CN113380991A - Silicon-carbon composite and preparation method thereof, negative electrode material, negative electrode plate, lithium ion battery and application thereof - Google Patents
Silicon-carbon composite and preparation method thereof, negative electrode material, negative electrode plate, lithium ion battery and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 32
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 108
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 107
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- 230000002349 favourable effect Effects 0.000 description 3
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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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- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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
- H01M4/36—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
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- 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
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Abstract
The invention discloses a silicon-carbon compound and a preparation method thereof, wherein sodium chloride template agent with small particle size is obtained by recrystallizing the sodium chloride template agent in the preparation process, so as to prepare the carbon-silicon compound with a unique double-layer carbon coating structure, wherein a first carbon coating layer uniformly coats the surface of silicon particles to form silicon-carbon particles with a core-shell structure, and the silicon-carbon particles are distributed in holes inside a second carbon coating layer; the carbon coating structure of the carbon-silicon composite improves the overall conductivity of the composite material, and simultaneously serves as a protective layer on the surface of silicon particles to inhibit side reactions between the silicon particles and electrolyte, so that the gram capacity and the cycle performance of the lithium ion battery silicon-carbon composite serving as a negative electrode material are improved.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to the field of preparation of lithium ion battery materials, and specifically relates to a silicon-carbon composite and a preparation method thereof, a negative electrode material, a negative electrode plate, a lithium ion battery and application thereof.
Background
Lithium ion batteries have been widely used in various fields, such as consumer electronics, electric vehicles, electric tools, energy storage power supplies, etc., due to their advantages of long cycle life, high energy density, etc.; with the continuous expansion of the application field, people also put higher requirements on the performance of the lithium ion battery. High specific energy, high power, low cost, long service life and high safety become targets of future development of lithium ion batteries, and the negative electrode of the lithium ion battery is an important component of the battery, and the structure and the performance of the negative electrode directly influence the capacity and the cycle performance of the battery. Research and development of negative electrode materials with good electrochemical properties are hot spots in the field of lithium ion battery research.
At present, most of commercial lithium ion batteries adopt graphite materials as negative electrodes, the theoretical specific capacity is only 372mAh/g, and the development requirements of the lithium ion batteries are difficult to meet. The theoretical specific capacity of the silicon is up to 4200mAh/g, and the silicon has wide source, low price and environmental protection, and is a potential lithium ion battery cathode material. However, silicon is easy to expand in volume during charging and discharging, resulting in electrode pulverization and dropping, and poor battery cycle performance. The composite structure design of silicon material is considered as one of the main approaches to improve the electrochemical performance, and the carbon material is the first choice due to the high conductivity and the diversity of the structure. However, various problems exist in the structure and the preparation method of the current silicon-carbon composite, and the published patent application No. cn201810783639.x is a preparation method and application of a lithium ion battery silicon-carbon composite negative electrode material with a porous structure, and the silicon-carbon composite material with the porous structure is prepared, wherein nano-silicon composite material is embedded in carbon pores, and although the structure can relieve the volume expansion of silicon in the circulation process to a certain extent, silicon particles are still exposed and are difficult to avoid direct contact with electrolyte.
Therefore, it is necessary to provide a silicon-carbon composite and a preparation method thereof, which are applied to a lithium ion battery to solve the above technical problems.
Disclosure of Invention
In view of the defects of the prior art, the main object of the present invention is to provide a silicon-carbon composite and a preparation method thereof, wherein the silicon-carbon composite is used as a lithium ion battery negative electrode material to prepare a negative electrode plate and a lithium ion battery, and the silicon-carbon composite utilizes a unique double-layer carbon coating structure thereof, so that the volume expansion of silicon in a circulation process can be effectively improved, the conductivity of the composite material is improved, the circulation performance of the lithium ion battery is improved, and the high specific capacity and the excellent circulation performance of the lithium ion battery are realized.
