CN108682830B - Silicon-carbon composite negative electrode material of lithium ion battery and preparation method thereof - Google Patents
Silicon-carbon composite negative electrode material of lithium ion battery and preparation method thereof Download PDFInfo
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- CN108682830B CN108682830B CN201810592172.0A CN201810592172A CN108682830B CN 108682830 B CN108682830 B CN 108682830B CN 201810592172 A CN201810592172 A CN 201810592172A CN 108682830 B CN108682830 B CN 108682830B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the field of energy storage research, and particularly relates to a lithium ion battery silicon-carbon composite negative electrode material and a preparation method thereof, wherein the preparation method comprises the following steps: (1) uniformly mixing the graphene precursor, the blowing agent, graphite and nano silicon, and drying to obtain a solid material; (2) compacting the solid material into a green body by using film pressing forming equipment; (3) carrying out heat treatment on the compacted blank, and sintering at high temperature to obtain a silicon-carbon composite anode material; the silicon-carbon composite negative electrode material prepared by the preparation method is applied to a lithium ion battery, and has higher charging specific capacity and excellent cycling stability.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a silicon-carbon composite negative electrode material of a lithium ion battery and a preparation method thereof
Background
At present, the cathode material of the commercial lithium ion battery is mainly a graphite cathode material, however, with the improvement of the requirement of the electric automobile and the large-scale equipment on the energy density of the battery, the graphite cathode material cannot meet the actual requirement due to the low theoretical capacity (372mAh/g), and therefore, the development of the cathode material with high energy density is urgently needed.
Silicon is considered to have the potential of replacing graphite cathode materials in the next generation due to the fact that the silicon has high theoretical capacity (4200mAh/g) and lower lithium extraction potential (< 0.05V), the voltage platform is slightly higher than that of graphite, lithium extraction on the silicon surface is difficult to cause during charging and discharging, and safety performance is better. However, silicon also has problems when used as a negative electrode material of a lithium ion battery, and during the charge and discharge cycle, lithium ion intercalation and deintercalation can cause the volume of the material to expand and contract by 300%, and the generated mechanical stress can cause the material to be gradually pulverized and the structure to collapse, so that an active substance is finally dropped on a current collector, and the cycle performance of the lithium ion battery is greatly reduced. In addition, since silicon is a semiconductor material, poor conductivity further limits the application of silicon to lithium ion battery negative electrode materials. Therefore, a host material capable of not only increasing the conductivity of the material but also suppressing the volume expansion of the silicon material, thereby improving the electrochemical performance, is urgently needed to be found.
Graphene is considered as a star material due to the unique flexible two-dimensional planar structure, ultrahigh conductivity and specific surface area, so that the graphene and nano silicon are compounded to form the graphene/nano silicon composite material, the volume expansion of the nano silicon in the charging and discharging process can be relieved, the conductivity of the material can be improved, and the electrochemical performance of the material can be improved.
However, most of the methods for preparing graphene/nano silicon composite materials disclosed in the prior art adopt a process of preparing graphene and then compounding the graphene with silicon materials, which results in high cost and is not suitable for industrialization. Huang et al (Journal of physical chemistry Letters,2012,3(13):1824) use atomization method to prepare graphene and silicon aerosol, and prepare core-shell structured folded graphene and silicon composite material through pretreatment and calcination, wherein the composite material has no specific capacity decay phenomenon after 200 weeks of circulation in a button cell. Guo (chemical communications,2012,48(16):2198-200) adopts freeze drying and thermal reduction methods to prepare silicon-carbon composite materials in which nano-silicon is embedded on graphene nano-sheets.
Chinese patent CN201510252804.5 discloses a preparation method of graphene-based silicon-carbon composite negative electrode material, which comprises the following steps: the preparation method comprises the steps of firstly preparing three-dimensional graphene particles, and then depositing nano-silicon on the surface of graphene by a deposition method, so that the process is complex, the cost is high, and the deposited nano-silicon is easy to agglomerate in the sintering process, so that the cycle performance of the electrode material is reduced.
