CN108232141B - High-compaction lithium ion battery silicon-carbon composite negative electrode material and preparation method thereof - Google Patents
High-compaction lithium ion battery silicon-carbon composite negative electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-compaction lithium ion battery silicon-carbon composite negative electrode material and a preparation method thereof. The silicon-carbon composite material is a sheet structure consisting of a silicon-based material and a carbon material. The preparation method comprises the following steps: uniformly mixing a silicon-based material, a carbon material, a surfactant and an adhesive, adding a solvent, and carrying out ball milling to obtain uniformly dispersed slurry; drying the slurry to remove the solvent, and then pyrolyzing the slurry at high temperature under the protection of inert atmosphere; the obtained black powder was subjected to surface coating treatment and pyrolysis. The silicon-carbon composite material provided by the invention has high specific capacity, excellent cycle performance and compaction performance when being used as a lithium ion battery cathode material, and the preparation method provided by the invention is simple and easy to regulate and control, and is beneficial to industrial production.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a high-compaction silicon-carbon composite negative electrode material, a preparation method thereof, a battery negative electrode containing the silicon-carbon composite material and a lithium ion battery.
Background art:
the lithium ion battery has the advantages of high specific capacity, high energy density and power density, no self-discharge, environmental protection and the like, and thus, the lithium ion battery becomes a hot spot of scientific research and industrial development at present. With the rapid development in the fields of portable electronic products, electric vehicles, energy storage power stations, and the like, performance indexes of lithium ion batteries, such as energy density, power density, cycle life, and the like, need to be further improved. At present, the cathode material in the commercial lithium ion battery is mainly a graphite material, and the theoretical capacity of the graphite material is 372mAh/g, so that the further improvement of the energy density of the lithium ion battery is limited. Therefore, the development of high capacity negative electrode materials is a key to solving energy problems in today's society.
Novel high specific capacity negative electrode materials represented by silicon-based materials have received much attention. The silicon-based negative electrode material has high lithium storage capacity and a lower voltage platform, and is an ideal negative electrode material of a next-generation lithium ion battery. However, the silicon-based material has a huge volume expansion rate (> 300%) and low electrical conductivity during lithium deintercalation, and the coulombic efficiency of the first turn is very low, so that the silicon-based material has not been widely used so far. The current solution is to compound silicon-based materials with carbon materials to improve the conductivity and cycling stability of the materials: the carbon material has high conductivity and good compatibility with conventional electrolyte, and the silicon-based material is uniformly dispersed in the carbon material, so that the overall conductivity of the composite material can be obviously improved; the silicon-based material is uniformly dispersed in the carbon material, and the carbon material can effectively buffer the volume expansion of the silicon-based material, so that the overall volume expansion rate of the composite material is reduced, and the circulation stability of the composite material is improved. Therefore, the compounding of the silicon-based material and the carbon material is widely researched, but the development of the silicon-carbon composite material which is low in cost, can be prepared in a large scale and is resistant to high compaction is still a technical problem in the field on the premise of not influencing the capacity exertion.