A silicon-carbon composite comprising silicon particles, a first carbon coating layer and a second carbon coating layer; the silicon-carbon composite material comprises a first carbon coating layer, a second carbon coating layer and a third carbon coating layer, wherein the first carbon coating layer uniformly coats the surfaces of silicon particles to form silicon-carbon particles with core-shell structures, the second carbon coating layer is internally provided with a porous communicated structure, the silicon-carbon particles are distributed in holes in the second carbon coating layer, and pores exist between the first carbon coating layer and the second carbon coating layer.
Preferably, the particle size of the silicon particles is 5-200nm, and the thickness of the first carbon coating layer is 1-30 nm.
The preparation method of the silicon-carbon composite comprises the following steps:
preparing a sodium chloride template agent, dissolving commercial sodium chloride in water to prepare a saturated sodium chloride solution, separating sodium chloride crystals from the saturated sodium chloride solution by using absolute ethyl alcohol, filtering, washing for multiple times by using absolute ethyl alcohol, and drying to obtain the sodium chloride template agent;
ball-milling and mixing, namely putting the sodium chloride template, the organic carbon source and the silicon particles into a ball-milling tank according to a ratio, adding absolute ethyl alcohol, carrying out ball-milling and mixing, and drying slurry after ball milling to obtain a mixed material;
performing heat treatment, namely carbonizing the mixed material at a constant temperature for 0.5-5 hours at a specific reaction temperature in an inert atmosphere, and cooling to obtain a heat treatment product;
and removing the sodium chloride template agent, dispersing the heat treatment product in deionized water, washing for multiple times until the conductivity of the solution is close to 0, and drying the obtained product to obtain the silicon-carbon composite.
Preferably, the grain size of the sodium chloride template is 1-10 μm.
The lithium ion battery negative electrode material comprises the silicon-carbon composite, and the silicon-carbon composite is prepared by the preparation method.
The negative plate of the lithium ion battery comprises a negative current collector and negative materials arranged on two sides of the negative current collector, wherein the negative materials comprise the silicon-carbon composite, and the silicon-carbon composite is prepared by the preparation method.
A lithium ion battery comprises a negative electrode material, wherein the negative electrode material comprises the silicon-carbon composite, and the silicon-carbon composite is prepared by the preparation method.
The lithium ion battery as described above is applied to electronic products, electric vehicles, or vehicles including automobiles, bicycles, motorcycles, and the like.
Compared with the prior art, the silicon-carbon composite and the preparation method thereof provided by the invention have the advantages that the sodium chloride template with small particle size is obtained by recrystallizing the sodium chloride template in the preparation process, so that the carbon-silicon composite with a special structure is prepared, and comprises silicon particles, a first carbon coating layer and a second carbon coating layer; the first carbon coating layer uniformly coats the surfaces of the silicon particles to form silicon-carbon particles with a core-shell structure, the second carbon coating layer is internally provided with a porous communicated structure, the silicon-carbon particles are distributed in holes in the second carbon coating layer, and pores are formed between the first carbon coating layer and the second carbon coating layer; the carbon-silicon composite adopts double-layer carbon coating to improve the overall conductivity of the composite material, and simultaneously, the carbon-silicon composite is used as a protective layer on the surface of silicon particles to inhibit side reactions between the carbon-silicon composite and electrolyte; in addition, the pores formed among the silicon-carbon particles and between the silicon-carbon particles and the second carbon coating layer provide buffer spaces for the volume expansion of the silicon particles in the charging and discharging processes, and are favorable for improving the cycle stability of the composite material; through the design, the improvement of gram capacity and cycle performance when the silicon-carbon composite of the lithium ion battery is used as a cathode material is realized, and a new idea of electrode design is developed; in addition, the sodium chloride template agent adopted in the preparation of the silicon-carbon composite is easy to recover, the source of the adopted organic carbon source is rich, and the preparation method has the advantages of simple process, strong controllability and the like, and has a large-scale industrial application prospect.