Chinese patent CN201710544133.9 discloses a preparation method of a graphene-silicon carbon lithium ion battery cathode material, which comprises the following steps: graphene coating of nano silicon particles, carbon coating of the primary composite material, carbonization and mixing; however, the graphene and silicon sand milling process of the method is easy to cause silicon to be oxidized into silicon dioxide, so that the capacity of the silicon-based composite material is reduced.
Disclosure of Invention
In view of the defects of the prior art, one of the purposes of the present invention is to provide a preparation method of a silicon-carbon composite negative electrode material, which can realize uniform coating of a nano silicon material while preparing graphene.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a silicon-carbon composite negative electrode material comprises the following steps:
dispersing a graphene precursor, a blowing agent, graphite and nano silicon into a solvent, uniformly mixing, and drying to obtain a solid material;
compacting the solid material obtained in the step one into a green body by using film pressing forming equipment;
and step three, carrying out heat treatment on the blank obtained in the step two in a protective gas atmosphere, and then sintering at high temperature to obtain the silicon-carbon composite anode material.
Preferably, the blank obtained in the step two is placed in sintering equipment, the temperature is firstly raised to 150-180 ℃ in the protective gas atmosphere, the temperature is kept for 2-5 h, then the temperature is continuously raised to 800-1800 ℃ for sintering, the sintering time is 1-5 h, and the silicon-carbon composite negative electrode material is obtained after natural cooling to the room temperature.
Preferably, in the first step, the weight ratio of the graphene precursor to the blowing agent to the graphite to the nano-silicon is (1-1.8): (7-18): (0.5-1.5): (5-12); more preferably (1-1.5): (7-15): (0.5-1): (5-10), particularly preferably (1-1.5): (5-10): (0.5-0.8): (7-9).
Preferably, the graphene precursor is a combination of 1 or more than 2 of sucrose, glucose, starch or asphalt, and further preferably glucose or asphalt;
preferably, the asphalt is 1 or a combination of more than 2 of high-temperature asphalt, emulsified asphalt or low-temperature asphalt.
Preferably, the graphite is artificial graphite, microcrystalline graphite or natural graphite 1 or 2 or more, more preferably natural graphite, and the shape of the graphite is 1 of flake, sphere or sphere.
Preferably, the median particle diameter (D) of the graphite50) 8 to 18 μm, for example, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 14 μm, 16 μm, 17 μm, 17.5 μm, 17.8 μm or 17.9 μm, etc., more preferably 8 to 12 μm, and particularly preferably 10 to 12 μm.
Preferably, in the first step, the blowing agent is 1 or a combination of more than 2 of ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium carbonate or ammonium bicarbonate.
Preferably, in the step one, the solvent is deionized water, alcohols, ethers, alkanes, ketones, aromatics, and more preferably 1 or a combination of 2 or more of methanol, ethanol, N-butanol, ethylene glycol, isopropanol, acetone, N-methylpyrrolidone, N-hexane, cyclohexane, benzene, toluene, xylene, styrene, dichloromethane, trichloroethylene ethanol, dimethylformamide, dimethylsulfoxide, and tetrahydrofuran.
Preferably, the nano-silicon has a median particle diameter (D)50) 5 to 170nm, for example, 5nm, 10nm, 20nm, 42nm, 66nm, 80nm, 100nm, 120nm, 130nm, 140nm, 155nm, 165nm or 169nm, more preferably 30 to 130nm, particularly preferably 50 to 80 nm.
Preferably, the drying method in the step one may be a drying method conventional in the art, and further preferably 1 of freeze drying, vacuum drying and spray drying;
preferably, the drying temperature is 60-100 ℃, more preferably 60-90 ℃, and particularly preferably 70-80 ℃.
Preferably, the pressure of the film pressing forming equipment in the second step is 7-50 mPa, more preferably 8-20 mPa, and particularly preferably 8-10 mPa;
the research of the invention shows that the pressure of the compacted green body has great influence on the final composite material, the composite material is compacted due to overlarge pressure, and the graphene precursor in a molten state cannot flow around in the sintering process, so that the surfaces of nano-silicon and graphite in the composite material cannot be uniformly coated;
preferably, the pressure maintaining time of the film pressing forming equipment in the second step is 1-10 min, more preferably 2-8 min, and particularly preferably 3-6 min;
preferably, the sintering process in the third step is performed under a protective atmosphere, wherein the protective atmosphere is nitrogen or argon;
preferably, the temperature rise rate of the heating process in the third step is 0.5-10 ℃/min, more preferably 2-8 ℃/min, and particularly preferably 3-6 ℃/min.
