CN111180713B - Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof - Google Patents
Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof Download PDFInfo
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- CN111180713B CN111180713B CN202010084394.9A CN202010084394A CN111180713B CN 111180713 B CN111180713 B CN 111180713B CN 202010084394 A CN202010084394 A CN 202010084394A CN 111180713 B CN111180713 B CN 111180713B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
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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
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- 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
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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
- 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
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- 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 lithium ion battery cathode materials and electrochemistry, and particularly relates to a silicon-carbon cathode material for a lithium ion battery and a preparation method thereof, wherein the cathode material is of a core-shell structure, the core is nano-silicon, cracked carbon and a single-walled carbon nanotube, and the shell is a carbon coating layer formed by vapor deposition; the grain diameter of the nano silicon is 5-100 nm; the softening point of the cracking carbon is less than 300 ℃, and the carbon residue rate is more than 40%; the diameter of the single-walled carbon nano is 5-20 nm, preferably 5-10 nm; the length of the tube is 30-500 nm, preferably 30-100 nm, and the thickness of the carbon coating layer is 10-200 nm; the preparation method comprises the following steps: (1) The cracking carbon precursor and the single-walled carbon nanotube are homogeneously compounded; (2) nano-silicon CVD deposition in cracked carbon; (3) mechanically shaping; (4) carbon coating; the silicon-carbon cathode material prepared by the invention has the advantages of simple process, excellent performance and environmental friendliness.
Description
Technical Field
The invention belongs to the field of lithium ion battery cathode materials and electrochemistry, and particularly relates to a silicon-carbon cathode material for a lithium ion battery and a preparation method thereof.
Background
In recent years, with the development of science and technology and the improvement of living standard of people, people put forward higher demands on lithium ion batteries, such as longer service time, lighter weight and the like, but the theoretical specific capacity of the conventional graphite negative electrode material is only 372mAh/g at present, and the demand of high specific capacity batteries can not be met, so that the development of a high-performance novel electrode material becomes a research hotspot. Silicon has ultrahigh theoretical specific capacity (4200 mAh/g) and lower lithium removal potential (< 0.5V), and the voltage platform of silicon is slightly higher than that of graphite, so that surface lithium precipitation is difficult to cause during charging, and the safety performance is better. Therefore, developing a preparation method of the silicon-carbon anode material with simple process, excellent performance and environmental friendliness is an important research direction in the field of lithium ion batteries.
Disclosure of Invention
Aiming at the defects of the prior art, one of the purposes of the invention is to provide a silicon-carbon negative electrode material for a lithium ion battery, wherein the negative electrode material is of a core-shell structure, the core is nano-silicon, cracked carbon and a single-walled carbon nanotube, and the shell is a carbon coating layer formed by vapor deposition;
the grain diameter of the nano silicon is 5-100 nm;
the softening point of the cracking carbon is less than 300 ℃, and the carbon residue rate is more than 40%;
the pipe diameter of the single-wall carbon nano is 5-20 nm, preferably 5-10 nm; the length of the tube is 30-500 nm, preferably 30-100 nm;
the thickness of the carbon coating layer is 10-200 nm.
Preferably, the composite negative electrode material contains 40wt% -60 wt% of nano silicon, 20wt% -40 wt% of cracked carbon, 5wt% -15 wt% of single-walled carbon nanotubes and 10wt% -30 wt% of carbon coating layers.
More preferably, the median particle diameter of the negative electrode material is 5 to 10 μm; ratio table of the negative electrode materialThe area is 3 to 5m2(iv) g; the powder compaction density of the negative electrode material is 1.4-1.6 g/cm3。
The invention also relates to a preparation method of the silicon-carbon negative electrode material for the lithium ion battery, which is characterized by comprising the following steps of:
(1) Adding a dispersing agent into the single-walled carbon nanotube suspension, diluting until the solid content is 0.01-0.1%, adding a cracking carbon precursor, performing ultrasonic dispersion, and stirring and drying to obtain a silicon-carbon negative electrode material precursor 1;
(2) Placing the cathode material precursor 1 in the step (1) in a vapor deposition furnace (CVD furnace for short), introducing protective gas, introducing silicon source gas, heating to raise the temperature, and depositing nano silicon in cracking carbon to obtain a cathode material precursor 2;
(3) Mechanically shaping the cathode material precursor 2 in the step (2) to obtain a cathode material precursor 3 with concentrated particle size distribution and regular appearance;
(4) And (4) placing the cathode material precursor 3 in the step (3) in a vapor deposition furnace, introducing protective gas, introducing carbon source gas, heating to raise the temperature and form a carbon coating layer, and thus obtaining the silicon-carbon cathode material.