CN103123967A discloses a SiO/C composite negative electrode material of a lithium ion battery and a preparation method thereof, and the steps comprise: uniformly dispersing graphite, ethyl orthosilicate and polyvinylpyrrolidone in a solvent; adjusting the pH value to 8-9, removing the solvent, and pyrolyzing the mixture in an inert atmosphere; and mixing an ethanol solution of citric acid with the product, performing ball milling, and performing pyrolysis in an inert atmosphere to obtain the SiO/C composite negative electrode material. According to the invention, liquid ethyl orthosilicate is used as a silicon source, so that silicon oxide generated by hydrolysis can be uniformly dispersed in graphite, and a carbon source is introduced by thermally hydrolyzing an ethanol solution of citric acid, so that the defects of poor cycle stability and high calcination temperature of the conventional SiO/C composite negative electrode material are overcome, and the SiO/C composite negative electrode material of the lithium ion battery with high specific capacity and good cycle stability and the preparation method thereof are provided. But the method requiresThe steps of removing the solvent and pyrolyzing under inert atmosphere are repeated, the operation process is complicated, simultaneously, the method takes tetraethoxysilane as a silicon source, the oxygen content of the hydrolysate is not easy to control, and the commercialization is not facilitated. CN103022446A discloses a silicon oxide/carbon negative electrode material of a lithium ion battery and a preparation method thereof, the silicon oxide/carbon negative electrode material of the lithium ion battery disclosed by the invention is a three-layer composite material with a core-shell structure, a graphite material is adopted as an inner core, porous silicon oxide is adopted as an intermediate layer, and organic pyrolytic carbon is an outermost coating layer; the preparation method comprises the steps of preparing porous SiOxThe preparation and carbon coating process; however, this method requires the addition of a reactive metal to reduce a portion of SiOxAlthough the obtained product structure can perform self-absorption on the volume expansion effect of silicon particles in the charging and discharging processes, the introduction of active metal can greatly reduce the mass specific capacity of the material, and simultaneously improve the overall activity of the material, so that the preparation difficulty is increased, and the commercialization is difficult. CN105655564A discloses SiO with core-shell structurex/C composite material and preparation method thereof, SiO in the inventionxThe surface of the particle is provided with an amorphous conductive carbon layer, and free space is arranged among the silicon-carbon composite material particles, so that huge volume expansion generated in the charging and discharging process can be buffered, and the cycle performance of the material is improved. However, the preparation of the material requires the formation of SiOxThe surfaces of the particles are coated with amorphous conductive carbon layers in the environment of organic carbon source gas, hydrogen and inert gas, and the method has low efficiency and high requirement on equipment and is not suitable for large-scale preparation; the material disclosed by the invention is of a core-shell structure with gaps, and when the material is used as a negative electrode material with high compaction density, the original appearance is difficult to maintain, and the cycle performance is poor.
The flaky silicon-carbon composite negative electrode material is prepared by a method of secondary granulation and surface coating of a silicon-based material and a carbon material. Compared with other preparation methods, the method is simple and efficient, the obtained flaky material has a stable structure, the original shape of the material can be kept without being broken under a high-pressure physical system, the material has better cycle performance and compaction performance, and the rate capability of the flaky material is more excellent. When used as the negative electrode material of lithium ion batteryEven at 1.5g/cm3Still shows high charge-discharge capacity and excellent cycle and rate performance under the high compact density condition.
Disclosure of Invention
The invention aims to solve the problem that the existing silicon-based composite material is poor in cycle performance and compaction performance, and provides a high-compaction silicon-carbon composite negative electrode material and a preparation method thereof, so that the cycle life and the energy density of the current lithium ion battery negative electrode material are prolonged.
In order to achieve the above object, the present invention provides a method for preparing a high-compaction silicon-carbon composite anode material, comprising the following steps:
1) mixing and ball-milling a silicon-based material, poly (diallyldimethylammonium chloride) and water, and combining the silicon-based material and the poly (diallyldimethylammonium chloride) to obtain slurry A with positive charges on the surfaces of silicon-based material particles;
2) mixing and ball-milling a carbon material, a surfactant and water to obtain slurry B with negative charges on the surface of the carbon material;
3) mixing the slurry A and the slurry B, adding an adhesive, performing ball milling, adding a proper amount of water, adjusting to a proper solid content, and performing spray drying to obtain black powder;
4) and (3) performing high-temperature pyrolysis on the black powder, performing surface coating treatment, and performing pyrolysis to obtain the high-compaction lithium ion battery silicon-carbon composite negative electrode material.
In the step (1), the silicon-based material is one or more of amorphous silicon, silicon oxide, silicon nanoparticles, a silicon thin film, a silicon nanotube, a silicon nanowire, porous silicon and hollow silicon, preferably one or more of amorphous silicon, silicon oxide, silicon nanoparticles and porous silicon.
In the step (1), the molecular weight of the polydiallyldimethylammonium chloride is 50000-300000, preferably 100000-200000.