Preferably, the temperature of the heat treatment process in the third step is 160-180 ℃;
preferably, the heat preservation time of the heat treatment process in the third step is 3-5 h;
preferably, the temperature rise rate of the temperature rise in the third step until the sintering process is 0.5-10 ℃/min, more preferably 2-8 ℃/min, and particularly preferably 3-6 ℃/min.
Preferably, the sintering temperature in the sintering process in the third step is 900-1200 ℃, and further preferably 900-1100 ℃;
preferably, the sintering time in the sintering process in the third step is 2-5 h, and further preferably 2-4 h;
preferably, the preparation method of the silicon-carbon composite anode material comprises the following steps:
adding a graphene precursor and a blowing agent into a solvent, stirring and mixing to form a uniform solution, then adding graphite and nano-silicon into the solution, uniformly mixing, and drying to obtain a mixed material;
compacting the mixed material obtained in the step one by using film pressing forming equipment to obtain a blank;
and step three, placing the blank obtained in the step one in a sintering furnace, firstly heating to 150-180 ℃ at a heating rate of 0.5-10 ℃/min under the atmosphere of protective gas, keeping the temperature for 2-5 h, then continuously heating to 800-1800 ℃ at a heating rate of 0.5-10 ℃/min for sintering, wherein the sintering time is 1-5 h, and naturally cooling to room temperature to obtain the silicon-carbon composite negative electrode material.
Uniformly mixing a graphene precursor, a blowing agent, graphite and a nano-silicon liquid phase, and drying to obtain a mixed material, wherein in the mixed material, the graphene precursor is coated on the surfaces of the nano-silicon and the graphite, and the blowing agent is dispersed in each material; compacting the mixed material by using a film pressing forming device to obtain a blank; the process of compacting the mixed material into a green body helps to: a. the blowing agent in the blank body is in surface-to-surface contact with the graphene precursor, so that the pressure generated when the blowing agent is decomposed in the subsequent high-temperature sintering process is utilized to the maximum extent, and the graphene precursor coated with the nano silicon is stripped in situ; b. the blowing agent can be uniformly dispersed on the surface or the inner layer of the graphene precursor; c. the nano silicon is uniformly dispersed on the surface of the graphene and between graphene sheets in situ to avoid oxidation; d. the nano silicon is prevented from agglomerating in the sintering stage; finally, carrying out heat treatment and high-temperature sintering on the blank to obtain the silicon-carbon composite anode material; the sintering process is a key process for preparing graphene, the graphene precursor is in a molten state in the first-stage heat treatment process, the bond energy between molecules is minimum and the distance between molecules is maximum, meanwhile, the molecular layer in the molten state can be pulled open by gas pressure generated in the decomposition process of the blowing agent at the temperature to prepare a single-layer molecular layer, the molecular layer is gradually carbonized to graphitize along with the rise of the temperature in the second stage, and finally the graphene is prepared.
It should be noted that the temperature of the first stage heat treatment process in the sintering process must be based on the softening point temperature of the graphene precursor material and the decomposition temperature of the blowing agent, for example, the softening point temperature of the graphene precursor glucose is 110 ℃, the decomposition temperature of the blowing agent ammonium nitrate is 120 ℃, the temperature of the first stage heat treatment process needs to be set at 120-130 ℃, and the holding temperature of the second stage sintering process is preferably set at 1000 ℃ or above, so as to facilitate the graphitization of the amorphous carbon.
Another object of the present invention is to provide a silicon-carbon composite material prepared by the above method, wherein the composite material has a core-shell structure, wherein the core is formed by compounding graphite and nano-silicon coated on the surface of the graphite, and the shell is formed by graphene and nano-silicon uniformly dispersed between graphene sheets; fig. 1 is a schematic structural diagram of the silicon-carbon composite negative electrode material of the present invention.