Preferably, the single-walled carbon nanotube suspension in the step (1) is an aqueous system or an N-methylpyrrolidone system; the pipe diameter of the single-walled carbon nanotube is 5-20 nm, preferably 5-10 nm; the length of the tube is 10-500 nm, preferably 30-100 nm; the mass ratio of the single-walled carbon nanotube in the slurry is 0.1-1%, preferably 0.5-0.8%; the dispersing agent is triethyl hexyl phosphoric acid, sodium dodecyl sulfate, methyl amyl alcohol, cellulose derivatives, polyacrylamide, guel gum, fatty acid polyglycol ester, polyvinylpyrrolidone, stearic acid monoglyceride, barium stearate or polyethylene glycol; the cracking carbon is 1 or at least 2 of asphalt, epoxy resin, phenolic resin, furfural resin, urea-formaldehyde resin and polyvinyl alcohol; the ultrasonic frequency is 50-100 kHz, and the ultrasonic time is 1-5 h.
Preferably, the specific process steps of the vapor deposition in the step (2) are as follows:
adding the cathode material precursor 1 obtained in the step (1) into an inner container of a vapor deposition furnace, introducing nitrogen to remove air until the oxygen content is lower than 100ppm, then heating to 600-900 ℃ at the heating rate of 1-5 ℃/min, roasting for 2-6 h, introducing organic silicon source gas for chemical vapor deposition for 1-5 h at the flow rate of 5-10L/min, and then sintering at constant temperature for 2-4 h to uniformly deposit nano silicon on the cathode material precursor 1 to obtain a cathode material precursor 2;
the organic silicon source gas is one or the combination of more than two of silane, dichlorosilane, trichlorosilane, silicon tetrachloride and silicon tetrafluoride;
the protective gas is one or the combination of more than two of nitrogen, helium, neon and argon.
Preferably, the mechanical shaping in step (3) comprises crushing, grading and fusing, and the specific process steps are as follows:
and (3) treating the anode material precursor 2 obtained in the step (2) by a grinder, adjusting the strength of a main machine to be 30-50 Hz, adjusting the classification strength to be 30-50 Hz, controlling the granularity D50 to be 5-10 mu m, removing fine powder by classification, adding the powder into a fusion machine, adjusting the rotating speed to be 500-1000 rpm, adjusting the width of a cutter gap to be 0.05-1 cm, preferably 0.4-1 cm, fusing for at least 0.5h, and obtaining an anode material precursor 3 with centralized particle size distribution and regular appearance.
Preferably, the temperature rise rate of the vapor deposition process in the step (4) is 1 to 3 ℃/min, the carbon deposition temperature is 600 to 900 ℃, the flow rate of the organic carbon source gas is 1 to 5L/min, and the reaction duration is 1 to 4h.
The organic carbon source gas is one or the combination of more than two of methane, ethane, acetylene, natural gas and liquefied petroleum gas;
the protective gas is one or the combination of more than two of nitrogen, helium, neon and argon.
The invention also relates to a lithium ion battery, which is characterized in that the lithium ion battery cathode material is any one of the silicon-carbon cathode materials for the lithium ion battery
The silicon-carbon anode material designed by the invention has high specific capacity, excellent cycle performance, high-rate charge-discharge performance (the cycle capacity retention rate is more than 94% after 500 times) and primary efficiency (more than 93%), and is simple in preparation process, low in cost and suitable for industrialization.
Drawings
The invention is further described below with reference to the accompanying drawings.
Fig. 1 is a schematic structural diagram of a silicon carbon negative electrode material prepared in example 1.