Drawings
FIG. 1 is a schematic structural diagram of a silicon-carbon composite of the present invention;
FIG. 2 is a schematic structural diagram of silicon-carbon particles in a silicon-carbon composite according to the present invention;
FIG. 3 is an XRD pattern of a silicon carbon composite prepared according to the present invention;
FIG. 4 is an SEM image of a silicon-carbon composite prepared according to the present invention;
FIG. 5 is a TEM image of a silicon-carbon composite prepared by the present invention;
FIG. 6 is an SEM image of a silicon-carbon composite prepared in comparative example 1;
FIG. 7 is an SEM image of a silicon-carbon composite prepared in comparative example 2;
FIG. 8 is a graph showing specific capacity after 50 cycles of the silicon carbon composites prepared in examples and comparative examples;
fig. 9 is a graph of the cycling performance of the silicon carbon composite of the present invention at different current densities.
Detailed Description
It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The silicon-carbon composite of the present invention, as shown in fig. 1 and 2, is composed of three parts: silicon particles 11, a first carbon coating layer 12, and a second carbon coating layer 2; the first carbon coating layer 12 uniformly coats the silicon particles 11 to form silicon carbon particles 1 with a core-shell structure, the second carbon coating layer 2 is internally provided with a porous communicated structure, the silicon carbon particles 1 are distributed in holes inside the second carbon coating layer 2, and a large number of pores are formed between the first carbon coating layer 12 and the second carbon coating layer 2. Here, the second carbon clad layer 2 may be regarded as a sponge layer structure in which a large number of holes are distributed and communicated with each other, which provides a lithium ion transport path when the silicon-carbon composite is used as a negative electrode material; the silicon carbon particles are filled in the holes, and because the space occupied by the holes in the second carbon coating layer 2 is slightly larger than the volume of the silicon carbon particles, the second carbon coating layer 2 is not directly coated on the first carbon coating layer 12 and only coats the silicon carbon particles 1, a large number of holes are formed between the first carbon coating layer 12 and the second carbon coating layer 2, and the silicon carbon particles 1 are communicated with each other through the holes.
It should be further noted that the particle size of the silicon particle 1 in this embodiment is 5-200nm, but it is needless to say that the particle size of the silicon particle 1 is preferably 30-100nm in order to obtain a silicon-carbon composite with better performance; in addition, the first carbon coating layer 12 and the second carbon coating layer 2 are both carbon thin layers obtained by pyrolysis of an organic carbon source, and the thicknesses of the carbon thin layers are both nano-scale, wherein the thickness of the first carbon coating layer 12 is 1-30nm, and similarly, the thickness of the first carbon coating layer 12 is preferably 3-10 nm; the second carbon coating layer 2 has a pore wall thickness of 1 to 30nm for forming pores due to its special structure, and of course, for better effect, the pore wall thickness is preferably 3 to 10 nm; mainly, the carbon coating layer with proper thickness can increase the conductivity of the whole silicon-carbon composite, does not cause great obstruction to the transportation of lithium ions, and is more beneficial to the whole performance of the electrochemical performance of the silicon-carbon composite.
When the silicon-carbon composite is used as a lithium ion battery cathode material, silicon particles directly participate in electrochemical reaction to provide capacity for a lithium ion battery, the first carbon coating layers 12 coated on the surfaces of the silicon particles 11 and the second carbon coating layers 2 distributed on the outer layers of the silicon-carbon particles 1 provide electron transport channels for the cathode material, and the overall conductivity of the silicon-carbon composite can be improved; meanwhile, the first carbon coating layer 12 and the second carbon coating layer 2 are also protective layers of silicon particles, and can inhibit side reactions between the silicon particles and electrolyte; meanwhile, the pores among the silicon-carbon particles 1 and between the first carbon coating layer 12 (silicon-carbon particles) and the second carbon coating layer 2 provide buffer spaces for the volume expansion of the silicon particles in the charging and discharging processes, and are helpful for improving the cycle stability of the silicon-carbon composite.