In step (1), the solid content of the slurry A is 15 to 30%, preferably 20 to 25%.
In the step (2), the carbon material is one or more of mesocarbon microbeads, hard carbon, soft carbon, crystalline graphite, graphene, carbon nanotubes and acetylene black, and preferably one or more of crystalline graphite, graphene, mesocarbon microbeads and acetylene black.
In the step (2), the surfactant is an anionic surfactant and a nonionic surfactant, such as a combination of sodium dodecyl sulfate and polyvinylpyrrolidone, a combination of sodium dodecyl sulfate and polyethylene glycol, a combination of anionic polyacrylamide and polyvinylpyrrolidone, a combination of anionic polyacrylamide and polyethylene glycol, preferably a combination of sodium dodecyl sulfate and polyvinylpyrrolidone, and a combination of anionic polyacrylamide and polyethylene glycol.
In the step (2), the solid content of the slurry B is 15 to 30%, preferably 20 to 25%.
In the step (3), the binder is one or more of asphalt, phenolic resin, chitosan, sucrose, glucose, starch and polyfurfuryl alcohol, preferably one or more of asphalt, phenolic resin and chitosan.
In step (3), the solid content is 10 to 20%, preferably 14 to 18%.
In the step (3), the content of the silicon-based material in the mixed slurry is 10-40 wt%.
In the steps (1) to (3), the ball milling is planetary high-energy ball milling, and the diameter of the zirconia ball is 0.1-10 mm.
In the steps (1) - (3), the rotation speed of the ball mill is 800r/min, preferably 600r/min, of 300-.
In the steps (1) to (2), the ball milling time is 0.5 to 2 hours, preferably 1 to 1.5 hours.
In the step (3), the ball milling time is 2-6h, preferably 3-5 h.
In the step (3), the spray drying is centrifugal spray drying, and the rotating speed is 10000-30000r/min, preferably 18000-26000 r/min.
In the step (3), the temperature of the spray drying air inlet is 160-300 ℃, preferably 180-250 ℃, the temperature of the spray drying discharge outlet is 80-120 ℃, preferably 90-100 ℃, and the evaporation capacity of the solvent is 20-60L/h, preferably 30-50L/h.
In the step (4), the pyrolysis temperature is 600-1200 ℃, and preferably 800-1000 ℃;
in the step (4), the pyrolysis temperature rise speed is 0.5-10 ℃/min, preferably 1-8 ℃/min.
In the step (4), the thermal insulation time of the pyrolysis is 2-8h, preferably 3-6 h.
In the step (4), the pyrolysis equipment is one of an atmosphere box furnace, a rotary furnace, a tube furnace or a pushed slab kiln.
In the step (4), the pyrolysis is performed under the protection of an inert atmosphere, wherein the inert atmosphere is one or a combination of nitrogen, argon and helium.
In the step (4), the surface coating method comprises a solid phase coating method and a gas phase coating method; the coating agent of the solid phase coating method is one or more of coal pitch, petroleum pitch, needle coke or petroleum coke; the gas phase coating method is a chemical vapor deposition method, and the coating agent is one or two of acetylene or methane.
In the step (4), the solid-phase coating equipment is a solid-phase coating machine; the vapor phase coating equipment is a CVD chemical vapor deposition furnace.
In the step (4), the amount of the solid-phase coated coating agent is 5-20 wt%, preferably 8-15 wt% of the mass of the composite material.
In the step (4), the coating layer coated on the surface is amorphous carbon; the thickness of the coating layer is 10-300 nm.
In the step (4), the mass flow rate of the gas phase coating gas is 20-1000sccm, preferably 100-600 sccm.
The invention also provides a high-compaction silicon-carbon composite negative electrode material prepared by the preparation method. The silicon-carbon composite material is a sheet structure consisting of a silicon-based material and a carbon material, wherein the silicon-based material is uniformly dispersed in the carbon material.
The application provided by the invention is the application of the high-compaction silicon-carbon composite material as the negative electrode material of the lithium ion battery, and the lithium ion battery contains the silicon-carbon composite negative electrode material provided by the invention or the silicon-carbon composite negative electrode material prepared by the preparation method provided by the invention.