1 is a carbon coating layer formed by vapor deposition; 2 is nano silicon; 3 is cracked carbon; 4 single-walled carbon nanotubes.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
A preparation method of a silicon-carbon negative electrode material for a lithium ion battery comprises the following steps:
(1) Adding a dispersing agent into a suspension of single-walled carbon nanotubes, wherein the single-walled carbon nanotubes are an N-methylpyrrolidone system, the pipe diameter is 5-10 nm, the pipe length is 30-100 nm, the mass is 100g, the mass percentage of the single-walled carbon nanotubes in the suspension is 0.1%, the dispersing agent is sodium dodecyl sulfate, the mass is 5g, then diluting the suspension with N-methylpyrrolidone until the mass content of the single-walled carbon nanotubes is 0.01%, uniformly stirring, adding domestic asphalt, the softening point of the asphalt is 230 ℃, the carbon residue rate is 63%, the mass is 500g, starting ultrasonic dispersion, the ultrasonic frequency is 100KHz, the ultrasonic time is 5h, slowly stirring, and drying to obtain a silicon carbon negative electrode material precursor 1;
(2) Adding the cathode material precursor 1 in the step (1) into an inner container of a vapor deposition furnace, introducing nitrogen to remove air until the oxygen content is lower than 100ppm, then heating to 900 ℃ at a heating rate of 1 ℃/min, roasting for 6h, introducing silane gas for chemical vapor deposition for 5h with the flow of 5L/min, then sintering at constant temperature for 4h to uniformly deposit nano-silicon on the cathode material precursor 1, and controlling the mass of the nano-silicon to be 400g to obtain a cathode material precursor 2;
(3) Treating the anode material precursor 2 obtained in the step (2) by a grinder, adjusting the intensity of a main machine to be 50Hz, adjusting the classification intensity to be 50Hz, controlling the granularity D50 to be 5 +/-1 mu m, removing fine powder by classification, adding the powder into a fusion machine, adjusting the rotating speed to be 1000rpm, adjusting the cutter gap width to be 0.05cm, fusing for 1h, and obtaining an anode material precursor 3 with centralized granularity distribution and regular appearance;
(4) And (3) placing the cathode material precursor 3 in the step (3) in a vapor deposition furnace, introducing nitrogen to remove air until the oxygen content is lower than 200ppm, then heating to 900 ℃ at the heating rate of 3 ℃/min, introducing methane to perform vapor deposition for 1h, controlling the reaction time to be 4h, and forming a uniform carbon coating layer with the mass ratio of 10wt% to be uniform to obtain the silicon-carbon cathode material.
Example 2
A preparation method of a silicon-carbon negative electrode material for a lithium ion battery comprises the following steps:
(1) Adding a dispersing agent into a single-walled carbon nanotube suspension, wherein the single-walled carbon nanotube is an N-methylpyrrolidone system, the pipe diameter is 10-20 nm, the pipe length is 100-500 nm, the mass is 100g, the mass proportion of the single-walled carbon nanotube in the suspension is 0.1%, the dispersing agent is polyacrylamide, the mass is 5g, diluting the suspension with N-methylpyrrolidone until the mass content of the single-walled carbon nanotube is 0.03%, uniformly stirring, adding phenolic resin, the softening point of the phenolic resin is 180 ℃, the carbon residue rate is 51%, the mass is 600g, starting ultrasonic dispersion, the ultrasonic frequency is 80KHz, the ultrasonic time is 3h, slowly stirring, and drying to obtain a silicon carbon negative electrode material precursor 1;
(2) Adding the cathode material precursor 1 in the step (1) into an inner container of a vapor deposition furnace, introducing argon to remove air until the oxygen content is lower than 100ppm, then heating to 800 ℃ at a heating rate of 3 ℃/min, roasting for 4h, introducing trichlorosilane gas for chemical vapor deposition for 3h at a flow rate of 7L/min, then sintering at a constant temperature for 2h to uniformly deposit nano-silicon on the cathode material precursor 1, and controlling the mass of the nano-silicon to be 500g to obtain a cathode material precursor 2;
(3) Treating the anode material precursor 2 obtained in the step (2) by a grinder, adjusting the intensity of a main machine to 45Hz, adjusting the classification intensity to 45Hz, controlling the granularity D50 to be 7 +/-1 mu m, removing fine powder by classification, adding the powder into a fusion machine, adjusting the rotating speed to 800rpm, adjusting the cutter gap width to 0.1cm, fusing for 1h, and obtaining an anode material precursor 3 with centralized granularity distribution and regular appearance;
(4) And (3) placing the cathode material precursor 3 in the step (3) in a vapor deposition furnace, introducing argon to remove air until the oxygen content is lower than 100ppm, then heating to 800 ℃ at the heating rate of 2 ℃/min, introducing acetylene to carry out vapor deposition for 3h, controlling the reaction time to be 2h, and forming a uniform carbon coating layer with the mass ratio of 15wt% to be uniform, thereby obtaining the silicon-carbon cathode material.