Preferably, the content of the nano-silicon distributed on the graphite surface is lower than 50%, and the content of the nano-silicon embedded between graphene sheets is higher than 50%, so that the distribution mode can obviously improve the conductivity of the composite material and reduce the volume expansion effect of the nano-silicon material in the charging and discharging processes.
Preferably, the content of nano silicon in the silicon-carbon composite negative electrode material is 3-25 wt%, the content of graphene is 1-10 wt%, and the content of graphite is 20-70 wt%.
Preferably, the graphene in the silicon-carbon composite negative electrode material is prepared by carrying out heat treatment on a graphene precursor;
preferably, the silicon-carbon composite anode material has a median particle diameter (D)50) 8 to 20 μm, for example, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 14 μm, 16 μm, 18 μm, 19.5 μm, 19.7 μm or 19.9 μm, and more preferably 13 to 15 μm;
preferably, the specific surface area of the silicon-carbon composite negative electrode material is 1-20 m2(ii) g, more preferably 1 to 12m2A specific preferred range is 1 to 3m2/g；
The invention also aims to provide a lithium ion battery, which comprises the silicon-carbon composite negative electrode material prepared by the preparation method.
Advantageous effects
Compared with the prior art, the method has the advantages that,
(1) the preparation method realizes the synchronization and integration of the preparation of the graphene and the silicon material coating process (namely, the silicon material is uniformly coated while the graphene is prepared), and compared with the existing method for preparing the graphene and then coating the silicon material, the preparation method has the advantages of simpler preparation process, no need of reagents such as sulfuric acid and potassium permanganate, environmental friendliness, low cost and suitability for industrialization.
(2) According to the preparation method, the green body is obtained by adopting compaction equipment, the silicon-coated graphene precursor is stripped in situ by pressure generated when a bubbling agent is decomposed to generate gas in the green body in the first-stage heat treatment process, so that the nano silicon is always in the inner layer of the graphene and cannot agglomerate due to high-temperature sintering, the nano silicon material can be uniformly dispersed among graphene sheet layers, the graphene has good mechanical property and electrical conductivity and can effectively relieve the deformation stress of silicon, and the excellent electrical conductivity and thermal conductivity provide rapid electronic conduction and thermal evacuation, so that the silicon-carbon composite negative electrode material obtained by the preparation method has high specific capacity and excellent cycling stability, the charging specific capacity under the current density of 1C is 625.35mAh/g, and the capacity retention rate of 300 cycles is 85.01%.
Drawings
FIG. 1 is a schematic structural diagram of a silicon-carbon composite negative electrode material according to the present invention;
FIG. 2 is a graph showing cycle performance of the Si-C composite anode material obtained in example 1;
Detailed Description
The present invention is described in further detail below with reference to specific examples, but the scope of the present invention is not intended to be limited thereto.
Example 1
Dissolving 1g of sucrose and 10g of ammonium carbonate in 30mL of deionized water, stirring for 30 minutes, adding 3g of graphite with the diameter of 10 micrometers of D50 and nano-silicon with the diameter of 50nm of 0.5g D50, stirring for 1 hour, placing in a forced air drying oven, setting the temperature at 90 ℃, drying for 12 hours to obtain a block-shaped body, compacting the block-shaped solid into a blank by using a film pressing forming device, wherein the pressure is 8mPa, and the pressure is maintained for 3 minutes. Placing the blank in a tubular furnace constant-temperature area, heating to 300 ℃ at a heating rate of 2 ℃/min under the protection of nitrogen, keeping the temperature for 3h, then continuing heating to 1000 ℃ and keeping the temperature for 3h, finally naturally cooling to room temperature, taking out a sample, crushing and sieving the sample to obtain the silicon-carbon composite negative electrode material with the median particle size D50 of 12.5 mu m
Example 2
Dissolving 1g of sucrose and 10g of ammonium nitrate in 30mL of water, stirring for 30 minutes, adding 10 μm of graphite 3g D50 and 80nm of nano-silicon 0.5g D50, stirring for 1 hour, placing in a forced air drying oven, drying the solution at 85 ℃ to obtain a block-shaped solid, compacting the block-shaped solid into a blank by a film pressing forming device, wherein the pressure is 10mPa, and the pressure is maintained for 6 minutes. And placing the blank in a tubular furnace constant-temperature area, heating to 120 ℃ at a heating rate of 2 ℃/min under the protection of nitrogen, keeping the temperature for 3h, then continuing heating to 1000 ℃, keeping the temperature for 3h, naturally cooling to room temperature, taking out a sample, crushing and sieving the sample to obtain the silicon-carbon composite negative electrode material with the median particle size D50 of 12.5 mu m.
