CN112234197B - Amorphous carbon-silicon-carbon nanofiber-graphite composite material and preparation method and application thereof - Google Patents
Amorphous carbon-silicon-carbon nanofiber-graphite composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an amorphous carbon-silicon-carbon nanofiber-graphite composite material and a preparation method and application thereof.
Description
Technical Field
The invention relates to a silicon-carbon composite negative electrode material, in particular to an amorphous carbon-silicon-carbon nanofiber-graphite composite material, a method for preparing the amorphous carbon-silicon-carbon nanofiber-graphite composite material by vapor deposition, and application of the amorphous carbon-silicon-carbon nanofiber-graphite composite material in a lithium ion battery negative electrode material, and belongs to the technical field of preparation of the lithium ion battery negative electrode material.
Background
Silicon is used as a high-capacity lithium ion battery cathode material with the greatest development prospect, and has the advantages of theoretical lithium storage capacity of 4200mAh/g, low possibility of lithium precipitation in the charging and discharging process, high safety performance and the like. However, silicon has poor conductivity, and the volume change rate is about 400% in the process of lithium intercalation and deintercalation, which causes collapse of the structure of the negative electrode material, pulverization of the material, and separation from the current collector, and greatly reduces the cycle stability of the battery. In addition, the volume effect in the charging and discharging process enables an SEI film to be broken and reconstructed, a large amount of lithium in the electrolyte is consumed, and the capacity of the battery is attenuated. The defects of silicon as the negative electrode material of the lithium ion battery seriously affect the commercialization application process of the silicon.
In order to solve the above problems, the development of commercialization of silicon as a lithium ion battery is promoted, and research on silicon-based negative electrode materials at home and abroad is mainly focused on compounding silicon with carbon materials such as amorphous carbon and graphite to prepare silicon-carbon composite negative electrode materials. This material combines the high capacity of silicon with the cycling properties of graphite. The currently common method is to prepare the silicon-carbon composite negative electrode material by a ball milling method, the bonding strength between the nano silicon prepared by the mechanical composite method and the substrate carbon is poor, and the silicon falls off from the surface of the substrate carbon due to the difference of the lithium-intercalated and lithium-deintercalated expansion and contraction coefficients of the silicon and the substrate after multiple charging and discharging. Chemical vapor deposition is another main preparation method for preparing the silicon-carbon composite negative electrode material, which is easy for industrial production, and usually, nano silicon is deposited on the surface of a substrate through chemical vapor deposition, so that the bonding strength of silicon and the substrate in the obtained nano silicon-carbon composite material is far higher than that of the nano silicon-carbon composite material prepared by a ball milling method, and the improvement of the battery performance of the composite negative electrode material is facilitated. The conventional chemical vapor deposition is to catalyze the deposition of silicon by using transition elements of the fourth period such as Fe, Co, Ni, Cu and the like as catalysts. The Fe, Co and Ni are magnetic elements, and the metal impurities in the negative electrode material can be dissociated due to the formation of the primary battery in the battery, so that the diaphragm is conducted due to the deposition on the surface of the diaphragm to form physical micro short circuit, and the safety performance of the battery is influenced. And trace impurities such as Cu, Mo and the like can influence the performance of the electrolyte, so that the electrochemical performance and the service life of the battery are caused. The technical indexes of the graphite cathode material of the national standard GB/T2433and 2009 lithium ion battery show that the content of a trace metal element Fe is less than 10ppm, and the content of Cu, Ni, Co and the like is less than 5 ppm. The ministry of industry and informatization of the people's republic of China issues ' lithium ion battery industry standard conditions ' to definitely stipulate that enterprises should have the detection capability of metal harmful impurities of positive and negative electrode materials of batteries, and the contents of harmful elementary substances such as iron, zinc, copper and the like in the positive and negative electrode materials of the batteries are respectively not more than 1 ppm. Meanwhile, the content of magnetic impurities in negative electrode materials such as carbon (graphite), lithium titanate, silicon carbon, amorphous carbon negative electrode materials (including soft carbon and hard carbon) and other negative electrode materials is less than 100 ppb. These requirements limit the application of chemical vapor deposition techniques to the preparation of carbon silicon composites.
