprises the following steps: grinding 1000g of crystalline silicon particles with the median particle size of 3 mu m and 2800g of dimethylformamide in a sand mill to obtain silicon particle slurry with the median particle size of 0.5 mu m, adding 10g of Super P powder into the slurry, continuing grinding for 30 minutes, dispersing 100g of coal pitch in 900g of dimethylformamide to prepare coal pitch suspension, pouring the coal pitch suspension into the sand mill to be fully mixed with the silicon particle/Super P slurry for 30 minutes, heating and vacuumizing the mixture by a VC mixer under the condition of stirring to carry out drying treatment, heating the dried material for 2 hours at 900 ℃ in an argon inert atmosphere to carbonize the coal pitch to obtain amorphous carbon bonded and coated silicon particle/Super P composite particles, crushing the carbonized material by a counter-roller machine, sieving the crushed material by a 100-mesh sieve, crushing by a jet mill to obtain irregular particles with the median particle size of 10 mu m, taking 250g of coal pitch and adding the crushed coal pitch into 1000g of dimethylformamide, adding 511g of the irregular particles while stirring, increasing the speed of a dispersion plate to 1000rpm, increasing the temperature of the stirring container to 150 ℃ under a nitrogen atmosphere, and continuing to disperse for 30 minutes after the temperature reaches 150 ℃; heating to 200 ℃, keeping stirring slowly until the dimethylformamide is completely evaporated to dryness, keeping the obtained coal tar pitch-coated material at 300 ℃ for 2 hours in an inert atmosphere of argon, heating to 900 ℃ for carbonization for 2 hours, naturally cooling to room temperature, crushing and sieving to obtain silicon particles/Super P/amorphous carbon composite particles with amorphous carbon coating layers;
alternatively, the preparation method comprises the following steps: taking 1000g of polycrystalline silicon powder with the median particle size of 2 mu m and 2000g of dimethylacetamide, sanding in a sand mill until silicon nanoparticle slurry with the median particle size of 0.3 mu m is obtained, adding slurry containing 8g of single-walled carbon nanotubes into the silicon nanoparticle slurry, continuing sanding for 30 minutes, dispersing 160g of petroleum asphalt in 1440g of dimethylacetamide, pouring into the sand mill, fully mixing with the silicon nanoparticle slurry for 30 minutes, heating and vacuumizing by a VC mixer under the condition of stirring for drying, heating the dried material for 2 hours at 700 ℃ in an argon inert atmosphere to carbonize the petroleum asphalt, obtaining amorphous carbon bonded and coated silicon particle/single-walled carbon nanotube composite particles, crushing the carbonized material by a pair roller machine through a 100-mesh sieve, crushing by a jet mill to obtain irregular-shaped particles with the median particle size of 10 mu m, adding 326g of coal tar pitch into 1500g of dimethylformamide, adding 544g of the irregular-shaped particles while stirring, increasing the speed of a dispersion disc to 1000rpm, increasing the temperature of a stirring container to 150 ℃ under the nitrogen atmosphere, continuing to disperse for 30 minutes after the temperature reaches 150 ℃, then increasing the temperature to 200 ℃, and slowly stirring until the dimethylformamide is completely evaporated to dryness; and (3) keeping the obtained coal tar pitch-coated material at 300 ℃ for 2 hours in an argon inert atmosphere, then heating to 900 ℃ for carbonization for 2 hours, naturally cooling to room temperature, crushing and sieving to obtain the silicon particle/single-walled carbon nanotube/amorphous carbon composite particle with the amorphous carbon coating.
2. A silicon carbon composite material prepared according to the method of claim 1.
3. A lithium ion battery negative electrode material is characterized in that: a lithium ion battery negative electrode material prepared by using the silicon-carbon composite material of claim 2.
4. A lithium ion battery negative electrode, characterized in that: a lithium ion battery cathode prepared by the lithium ion battery cathode material of claim 3.
5. A lithium ion battery, characterized by: a lithium ion battery prepared using the lithium ion battery negative electrode of claim 4.
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| CN109713268A (en) * | 2018-12-25 | 2019-05-03 | 江西中汽瑞华新能源科技有限公司 | A kind of preparation method of lithium ion battery silicon-carbon cathode material |
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| CN111384373B (en) * | 2018-12-29 | 2021-06-01 | 安普瑞斯（南京）有限公司 | Silicon-carbon composite material for lithium ion battery and preparation method thereof |
| CN111384388B (en) * | 2018-12-29 | 2021-09-28 | 安普瑞斯（南京）有限公司 | High-energy-density lithium ion battery |
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| CN109830668B (en) * | 2019-02-28 | 2021-09-03 | 昆明理工大学 | Method for preparing lithium ion battery silicon-carbon negative electrode material by adopting carbon nano tube |
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