Example 3
A preparation method of a silicon-carbon negative electrode material for a lithium ion battery comprises the following steps:
(1) Adding a dispersing agent into a suspension of single-walled carbon nanotubes, wherein the single-walled carbon nanotubes are water systems, the pipe diameters of the single-walled carbon nanotubes are 5-10 nm, the pipe lengths of the single-walled carbon nanotubes are 30-100 nm, the mass of the single-walled carbon nanotubes is 100g, the mass percentage of the single-walled carbon nanotubes in the suspension is 0.1%, the dispersing agent is polyvinylpyrrolidone, the mass of the polyvinylpyrrolidone is 5g, the suspension is diluted by pure water until the mass content of the single-walled carbon nanotubes is 0.07%, stirring uniformly, adding epoxy resin, the softening point of the epoxy resin is 140 ℃, the carbon residue rate of the epoxy resin is 47%, the mass of the epoxy resin is 700g, starting ultrasonic dispersion, the ultrasonic frequency is 60KHz, the ultrasonic time is 4h, slowly stirring, and drying to obtain a silicon carbon negative electrode material precursor 1;
(2) Adding the cathode material precursor 1 in the step (1) into an inner container of a vapor deposition furnace, introducing neon to remove air until the oxygen content is lower than 100ppm, then heating to 700 ℃ at a heating rate of 4 ℃/min, roasting for 3h, introducing silicon tetrachloride gas for chemical vapor deposition for 2h at a flow rate of 8L/min, then sintering at a constant temperature for 3h to uniformly deposit nano-silicon on the cathode material precursor 1, and controlling the mass of the nano-silicon to be 600g to obtain a cathode material precursor 2;
(3) Treating the anode material precursor 2 obtained in the step (2) by a grinder, adjusting the intensity of a main machine to 40Hz, adjusting the classification intensity to 40Hz, controlling the granularity D50 to be 8 +/-1 mu m, removing fine powder by classification, adding the powder into a fusion machine, adjusting the rotating speed to 700rpm, adjusting the cutter gap width to 0.4cm, fusing for 1h, and obtaining an anode material precursor 3 with centralized granularity distribution and regular appearance;
(4) And (3) placing the cathode material precursor 3 in the step (3) in a vapor deposition furnace, introducing nitrogen to remove air until the oxygen content is lower than 200ppm, then heating to 700 ℃ at the heating rate of 3 ℃/min, introducing methane to perform vapor deposition for 3h, controlling the reaction time to be 3h, and forming a uniform carbon coating layer with the mass ratio of 20wt% to be uniform to obtain the silicon-carbon cathode material.
Example 4
A preparation method of a silicon-carbon negative electrode material for a lithium ion battery comprises the following steps:
(1) Adding a dispersing agent into a suspension of single-walled carbon nanotubes, wherein the single-walled carbon nanotubes are water systems, the pipe diameter is 10-20 nm, the pipe length is 100-500 nm, the mass is 100g, the mass percentage of the single-walled carbon nanotubes in the suspension is 0.8%, the dispersing agent is barium stearate, the mass is 5g, the suspension is diluted by pure water until the mass content of the single-walled carbon nanotubes is 0.1%, stirring uniformly, adding furfural resin, the softening point of the furfural resin is 120 ℃, the residual carbon rate is 47%, the mass is 800g, starting ultrasonic dispersion, the ultrasonic frequency is 50KHz, the ultrasonic time is 1h, slowly stirring, and drying to obtain a silicon carbon negative electrode material precursor 1;
(2) Adding the cathode material precursor 1 in the step (1) into an inner container of a vapor deposition furnace, introducing helium gas to remove air until the oxygen content is lower than 100ppm, heating to 600 ℃ at a heating rate of 3 ℃/min, roasting for 4h, introducing silicon tetrafluoride gas for chemical vapor deposition for 1h at a flow rate of 10L/min, then sintering at a constant temperature for 2h to uniformly deposit nano silicon on the cathode material precursor 1, and controlling the mass of the nano silicon to be 700g to obtain a cathode material precursor 2;
(3) Treating the anode material precursor 2 obtained in the step (2) by a grinder, adjusting the strength of a main machine to be 30Hz, adjusting the classification strength to be 30Hz, controlling the granularity D50 to be 10 +/-1 mu m, removing fine powder by classification, adding the powder into a fusion machine, adjusting the rotating speed to be 500rpm, adjusting the cutter gap width to be 1cm, fusing for 1h, and obtaining an anode material precursor 3 with centralized granularity distribution and regular appearance;
(4) And (4) placing the cathode material precursor 3 in the step (3) in a vapor deposition furnace, introducing helium gas to remove air until the oxygen content is lower than 100ppm, heating to 600 ℃ at the heating rate of 3 ℃/min, introducing natural gas to perform vapor deposition for 1h at the flow rate of 5L/min, and controlling the reaction time to be 2h to form a uniform carbon coating layer with the mass ratio of 30wt%, so as to obtain the silicon-carbon cathode material.