Example 3
Dissolving 2g of glucose and 10g of ammonium bisulfate in 30mL of water, stirring for 30min, adding 3g of 10 mu m graphite and 80nm nano-silicon of 0.5g D50, stirring for 2h, drying the solution in a forced air drying oven at 90 ℃ to obtain a block body, compacting the block body into a blank by a film pressing forming device, wherein the pressure is 10mPa, and the pressure is maintained for 3 min. And placing the blank body in a tubular furnace constant-temperature area, placing the blank body in the tubular furnace constant-temperature area, heating to 220 ℃ at a heating rate of 2 ℃/min under the protection of nitrogen, keeping the temperature for 3h, then continuing heating to 1000 ℃ and keeping the temperature for 3h, finally naturally cooling to room temperature, taking out a sample, crushing and sieving the sample to obtain the silicon-carbon composite negative electrode material with the median particle size D50 of 12.5 microns.
Example 4
Dissolving 10g of glucose and 80g of ammonium bicarbonate in 120mL of water, stirring for 4h, adding 30g of 10 mu m graphite and 5g of nano silicon with the D50 of 80nm, stirring for 1h, drying in a spray drying device at the temperature of a discharge port of 110 ℃ to obtain a block body, compacting the block body into a blank body by a film pressing forming device at the pressure of 20mPa, and maintaining the pressure for 3 min. And placing the blank in a constant temperature area of a box-type atmosphere furnace, placing the blank in a constant temperature area of a tube furnace, heating to 150 ℃ at a heating rate of 2 ℃/min under the protection of nitrogen, keeping the temperature for 3h, then continuing heating to 1000 ℃ and keeping the temperature for 3h, finally naturally cooling to room temperature, taking out a sample, crushing and sieving the sample to obtain the silicon-carbon composite negative electrode material with the median particle size D50 of 12.5 microns.
Example 5
Dissolving 10g of sucrose and 80g of ammonium bicarbonate in 120mL of water, stirring for 4h, adding 30g of 10 mu m graphite and 5g of nano silicon with the D50 of 100nm, stirring for 1h, drying in a spray drying device at the temperature of a discharge port of 110 ℃ to obtain a block, compacting the block into a blank by a film pressing forming device at the pressure of 15mPa, and maintaining the pressure for 5 min. And placing the blank in a constant temperature area of a box-type atmosphere furnace, placing the blank in a constant temperature area of a tube furnace, heating to 150 ℃ at a heating rate of 2 ℃/min under the protection of nitrogen, keeping the temperature for 3h, then continuously heating to 1000 ℃, keeping the temperature for 3h, and finally naturally cooling to room temperature and sieving to obtain the silicon-carbon composite negative electrode material.
Example 6
10g of sucrose and 70g of ammonium bicarbonate are dissolved in 120mL of water and stirred for 4h, then 24g of 10 mu m graphite and 4.5g of nano silicon with the D50 of 50nm are added, stirred for 1h, placed in spray drying equipment for drying, the temperature of a discharge port is 120 ℃, a block-shaped body is obtained, the block-shaped solid is compacted into a blank body by film pressing forming equipment, the pressure is 10mPa, and the pressure is maintained for 3 min. And placing the blank in a constant temperature area of a box-type atmosphere furnace, placing the blank in a constant temperature area of a tube furnace, heating to 150 ℃ at a heating rate of 2 ℃/min under the protection of nitrogen, keeping the temperature for 3h, then continuing heating to 1000 ℃ and keeping the temperature for 3h, finally naturally cooling to room temperature, taking out a sample, crushing and sieving the sample to obtain the silicon-carbon composite negative electrode material with the median particle size D50 of 12.5 microns.