Disclosure of Invention
Aiming at the problems caused by the existence of trace metal in the existing chemical vapor deposition technology for catalyzing silicon deposition by a metal catalyst, the first purpose of the invention is to provide a method for obtaining an amorphous carbon-silicon-carbon nanofiber-graphite composite material by metal-catalyzed vapor deposition of carbon nanofibers, then removing metal at high temperature, then catalyzing chemical vapor deposition of silicon by using the carbon nanofibers, and finally performing chemical vapor deposition of amorphous carbon.
The invention also aims to provide the amorphous carbon-silicon-carbon nanofiber-graphite composite material which has low metal impurity residue, stable carbon-silicon combination and good electrochemical performance.
The third purpose of the invention is to provide an application of the amorphous carbon-silicon-carbon nanofiber-graphite composite material as a lithium ion battery negative electrode material, so that a lithium ion battery with good cycle stability can be obtained.
In order to achieve the above technical objects, the present invention provides a method for preparing an amorphous carbon-silicon-carbon nanofiber-graphite composite material, comprising the steps of:
1) uniformly mixing a metal catalyst and natural graphite, depositing carbon nanofibers on the surface of the natural graphite through chemical vapor deposition, and removing the metal catalyst through high-temperature volatilization to obtain a carbon nanofiber-natural graphite composite material;
2) depositing silicon on the surface of the carbon nanofiber-natural graphite composite material through chemical vapor deposition to obtain a silicon-carbon nanofiber-natural graphite composite material;
3) amorphous carbon is deposited on the surface of the silicon-carbon nanofiber-natural graphite composite material through chemical vapor deposition, and the amorphous carbon-silicon-carbon nanofiber-graphite composite material is obtained.
According to the technical scheme, the metal catalyst is compounded with graphite, the metal catalyst is used for catalyzing the in-situ generation of the carbon nanofiber on the surface of the graphene, the metal catalyst is used for catalyzing the surface of the carbon nanofiber generated by chemical vapor deposition to generate a plurality of defects, and the defects become high-activity catalytic active centers, so that the in-situ generation of silicon can be catalyzed in the chemical vapor deposition process. Generally, chemical vapor deposition silicon mainly utilizes metal catalysts to promote the generation of silicon, but the metal catalysts are difficult to remove after the silicon is deposited, so that the metal catalysts are remained to influence the electrochemical performance of the silicon. Therefore, according to the technical scheme of the invention, the metal catalyst can be efficiently removed directly through high-temperature volatilization after the carbon nano fiber is generated, and the generated carbon nano fiber has the characteristic of promoting silicon deposition by high-activity catalysis, so that the residue of the metal catalyst in the composite material is avoided. Meanwhile, the carbon nanofiber has high specific surface area and high conductivity, and is compounded with silicon in situ by utilizing the carbon nanofiber with high specific surface area, so that the stability and the dispersibility of the silicon are improved, and meanwhile, an electron transmission channel is provided by utilizing the good conductivity of the carbon nanofiber. According to the technical scheme, after the silicon is deposited, the amorphous carbon is further deposited, the existence of the amorphous carbon layer enables the electrolyte not to be in direct contact with the silicon in the electrode, and the repeated formation and damage of an SEI film in the electrode circulation process are avoided, so that stable circulation is carried out.
As a preferable technical solution, the metal-based catalyst and the natural graphite are mixed by a dry method or a wet method. The dry mixing is to directly mechanically mix the natural graphite and the metal catalyst, such as grinding, ball milling and the like. The wet mixing is mainly to dissolve the metal catalyst in the solvent, then to mix with the natural graphite and dry. Preferably, wet mixing is adopted, and the metal salt is uniformly loaded on the graphene, so that the carbon nano-fibers can be uniformly generated on the surface of the graphene.
In a preferred embodiment, the metal catalyst is a metal compound containing at least one of iron, nickel, copper, and cobalt. Specific metal-based catalysts are, for example, ferric chloride, nickel nitrate, copper sulfate, cobalt chloride, and the like.
As a preferable technical scheme, the mass of the metal catalyst is 0.01-10% of the total mass of the metal catalyst and the natural graphite.