The invention also provides a preparation method of the silicon-carbon composite with the unique structure, which comprises the following steps:
preparing a sodium chloride template agent, dissolving commercial sodium chloride in deionized water to prepare a saturated sodium chloride solution, gradually adding absolute ethyl alcohol under rapid stirring to separate sodium chloride crystals from the saturated sodium chloride solution, filtering when no more crystal grains are separated out, washing the crystal grains with absolute ethyl alcohol for multiple times, and drying the crystal grains to obtain the sodium chloride template agent; wherein the grain size of the sodium chloride template agent is 1-10 μm;
ball-milling and mixing, namely mixing a sodium chloride template, an organic carbon source and silicon particles according to the mass ratio (10-500): (0.2-10): 1, putting the mixture into a ball milling tank, adding a proper amount of absolute ethyl alcohol, carrying out ball milling mixing by adopting a planetary ball mill, wherein the rotating speed of the ball mill is 300-500 rpm, the ball milling time is 10-120 min, and drying slurry after ball milling at 60-100 ℃ to obtain a mixed material; wherein the organic carbon source is any one of sucrose, citric acid, glucose, chitosan, amino acid and starch;
performing heat treatment, namely putting the mixed material into an alumina crucible, putting the alumina crucible into a tubular furnace, heating to 150 ℃ at the speed of 2-10 ℃/min under an inert atmosphere (argon and/or nitrogen), preserving heat for 0.5-2 h, heating to a specific reaction temperature, carbonizing at a constant temperature for 0.5-5 h, and cooling along with the furnace to obtain a heat treatment product; the specific reaction temperature is 500-800 ℃; the preferable reaction temperature is 600-750 ℃, and the reason for limiting the temperature is that if the reaction temperature is too low, the organic carbon source cannot be fully carbonized, and the obtained carbon coating layer has poor conductivity; if the temperature is too high, the melting point of sodium chloride (the melting point of sodium chloride is 801 ℃) can be reached or exceeded, the template effect cannot be realized after the sodium chloride is dissolved, and the growth and distribution of the carbon layer are difficult to be effectively guided.
And removing a sodium chloride template agent, dispersing the heat treatment product in deionized water, filtering, washing with the deionized water for multiple times until the conductivity of the solution is close to 0, indicating that the sodium chloride is fully removed, and drying the obtained product at 60-100 ℃ to obtain the silicon-carbon composite.
The preparation of the sodium chloride template in the preparation method of the silicon-carbon composite is indispensable, and as the size of commercial sodium chloride crystals generally reaches 50-200 mu m and is different in size, sodium chloride crystal grains with smaller size can be synthesized by the preparation steps of the sodium chloride template, and SEM tests show that the size of the sodium chloride template crystal grains prepared in the invention is uniform and is about 1-10 mu m; the small-particle-size sodium chloride template is adopted, so that the growth and distribution of a carbon layer can be guided in the subsequent heat treatment stage, and a first carbon coating layer and a second carbon coating layer which are thinner are obtained, the carbon coating layers tend to coat the surfaces of silicon particles and leave certain pores, and the structure is favorable for relieving the volume expansion of the silicon particles in the charging and discharging processes and can avoid the side reaction caused by the direct contact of silicon and electrolyte; while a thicker carbon layer can only be obtained by using commercial sodium chloride with large particle size, silicon particles tend to be distributed on the surface of the carbon layer, and the problem of volume expansion of silicon in the circulating process is difficult to effectively relieve by the carbon layer. Through the design, the improvement of gram capacity and cycle performance when the silicon-carbon composite of the lithium ion battery is used as a cathode material is realized, and a new idea of electrode design is developed; in addition, the sodium chloride template agent adopted in the preparation of the silicon-carbon composite is easy to recover, the source of the adopted organic carbon source is rich, and the preparation method has the advantages of simple process, strong controllability and the like, and has a large-scale industrial application prospect.