Comparative example 1
The difference from example 1 is that no cracked carbon precursor is added in step (1), and the rest is the same as example 1, and will not be described herein.
Comparative example 2
The difference from example 1 is that the cracking carbon precursor added in step (1) is sucrose, and the carbon residue rate is 8%, and the rest is the same as example 1, and the description is omitted here.
Comparative example 3
The difference from example 1 is that the precursor of the cracking carbon added in step (1) is glucose, and the carbon residue rate is 5%, and the rest is the same as example 1, and the description is omitted here.
Comparative example 4
The difference from embodiment 1 is that in step (2), a silicon source is not introduced by a vapor deposition method, but nano silicon dry powder is directly and uniformly mixed with the silicon-carbon anode material precursor 1, which is the same as embodiment 1 and is not described herein again.
Comparative example 5
The difference from example 1 is that the mechanical shaping in step (3) controls the particle size D50 to be 15-30 μm, and the fine powder is not removed by classification, and the description is omitted as in example 1.
Comparative example 6
The difference from example 1 is that the carbon coating layer in step (4) is not prepared by vapor deposition method, but is solid phase mixed coating, and the rest is the same as example 1, and will not be described again here.
Mixing and dissolving a negative electrode material, a conductive agent and a binder in a solvent according to a mass ratio of 93; then, a ternary positive pole piece prepared by a traditional mature process, 1mol/L LiPF6/EC + DMC + EMC (v/v = 1. On a LanD battery test system of Wuhanjinnuo electronics Co Ltd, the charge and discharge performance of the prepared cylindrical battery is tested, and the test conditions are as follows: and (3) charging and discharging at constant current of 0.2C at normal temperature, wherein the charging and discharging voltage is limited to 3.2V-4.3V.
The test results are shown in table 1:
table 1 results of performance testing of examples and comparative examples:
as shown in Table 1, the core-shell structure silicon-carbon anode material prepared by the method greatly improves the comprehensive performance of the anode material through various functional components, and has high compaction density (1.47-1.53 g/cm)3) Low specific surface area (3.2-4.4 m)2And/g), the discharge capacity can be more than 1700mAh/g, the first coulombic efficiency can be more than 89%, and the capacity retention rate can reach more than 91% after 300 cycles. Compared example 1, the first coulombic efficiency and the cycle performance of the negative electrode material are obviously reduced without adding the cracking carbon precursor and the low-carbon-residue-rate carbon source in the compared examples 2 and 3, the inventory efficiency is less than 83%, and the capacity retention rate after 300 cycles is less than 74%; comparative example 4, instead of introducing a silicon source by a vapor deposition method, nano silicon dry powder is directly and uniformly mixed with the silicon-carbon anode material precursor 1, and the obtained anode material powder is compacted, the specific surface area and the first reversible capacity are close to those of example 1, but the first coulombic efficiency is only 78.6%, and the cycle performance is also obviously reduced, only 82.7%; comparative example 5, in which the grain size controlled by mechanical shaping was too large, D50 was 15 to 30The obtained negative electrode material powder is more excellent in compacted specific surface area and first reversible capacity, which is similar to that of the negative electrode material powder in example 1, but the first coulombic efficiency is only 72.3%, and the capacity retention rate after 300 cycles is low and is 85.8%; in comparative example 5, the carbon coating layer is not prepared by a vapor deposition method, but is coated by solid phase mixing, and the powder compaction, specific surface area, first reversible capacity and first coulombic efficiency of the obtained negative electrode material are similar to those of example 1, but the capacity retention rate is lower after 300 weeks of circulation, and is only 82.6%.