Comparative example 1
1g of sucrose is dissolved in 30mL of deionized water and stirred for 30 minutes, then graphite with the particle size of 10 μm of 3g D50 and nano silicon with the particle size of 50nm of 0.5g of D50 are added and stirred for 1 hour, and then the mixture is placed in a forced air drying oven and dried for 12 hours at the temperature of 90 ℃ to obtain a block body. And placing the block-shaped body in a constant temperature area of a tubular furnace, heating to 1000 ℃ at a heating rate of 2 ℃/min, preserving heat for 3 hours, naturally cooling to room temperature, taking out a sample, crushing and sieving the sample to obtain the silicon-carbon negative electrode material, wherein the median particle size is 12.5 mu m.
The electrochemical cycle performance test is carried out on the silicon-carbon composite anode materials prepared in the examples 1-6 and the comparative example 1, and the specific steps are as follows: taking the materials prepared in the examples 1-6 and the comparative example 1 as negative electrode materials, mixing the negative electrode materials with a conductive agent (Super-P) and a binder sodium carboxymethyl cellulose (CMC) according to a mass ratio of 90: 6: 4, adding a proper amount of purified water as a dispersing agent to prepare slurry, coating the slurry on a copper foil, and preparing a negative electrode sheet through vacuum drying and rolling; the positive electrode is a metal lithium sheet, an electrolyte mixed by EC, DMC and EMC of 1: 1(v/v) is used in 1mol/L LiPF 6 three-component mixed solvent, a polypropylene microporous membrane is used as a diaphragm, and the CR2025 type button cell is assembled in a German Braun inert gas glove box system limited company MB200B type glove box filled with argon. Charge and discharge tests of the button cell on the Shanghai Chenghua CHI760E battery test system, constant current charge and discharge are carried out at 1C under normal temperature conditions, and the charge and discharge voltage is limited to 0.005-1.5V.
The electrochemical test results of the silicon-carbon composite negative electrode materials prepared in examples 1 to 6 and comparative example 1 are shown in table 1.
TABLE 1
The results in Table 1 show that the material prepared by the method has excellent cycling stability and rate capability, the charging specific capacity under the current density of 1C is 625.35mAh/g, the charging specific capacity after 300 cycles is 531.59mAh/g, and the capacity retention rate reaches 85.01%. In the silicon-carbon composite material prepared by the method, the graphene prepared by the gas pressure generated by the blowing agent is beneficial to improving the conductivity of the whole composite material, so that the de-intercalation depth of lithium ions, the first charge-discharge efficiency and the specific capacity are improved; in addition, the graphene can effectively inhibit the volume expansion of the nano silicon to avoid the structural collapse, so that the cycle life of the lithium ion battery is greatly prolonged; while comparative example 1 inhibits volume expansion only by the amorphous carbon-coated nano-silicon produced by glucose, the conductivity of the amorphous carbon is not high.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (15)
1. The preparation method of the silicon-carbon composite negative electrode material is characterized by comprising the following steps of:
dispersing a graphene precursor, a blowing agent, graphite and nano silicon into a solvent, uniformly mixing, and drying to obtain a solid material;
compacting the solid material obtained in the step one into a green body by using film pressing forming equipment;
step three, carrying out heat treatment on the blank obtained in the step two in the atmosphere of protective gas, and then sintering at high temperature to obtain a silicon-carbon composite anode material;
the pressure intensity of the film pressing forming equipment in the step two is 7-50 mPa; the temperature of the heat treatment in the third step is 160-180 ℃.
2. The preparation method according to claim 1, wherein in the first step, the graphene precursor, the blowing agent, the graphite and the nano-silicon are mixed in a weight ratio of (1-1.8): (7-18): (0.5-1.5): (5-12).
3. The preparation method according to claim 2, wherein in the first step, the weight ratio of the graphene precursor, the blowing agent, the graphite and the nano-silicon is (1-1.5): (7-15): (0.5-1): (5-10).