Example 1
The embodiment provides a preparation method of a silicon-carbon composite, which comprises the following steps:
preparation of sodium chloride template: dissolving 54g of commercial sodium chloride crystals into 150mL of deionized water to prepare a saturated solution, gradually adding absolute ethyl alcohol under rapid stirring to separate out sodium chloride crystals, filtering a reaction product when no more crystal grains are separated out, washing for multiple times by adopting the absolute ethyl alcohol, and drying to obtain the sodium chloride template agent.
Ball milling and mixing, namely putting 30g of prepared sodium chloride template agent, 0.6g of glucose and 0.3g of commercial silicon particles into a ball milling tank, adding a proper amount of absolute ethyl alcohol, mixing materials by adopting a planetary ball mill, wherein the rotating speed is 450rpm, the ball milling time is 60min, and drying the obtained slurry at 70 ℃ to obtain a mixed material.
And (3) performing heat treatment, namely putting the mixed material into an alumina crucible, putting the alumina crucible into a tubular furnace, heating to 150 ℃ at the speed of 5 ℃/min under the nitrogen atmosphere, preserving heat for 1h, heating to 700 ℃, carbonizing at constant temperature for 2h, and cooling along with the furnace to obtain a heat treatment product.
And (3) removing the sodium chloride template agent, dispersing the heat treatment product in deionized water, filtering, washing with the deionized water for multiple times until the conductivity of the solution is close to a 0 value, and drying the obtained product at 80 ℃ to obtain the final silicon-carbon composite.
The silicon-carbon composite obtained by the method comprises three parts: silicon particles, a first carbon coating layer and a second carbon coating layer; the silicon-carbon particle with the core-shell structure is formed by uniformly coating the surface of the silicon particle with the first carbon coating layer, the inside of the second carbon coating layer is of a porous communicated structure, the silicon-carbon particles are distributed in the holes inside the second carbon coating layer, a large number of holes are formed between the first carbon coating layer and the second carbon coating layer, the particle size of the silicon particle is 30-80 nm, the thickness of the first carbon coating layer is 3-8nm, and the thickness of the hole wall of the second carbon coating layer is 3-8 nm.
The phase and morphology of the silicon-carbon composite negative electrode material are characterized by adopting a plurality of testing methods, and the results are shown in figures 1-3. The XRD pattern (fig. 3) indicates that the main diffraction peaks of the silicon-carbon composite are all attributed to the silicon (Si) phase, and the carbon material in the silicon-carbon composite is presumed to be in an amorphous state. As can be seen from the SEM image (fig. 4), the surface of the silicon particles was uniformly coated with a thin carbon layer. As can be seen from the TEM image (FIG. 5), the particle size of the silicon particle is about 30-80 nm, the first carbon coating layer is distributed on the surface of the silicon particle, the thickness of the first carbon coating layer is about 3-8nm, the second carbon coating layer is coated on the periphery of the silicon-carbon particle, and a large number of pores are formed among the silicon-carbon particles and between the silicon-carbon particle and the second carbon coating layer. The above characterization results show that the silicon-carbon composite with the double-layer carbon coating structure is synthesized by the above preparation method.
Weighing the silicon-carbon composite, the conductive agent Super P and the binder polyacrylonitrile according to the mass ratio of 8:1:1, dissolving the silicon-carbon composite, the conductive agent Super P and the binder polyacrylonitrile in a proper amount of Dimethylformamide (DMF) to prepare slurry with proper viscosity, coating the slurry on copper foil, punching into small wafers (namely silicon-carbon composite negative plates) with the diameter of 12mm, and assembling the small wafers into a CR2032 button type lithium ion battery in a glove box for testing the electrochemical performance of materials.
The result shows that the silicon-carbon composite prepared in example 1 shows excellent electrochemical performance when applied to a lithium ion battery, the first and second discharge specific capacities of the negative electrode of the silicon-carbon composite are 1241mAh/g and 938mAh/g respectively at a current density of 0.2A/g, and the specific capacity is stabilized at 920mAh/g after 50 cycles (as shown in FIG. 8). Fig. 9 is a graph of cycle performance of the silicon-carbon composite negative electrode under different current densities, and it can be seen from fig. 9 that the silicon-carbon composite negative electrode can provide higher specific capacity when cycled under different current densities, and can still be stably tested after high-current charge and discharge, and exhibits excellent cycle stability.