As a preferred technical solution, the conditions of the chemical vapor deposition of the carbon nanofibers are as follows: aliphatic hydrocarbon is used as a carbon source, the pressure is normal pressure, the temperature is 500-1100 ℃, and the time is 0.5-3 hours. The aliphatic hydrocarbons are mainly short-chain gaseous aliphatic hydrocarbons, such as methane, acetylene, propylene, natural gas and the like.
As a preferred technical solution, the conditions of the high-temperature volatilization demetallization catalyst are as follows: the temperature is 1500-2500 ℃, and the time is 0.5-2 hours. Under the condition, the high-efficiency volatilization and removal of the metal catalyst can be realized.
As a preferred technical solution, the conditions of the chemical vapor deposition of silicon are as follows: silane and/or chlorosilane are/is used as a silicon source, the pressure is normal pressure, the temperature is 500-1100 ℃, and the time is 1-3 hours. Chlorosilanes such as dichlorodimethylsilane.
As a preferred technical scheme, the conditions of the chemical vapor deposition of the amorphous carbon are as follows: aliphatic hydrocarbon or aromatic hydrocarbon is used as a carbon source, the pressure is negative pressure or positive pressure, the temperature is 500-1100 ℃, and the time is 1-3 hours. The carbon source is specifically toluene, xylene, methane, acetylene, propylene, natural gas, or the like.
The invention also provides an amorphous carbon-silicon-carbon nanofiber-graphite composite material which is prepared by the preparation method.
The invention also provides an application of the amorphous carbon-silicon-carbon nanofiber-graphite composite material as a negative electrode material of a lithium ion battery.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
1. according to the technical scheme, silicon and carbon in the amorphous carbon-silicon-carbon nanofiber-graphite composite material are compounded by a chemical vapor deposition method, the silicon is uniformly dispersed, the bonding strength with the carbon is high, and the stability and the electrochemical activity of the composite material are greatly improved.
2. In the amorphous carbon-silicon-carbon nanofiber-graphite composite material adopting the technical scheme, the graphite-carbon nanofiber-carbon cladding layer forms a 3D conductive structure, so that the conductivity of the electrode is increased, the carbon nanofiber and the silicon nanofiber are distributed in a crossed manner and are closely connected, and the volume effect brought by silicon in a circulating process is effectively relieved.
3. According to the preparation process of the amorphous carbon-silicon-carbon nanofiber-graphite composite material, the carbon nanofibers are used for catalyzing chemical vapor deposition of silicon, so that the residue of metal catalysts can be reduced, the poisoning of trace metal elements to a battery is effectively avoided, the safety performance of the battery is improved, and the service life of the battery is prolonged.
4. The preparation method of the amorphous carbon-silicon-carbon nanofiber-graphite composite material is simple, low in cost and easy for industrial production.
5. The amorphous carbon-silicon-carbon nanofiber-graphite composite material prepared by the technical scheme of the invention is prepared by a chemical vapor deposition method, has the characteristics of controllable silicon size and loading capacity and controllable carbon coating thickness, and can be used for preparing silicon-carbon composite anode materials with different performance requirements according to design requirements.
Drawings
Fig. 1 is a Raman spectrum of pure powder Si, graphite G and amorphous carbon-silicon-carbon nanofiber-graphite composite C-Si-CNF-G (example 1).
Fig. 2 is a scanning electron microscope image, wherein a is graphite G, b is a silicon-carbon nanofiber-graphite composite material Si-CNF-G, and C is an amorphous carbon-silicon-carbon nanofiber-graphite composite material C-Si-CNF-G.
FIG. 3 is a graph of cycling curves for lithium ion batteries of different negative electrode materials, using a CR2032 half-cell test with lithium metal as the counter electrode; corresponding to graphite G, carbon nanofiber-graphite CNF-G and amorphous carbon-silicon-carbon nanofiber-graphite composite material C-Si-CNF-G respectively.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
Example 1
1. Weighing 50g of graphite powder and 2g of ferric chloride, mixing in an aqueous solution, drying at 80 ℃ for 12h in a forced air drying oven, grinding, and sieving by a 200-mesh sieve. And placing the sample in a chemical vapor deposition furnace, depositing for 0.5h at 800 ℃ under normal pressure by using methane as a carbon source, then placing the sample in a high-temperature furnace for heat treatment for 0.5h at 1500 ℃, and removing trace elements to prepare the carbon nanofiber-natural graphite composite material.