Compared with the prior art, the preparation method of the silicon-carbon composite material has the advantages that: the preparation method is simple, the raw materials are easy to obtain, the preparation method is suitable for large-scale production, the practicability is high, the prepared silicon-carbon composite material is of a sheet structure, the structure is stable, the original shape of the material can be kept without being broken under a high-pressure entity system, the material has better cycle performance and compaction performance, and the rate capability of the sheet material is more excellent. When used as the negative electrode material of the lithium ion battery, the concentration of the organic acid is even 1.5g/cm3Still shows high charge-discharge capacity and excellent cycle and rate performance under the high compact density condition.
Drawings
Fig. 1 is a scanning electron microscope photograph of a highly compacted silicon-carbon composite anode material prepared in example 1 of the present invention.
Fig. 2 is a high-magnification scanning electron microscope photograph of the highly compacted silicon-carbon composite negative electrode material prepared in example 1 of the present invention.
Fig. 3 is a charge-discharge curve of the highly compacted silicon-carbon composite anode material prepared in example 1 of the present invention as an anode material of a lithium ion battery.
Fig. 4 is a cycle performance curve of the highly compacted silicon-carbon composite anode material prepared in example 1 of the present invention as an anode material of a lithium ion battery.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
The electrochemical properties of the highly compacted silicon-carbon composite anode materials prepared in the following examples and comparative examples were tested according to the following methods: mixing the prepared high-compaction silicon-carbon composite negative electrode material, carbon black and carboxymethyl cellulose (CMC) binder according to a mass ratio of 90: 5: 5, mixing to prepare slurry, uniformly coating the slurry on a copper foil current collector, and carrying out vacuum drying and rolling until the compaction density is 1.5g/cm3Preparing a working electrode; a button cell was assembled from a lithium metal foil as a counter electrode, a glass fiber membrane (available from Whatman, UK) as a separator, and 1mol/L LiPF6 (solvent is a mixture of ethylene carbonate and dimethyl carbonate in a volume ratio of 1: 1) as an electrolyte in a German Braun inert gas glove box under argon atmosphere.
And (3) carrying out charge and discharge tests on the assembled battery on a LAND charge and discharge tester.
Example 1
1kg of SiO with a particle size of 50-100 nmxUniformly mixing the particles, 200g of poly (diallyldimethylammonium chloride) and 5L of water by ball milling for 1h to obtain slurry A; simultaneously, 2kg of thin-layer crystalline flake graphite with the particle size of 1-10 um, 100g of sodium dodecyl sulfate, 200g of polyvinylpyrrolidone and 10L of water are milled for 1 hour and uniformly mixed to obtain slurry B; uniformly mixing the slurry A and the slurry B, adding 7.5L of water and 500g of asphalt, and ball-milling for 3 hours to obtain uniform slurry with the solid content of 15%; carrying out spray drying treatment on the obtained slurry to remove water; under the protection of nitrogen, heating to 900 ℃ at the heating rate of 2 ℃/min, and carrying out thermal insulation pyrolysis for 3 hours to obtain black powder; putting the black powder into a CVD coating furnace, introducing acetylene gas at the gas mass flow of 500sccm, and depositing for 3h at 900 ℃; and (3) placing the coated material under the protection of nitrogen, heating to 1000 ℃ at the heating rate of 3 ℃/min, preserving heat for 3h, and naturally cooling to obtain the flaky highly-compacted silicon-carbon composite negative electrode material.
The morphology of the composite material is analyzed by a scanning electron microscope (SEM, Japanese Electron scanning Electron microscope JEOL-6701F), and FIG. 1 is a scanning electron microscope photo of the prepared high-compaction silicon-carbon composite negative electrode material, wherein the composite material is flaky, the surface is compact, the particle size is uniform, and the particle size range is 5-20 um. FIG. 2 is a high-magnification scanning electron micrograph of the composite material, from which it can be seen that SiO in the composite materialxThe particles and the thin-layer flake graphite are uniformly distributed and fused into a whole.