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 (3)
1. A silicon-carbon cathode material for a lithium ion battery is characterized in that the cathode material is of a core-shell structure, the core is nano silicon, cracked carbon and a single-walled carbon nanotube, and the shell is a carbon coating layer formed by vapor deposition;
the grain diameter of the nano silicon is 5-100 nm;
the pipe diameter of the single-wall carbon nano is 5 to 20nm; the length of the tube is 30 to 500nm;
the thickness of the carbon coating layer is 10-200 nm;
the composite cathode material contains 40-60 wt% of nano silicon, 20-40 wt% of cracked carbon, 5-15 wt% of single-walled carbon nanotubes and 10-30 wt% of carbon coating;
the median particle size of the negative electrode material is 5-10 mu m; the specific surface area of the negative electrode material is 3-5 m2(iv) g; the powder compaction density of the negative electrode material is 1.4-1.6 g/cm3；
The preparation method of the anode material comprises the following steps:
(1) Adding a dispersing agent into the single-walled carbon nanotube suspension, diluting until the solid content is 0.01-0.1%, adding a cracking carbon precursor, performing ultrasonic dispersion, and stirring and drying to obtain a silicon-carbon negative electrode material precursor 1;
(2) Placing the cathode material precursor 1 in the step (1) in a vapor deposition furnace, introducing protective gas, introducing silicon source gas, heating, and depositing nano silicon in cracking carbon to obtain a cathode material precursor 2;
(3) Mechanically shaping the cathode material precursor 2 in the step (2) to obtain a cathode material precursor 3 with concentrated particle size distribution and regular appearance;
(4) Placing the cathode material precursor 3 in the step (3) in a vapor deposition furnace, introducing protective gas, introducing carbon source gas, heating to form a carbon coating layer, and obtaining a silicon-carbon cathode material;
the single-walled carbon nanotube suspension in the step (1) is a water system or an N-methylpyrrolidone system; the mass ratio of the single-walled carbon nanotube in the suspension is 0.1 to 1 percent; the dispersing agent is triethyl hexyl phosphoric acid, sodium dodecyl sulfate, methyl amyl alcohol, cellulose derivatives, polyacrylamide, guel gum, fatty acid polyglycol ester, polyvinylpyrrolidone, stearic acid monoglyceride, barium stearate or polyethylene glycol; the cracking carbon precursor is 1 or at least 2 of asphalt, epoxy resin, phenolic resin, furfural resin, urea resin and polyvinyl alcohol; the ultrasonic frequency is 50 to 100kHz, and the ultrasonic time is 1 to 5h;
the vapor deposition process in the step (2) comprises the following specific steps:
adding the cathode material precursor 1 obtained in the step (1) into an inner container of a vapor deposition furnace, introducing protective gas to remove air until the oxygen content is lower than 100ppm, then heating to 600-900 ℃ at the heating rate of 1-5 ℃/min, roasting for 2-6 h, introducing organic silicon source gas for chemical vapor deposition for 1-5 h at the flow rate of 5-10L/min, and then sintering at constant temperature for 2-4 h to uniformly deposit nano silicon on the cathode material precursor 1 to obtain a cathode material precursor 2;
the organic silicon source gas is one or the combination of more than two of silane, dichlorosilane, trichlorosilane, silicon tetrachloride and silicon tetrafluoride;
the protective gas is one or the combination of more than two of nitrogen, helium, neon and argon;
the mechanical shaping in the step (3) comprises crushing, grading and fusion, and the specific process steps are as follows:
treating the anode material precursor 2 obtained in the step (2) by a pulverizer, adjusting the strength of a main machine to be 30-50 Hz, adjusting the classification strength to be 30-50Hz, controlling the granularity D50 to be 5-10 μm, removing fine powder by classification, adding the powder into a fusion machine, adjusting the rotation speed to be 500-1000 rpm, adjusting the cutter gap width to be 0.05-1 cm, fusing for at least 0.5h, and obtaining an anode material precursor 3 with centralized granularity distribution and regular appearance;
the temperature rise rate of the vapor deposition process in the step (4) is 1-3 ℃/min, the carbon deposition temperature is 600-900 ℃, the flow of the organic carbon source gas is 1-5L/min, and the reaction duration is 1-4 h;
the organic carbon source gas is one or the combination of more than two of methane, ethane, acetylene, natural gas and liquefied petroleum gas;
the protective gas is one or the combination of more than two of nitrogen, helium, neon and argon.
2. The silicon-carbon negative electrode material for the lithium ion battery according to claim 1, wherein: the pipe diameter of the single-wall carbon nano is 5-10nm; the length of the tube is 30 to 100nm; the mass ratio of the single-walled carbon nanotube in the suspension is 0.5 to 0.8 percent; the width of the cutter gap of the fusion machine is 0.4-1 cm.
3. A lithium ion battery, characterized in that the negative electrode material of the lithium ion battery is the silicon-carbon negative electrode material for lithium ion batteries according to claim 1 or 2.
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