To illustrate the advantages of the silicon carbon composite structure design of the present invention, the inventors also conducted the following comparative experiments:
comparative example 1
The present comparative example is different from example 1 in structure in that the silicon-carbon composite prepared in the present comparative example includes silicon particles and a carbon coating layer uniformly coated on the surfaces of the silicon particles.
The difference in the preparation method is that no sodium chloride template is used, and the other process steps are the same as those in example 1.
The morphology of the silicon-carbon composite prepared by the comparative example is shown in the SEM image of FIG. 6.
The same test method as that of example 1 is adopted to test the cycle performance of the silicon-carbon composite prepared in the comparative example 1 under 0.2A/g, as shown in FIG. 8, the figure shows that the initial specific discharge capacity of the silicon-carbon composite is 1556mAh/g, but the capacity value is rapidly attenuated along with the increase of the cycle number, and the specific discharge capacity of the 50 th cycle is only 159mAh/g, because when a sodium chloride template agent is not adopted, no pore exists in the composite structure, and the huge volume expansion of silicon particles in the charging and discharging processes cannot be effectively relieved, so that the electrode structure is seriously pulverized and the cycle stability is poor.
Comparative example 2
The structure of the present comparative example is a silicon carbon composite nanoplate, wherein the silicon particles are distributed on the surface of the carbon nanoplate.
The preparation method of the silicon-carbon composite of the comparative example is different from that of the example 1 in that commercial sodium chloride is directly used as a template, the sodium chloride is not subjected to dissolution recrystallization treatment (i.e. the preparation step of the sodium chloride template in the example 1 is not carried out), and other process steps are the same as those in the example 1.
The morphology of the silicon carbon composite in this comparative example is shown in the SEM image of fig. 7.
The same test method as that of example 1 is adopted to test the cycle performance of the silicon-carbon composite synthesized by the comparative example under 0.2A/g, as shown in FIG. 8, the initial specific discharge capacity of the silicon-carbon composite is 2026mAh/g, but the capacity value decays rapidly along with the increase of the cycle number, and the specific discharge capacity of the 50 th cycle is only 584 mAh/g; the reason is that when commercial sodium chloride is used as a template agent, the sodium chloride is large in size and reaches 50-200 microns, an organic carbon source cannot be guided to be carbonized to form a thin carbon layer in the heat treatment process, only thick carbon nanosheets can be obtained, silicon particles are distributed on the surfaces of the carbon nanosheets, no pores exist between silicon and carbon, huge volume expansion of the silicon particles in the charging and discharging process cannot be effectively relieved, and side reactions are easy to occur when the silicon particles are directly contacted with electrolyte, so that the electrode structure is seriously pulverized, and the circulation stability is poor.
Compared with the comparative examples 1 and 2, the silicon-carbon composite prepared by the embodiment can realize higher specific capacity and more excellent cycle performance, which is closely independent of the unique composite structure, and the double-layer carbon coating of the silicon-carbon composite in the embodiment improves the overall conductivity of the composite material, and simultaneously, the double-layer carbon coating serves as a protective layer on the surface of the silicon particle to inhibit side reactions between the silicon particle and electrolyte. The pores formed among the silicon-carbon particles and between the silicon-carbon particles and the second carbon coating layer provide buffer spaces for the volume expansion of the silicon particles in the charging and discharging processes, and are favorable for improving the cycle stability of the composite material.