Electrochemical analysis tests are carried out on the flaky high-compaction silicon-carbon composite negative electrode material obtained by the invention, and the results are shown in fig. 3. The charging and discharging interval is 0-2V, and the compaction density is 1.5g/cm3At a current density of 300mA/g (0.5C)The capacity of the material can reach 596.4mAh/g, the coulombic efficiency of the first circle is 88.2%, and the capacity retention rate of 50 circles of circulation is 97.9% (as shown in figure 4), so that the composite material obtained by the invention has higher capacity, excellent circulation performance and compaction performance. The test results of the obtained sheet-like highly compacted silicon-carbon composite anode material in a button cell are shown in table 2.
Example 2
The surfactant combination was changed from 100g of sodium lauryl sulfate and 200g of polyvinylpyrrolidone to 100g of anionic polyacrylamide and 200g of polyethylene glycol when preparing slurry B, and the other preparation steps were the same as in example 1. The results of the electrochemical performance tests of the obtained materials are shown in Table 2.
Comparative example 1
Slurry A was prepared without addition polymerization of diallyldimethylammonium chloride and the other preparation steps were the same as in example 1. The results of the electrochemical performance tests of the obtained materials are shown in Table 2.
Comparative example 2
The slurry B was prepared without adding the anionic surfactant sodium lauryl sulfate, and the other preparation steps were the same as in example 1. The results of the electrochemical performance tests of the obtained materials are shown in Table 2.
Comparative example 3
The preparation of slurry B was carried out in the same manner as in example 1 except that no nonionic surfactant, polyvinylpyrrolidone, was added. The results of the electrochemical performance tests of the obtained materials are shown in Table 2.
Comparative example 4
Slurry B was prepared without any surfactant, and the other preparation steps were the same as in example 1. The results of the electrochemical performance tests of the obtained materials are shown in Table 2.
Example 3
The binder pitch added when slurry a and slurry B were mixed was changed to a phenolic resin, and the other preparation steps were the same as in example 1. The results of the electrochemical performance tests of the obtained materials are shown in Table 2.
Example 4
The adhesive pitch added when slurry a and slurry B were mixed was changed to chitosan, and the other preparation steps were the same as in example 1. The results of the electrochemical performance tests of the obtained materials are shown in Table 2.
Comparative example 5
Slurry A and slurry B were mixed without the addition of a binder, and the other preparation steps were the same as in example 1. The results of the electrochemical performance tests of the obtained materials are shown in Table 2.
Example 5
The CVD gas phase coating is changed into the method of uniformly mixing black powder and 500g coal tar pitch and then adding the mixture into a solid phase coating machine for solid phase coating when the surface is coated, and other preparation steps are the same as the example 1. The results of the electrochemical performance tests of the obtained materials are shown in Table 2.
Comparative example 6
The other preparation steps were the same as in example 1, except that no surface coating was performed. The results of the electrochemical performance tests of the obtained materials are shown in Table 2.
TABLE 1 raw materials for examples and comparative examples
Note: PDDA is an English abbreviation for poly (diallyldimethylammonium chloride) used in the preparation of slurry A
TABLE 2 electrochemical performance test results of highly compacted Si-C composite negative electrode materials
In conclusion, the preparation method is simple and efficient, and the obtained sheet material is stable in structure, excellent in electrochemical performance and good in cycle performance under a high-pressure entity system.