4. The preparation method according to claim 1, wherein the heat treatment in step three is carried out for 2-5 h;
the sintering temperature in the sintering process is 900-1200 ℃;
the sintering time in the sintering process is 2-5 h;
the protective gas is nitrogen or argon.
5. The preparation method according to claim 4, wherein the sintering temperature in the sintering process in the third step is 900-1100 ℃;
the sintering time in the sintering process is 2-4 h.
6. The preparation method according to claim 1, wherein the graphene precursor is 1 or a combination of more than 2 of sucrose, glucose, starch or pitch;
the asphalt is 1 or more than 2 of high-temperature asphalt, emulsified asphalt or low-temperature asphalt;
the blowing agent is 1 or the combination of more than 2 of ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium carbonate or ammonium bicarbonate;
the solvent is deionized water, alcohols, ethers, alkanes, ketones and aromatics.
7. The method according to claim 6, wherein the solvent is 1 or a combination of 2 or more selected from methanol, ethanol, N-butanol, ethylene glycol, isopropanol, acetone, N-methylpyrrolidone, N-hexane, cyclohexane, benzene, toluene, xylene, styrene, dichloromethane, trichloroethylene ethanol, dimethylformamide, dimethyl sulfoxide and tetrahydrofuran.
8. The method according to claim 1, wherein the drying method in the first step is 1 of freeze drying, vacuum drying or spray drying.
9. The preparation method according to claim 1, wherein the pressure of the film pressing and forming equipment in the second step is 8-20 mPa;
and the pressure maintaining time of the film pressing forming equipment is 1-10 min.
10. The preparation method according to claim 9, wherein the pressure of the film pressing and forming equipment in the second step is 8-10 mPa;
and the pressure maintaining time of the film pressing forming equipment is 2-8 min.
11. The preparation method of the silicon-carbon composite negative electrode material is characterized by comprising the following steps of:
adding a graphene precursor and a blowing agent into a solvent, stirring and mixing to form a uniform solution, then adding graphite and nano silicon into the solution, stirring and mixing, and drying to obtain a mixed material;
secondly, putting the mixed material obtained in the first step into film pressing forming equipment and compacting to obtain a blank;
and step three, placing the compacted blank in a sintering furnace, firstly heating to 150-180 ℃ at a heating rate of 0.5-10 ℃/min under the atmosphere of protective gas, keeping the temperature for 2-5 h, then continuously heating to 800-1800 ℃ at a heating rate of 0.5-10 ℃/min, sintering for 1-5 h, and naturally cooling to room temperature to obtain the silicon-carbon composite negative electrode material.
12. The silicon-carbon composite negative electrode material is characterized by being prepared by the method of any one of claims 1 to 11, and the silicon-carbon composite negative electrode material is of a core-shell structure, wherein a core is formed by compounding graphite and nano-silicon coated on the surface of the graphite, and a shell is formed by graphene and nano-silicon uniformly dispersed among graphene sheet layers.
13. The silicon-carbon composite anode material according to claim 12,
the content of the nano silicon distributed on the surface of the graphite is lower than 50%, and the content of the nano silicon embedded between graphene sheets is higher than 50%;
the graphite is 1 or more than 2 of artificial graphite, microcrystalline graphite or natural graphite;
the shape of the graphite is 1 of sheet, sphere or sphere;
the median particle diameter (D50) of the graphite is 8-18 μm;
the median particle diameter (D50) of the nano silicon is 5-170 nm;
the silicon-carbon composite negative electrode material contains 3-25 wt% of nano silicon, 1-10 wt% of graphene and 20-70 wt% of graphite;
the median particle size (D50) of the silicon-carbon composite negative electrode material is 8-20 μm;
the specific surface area of the silicon-carbon composite negative electrode material is 1-20 m2/g。
14. The silicon-carbon composite anode material according to claim 13,
the median particle diameter (D50) of the graphite is 8-12 μm;
the median particle diameter (D50) of the nano silicon is 30-130 nm;
the median particle size (D50) of the silicon-carbon composite negative electrode material is 13-15 μm;
the silicon carbonThe specific surface area of the composite negative electrode material is 1-12 m2/g。
15. A lithium ion battery comprising the silicon carbon composite anode material according to claims 12 to 14.
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