The invention also provides a lithium ion battery manufactured by the silicon-carbon composite, wherein the lithium ion battery can be a lithium ion battery pack consisting of a plurality of lithium ion cores and can also be a lithium ion core; the lithium ion battery pack comprises a battery module, a circuit board, a shell and the like, the battery module, the circuit board and the like are assembled to form the lithium ion battery pack, the lithium ion battery pack has various specifications, can be adjusted and designed according to needs, and is not limited in the process, and the assembly mode of the lithium ion battery pack in the prior art can be applied to the invention; in addition, the lithium ion battery cell may be a lithium ion soft package battery cell, and may also be a lithium ion hard package battery cell, which are not limited herein.
The lithium ion battery can be applied to the fields of consumer electronics products, vehicles and electric tools, particularly in the field of consumer electronics, such as mobile phones, notebook computers, bracelets, intelligent sound boxes and the like; the field of transportation, such as applications in automobiles, motorcycles, bicycles, and the like; the electric tool field is like unmanned aerial vehicle, electric drill, electric screwdriver etc..
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
The above-mentioned serial numbers of the embodiments of the present invention are merely for description and do not represent the merits of the embodiments.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention in the specification or other related fields directly or indirectly are included in the scope of the present invention.
Claims (10)
1. A silicon carbon composite, characterized by: comprises silicon particles, a first carbon coating layer and a second carbon coating layer; the silicon-carbon composite material comprises a first carbon coating layer, a second carbon coating layer and a third carbon coating layer, wherein the first carbon coating layer uniformly coats the surfaces of silicon particles to form silicon-carbon particles with core-shell structures, the second carbon coating layer is internally provided with a porous communicated structure, the silicon-carbon particles are distributed in holes in the second carbon coating layer, and pores exist between the first carbon coating layer and the second carbon coating layer.
2. The silicon carbon composite of claim 1, wherein: the particle size of the silicon particles is 5-200nm, and the thickness of the first carbon coating layer is 1-30 nm.
3. A method for preparing a silicon-carbon composite according to claim 1 or 2, comprising the steps of:
preparing a sodium chloride template agent, dissolving commercial sodium chloride in water to prepare a saturated sodium chloride solution, separating sodium chloride crystals from the saturated sodium chloride solution by using absolute ethyl alcohol, filtering, washing for multiple times by using absolute ethyl alcohol, and drying to obtain the sodium chloride template agent;
ball-milling and mixing, namely putting the sodium chloride template, the organic carbon source and the silicon particles into a ball-milling tank according to a ratio, adding absolute ethyl alcohol, carrying out ball-milling and mixing, and drying slurry after ball milling to obtain a mixed material;
performing heat treatment, namely carbonizing the mixed material at a constant temperature under an inert atmosphere and at a specific reaction temperature, and cooling to obtain a heat treatment product;
and removing the sodium chloride template agent, dispersing the heat treatment product in deionized water, washing for multiple times until the conductivity of the solution is close to 0, and drying the obtained product to obtain the silicon-carbon composite.
4. A method of preparing a silicon-carbon composite as claimed in claim 3, wherein: the organic carbon source is any one of sucrose, citric acid, glucose, chitosan, amino acid and starch.
5. A method of preparing a silicon-carbon composite as claimed in claim 3, wherein: the grain size of the sodium chloride template agent is 1-10 mu m.
6. A lithium ion battery negative electrode material is characterized in that: comprising a silicon-carbon composite produced by the production method according to claims 3 to 5.
7. The utility model provides a lithium ion battery negative pole piece, includes that the negative pole current collector is in with the setting the negative electrode material of the negative pole current collector both sides, its characterized in that: the anode material comprises the silicon-carbon composite according to claim 1 or 2.
8. The negative electrode sheet of the lithium ion battery according to claim 7, wherein: the silicon-carbon composite is prepared by the preparation method according to the claims 3-5.
9. A lithium ion battery, characterized by: comprises a negative electrode material, the negative electrode material comprises silicon-carbon composite, and the silicon-carbon composite is prepared by the preparation method of claims 3-5.
10. The lithium ion battery of claim 9 is applied to an electronic product, an electric vehicle or a vehicle, wherein the vehicle comprises an automobile, a bicycle, a motorcycle, or the like.
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