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 (7)
1. A preparation method of a silicon-carbon composite negative electrode material of a high-compaction lithium ion battery comprises the following steps:
1) mixing and ball-milling a silicon-based material, poly (diallyldimethylammonium chloride) and water, and combining the silicon-based material and the poly (diallyldimethylammonium chloride) to obtain slurry A with positive charges on the surfaces of silicon-based material particles;
2) mixing and ball-milling a carbon material, a surfactant and water to obtain slurry B with negative charges on the surface of the carbon material;
3) mixing the slurry A and the slurry B, adding an adhesive, performing ball milling, adding a proper amount of water, adjusting to a proper solid content, and performing spray drying to obtain black powder;
4) carrying out high-temperature pyrolysis on the black powder, then carrying out surface coating treatment, and then carrying out pyrolysis to obtain the high-compaction lithium ion battery silicon-carbon composite negative electrode material;
the solid content of the slurry A in the step 1) is 20-25%;
in the step 2), the surfactant is a combination of sodium dodecyl sulfate and polyvinylpyrrolidone or a combination of anionic polyacrylamide and polyethylene glycol, and the solid content of the slurry B is 20-25%;
in the step 3), the adhesive is asphalt, and the solid content is 14-18%; the content of the silicon-based material in the mixed slurry is 10-40 wt%;
the silicon-based material is silicon oxide; the carbon material is flake graphite;
the silicon-carbon composite negative electrode material is a sheet structure composed of a silicon-based material and a carbon material, wherein the silicon-based material is uniformly dispersed in the carbon material.
2. The method of claim 1, wherein: the molecular weight of the polydiallyldimethylammonium chloride in the step (1) is 50000-300000.
3. The method of claim 1, wherein: the pyrolysis temperature of the high-temperature pyrolysis in the step (4) is 600-1200 ℃; the temperature rise speed of the high-temperature pyrolysis is 0.5-10 ℃/min; the pyrolysis time of the high-temperature pyrolysis is 2-8 h; the pyrolysis equipment for high-temperature pyrolysis is one of an atmosphere box furnace, a rotary furnace, a tube furnace or a pushed slab kiln.
4. The production method according to claim 3, characterized in that: the pyrolysis temperature of the high-temperature pyrolysis in the step (4) is 800-1000 ℃; the temperature rise speed of the high-temperature pyrolysis is 1-8 ℃/min; the pyrolysis time of the high-temperature pyrolysis is 3-6 h.
5. The method of claim 1, wherein: the surface coating method in the step (4) comprises a solid phase coating method and a gas phase coating method; the solid-phase coating equipment is a solid-phase coating machine; the gas phase coating equipment is a CVD chemical vapor deposition furnace; the coating agent of the solid phase coating method is one or more of coal pitch, petroleum pitch, needle coke or petroleum coke; the gas phase coating method is a chemical vapor deposition method, and the coating agent is one or more of acetylene, methane or gasified toluene.
6. The production method according to any one of claims 1 to 5, characterized in that: the particle size of the sheet structure is 1-50 μm, and the thickness is 0.1-3 μm.
7. The material prepared by the preparation method of any one of claims 1 to 6 is applied to serving as a negative electrode material of a lithium ion battery.
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| CN111384359A (en) * | 2018-12-28 | 2020-07-07 | 上高县荣炭科技有限公司 | Hard carbon substrate battery cathode structure with surface modification and preparation method thereof |
| CN110034289A (en) * | 2019-04-15 | 2019-07-19 | 南方科技大学 | A kind of silicon-carbon cathode material and preparation method thereof, cathode pole piece and lithium ion battery |
| CN110571425B (en) * | 2019-09-24 | 2020-10-27 | 中国科学院化学研究所 | Low-expansion-rate silicon-carbon composite material and preparation method thereof |
| CN112652742B (en) * | 2019-10-10 | 2022-07-12 | 中国石油化工股份有限公司 | Silicon-carbon composite material and preparation method and application thereof |
| CN111326723B (en) * | 2020-02-26 | 2021-11-05 | 博尔特新材料(银川)有限公司 | Silicon-carbon composite negative electrode material for lithium ion battery and preparation method thereof |
| CN112133893B (en) * | 2020-09-03 | 2021-11-16 | 深圳石墨烯创新中心有限公司 | Preparation method of silicon-carbon composite material for lithium ion battery and precursor thereof |
| CN112164780B (en) * | 2020-09-29 | 2022-05-31 | Oppo广东移动通信有限公司 | Silicon-based negative electrode material, preparation method thereof and related product |
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