2. And (2) putting 5g of the sample in the step (1) into a specific tool, placing the specific tool in a chemical vapor deposition furnace, depositing for 2 hours at 900 ℃ by using dichlorodimethylsilane as a silicon source and argon as a carrier gas, grinding the deposited sample, washing with deionized water for three times, performing suction filtration and drying to prepare the silicon-carbon nanofiber-natural graphite composite material.
3. And (3) putting the 2 pilot samples into a chemical vapor deposition furnace, carrying out carbon coating deposition for 1h at 600 ℃ under the negative pressure condition with the flow ratio of nitrogen, hydrogen and acetylene being 0.8:0.1:0.1, and preparing the amorphous carbon-silicon-carbon nanofiber-natural graphite silicon-carbon composite negative electrode material.
The Raman spectrum of the prepared amorphous carbon-silicon-carbon nanofiber-graphite composite material C-Si-CNF-G is shown in figure 1, compared with the D peak and the G peak of a graphite G substrate, the material C-Si-CNF-G has obviously more characteristic peaks of silicon, and the ratio of the D peak to the G peak is obviously changed, which shows the success of silicon deposition and the successful coating of amorphous carbon.
The scanning electron microscope image of the prepared amorphous carbon-silicon-carbon nanofiber-graphite composite material C-Si-CNF-G is shown in figure 2, figure 2.a is the electron microscope image of a single graphite particle, figure 2.b is a sample obtained by carbon fiber deposition and silicon fiber deposition in sequence, carbon fibers and silicon fibers are densely and alternately distributed on the surface of graphite, and figure 2.C is the appearance of the sample coated by amorphous carbon.
The composite negative electrode material, the conductive carbon black and the adhesive PVDF are mixed according to the proportion of 7: 1: 2, preparing a negative electrode material, taking lithium metal as a counter electrode, adopting a Celgard2400 polypropylene porous diaphragm, adopting an electrolyte solution of LiPF6 solution of 1mol/L, and preparing a CR2032 half-cell test by using an organic solvent which is a mixture with the volume ratio of EC to DMC of 1 to 1, wherein the test current density is 100 mA/g.
The cycle performance curve of the amorphous carbon-silicon-carbon nanofiber-graphite composite material C-Si-CNF-G is shown in figure 3, the reversible specific capacity of graphite G after 50 cycles is 330mAh/G, and the reversible specific capacity of carbon nanofiber-graphite CNF-G after 50 cycles is 378mAh/G, so that the conductivity and the ionic conductivity are improved due to the growth of surface carbon fibers, and the reversible specific capacity of the amorphous carbon-silicon-carbon nanofiber-graphite composite material C-Si-CNF-G after 50 cycles is 480mAh/G, so that the lithium storage capacity of the material is improved due to the growth of silicon nanofibers, and the cycle stability of the composite material is improved due to the coating of an amorphous carbon layer.
Example 2
1. Weighing 50g of graphite powder and 2g of nickel nitrate, mixing in an aqueous solution, drying at 80 ℃ for 12h in a forced air drying oven, grinding, and sieving by a 200-mesh sieve. And placing the sample in a chemical vapor deposition furnace, depositing for 0.5h at 900 ℃ and normal pressure by taking propylene as a carbon source, then placing the sample in a high-temperature furnace for heat treatment for 0.5h at 1500 ℃, and removing trace elements to prepare the carbon nanofiber-natural graphite composite material.
2. And (3) putting 5g of the sample in the step (1) into a specific tool, placing the specific tool in a chemical vapor deposition furnace, depositing for 1h at 900 ℃ by using dichlorodimethylsilane as a silicon source and argon as a carrier gas, grinding the deposited sample, washing with deionized water for three times, performing suction filtration and drying to prepare the silicon-carbon nanofiber-natural graphite composite material.
3. And (3) putting the 2 pilot samples into a chemical vapor deposition furnace, carrying out carbon coating deposition for 1h at 800 ℃ under the negative pressure condition with the flow ratio of nitrogen, hydrogen and acetylene being 0.9:0.05:0.05, and preparing the amorphous carbon-silicon-carbon nanofiber-natural graphite silicon-carbon composite negative electrode material.
The prepared amorphous carbon-silicon-carbon nanofiber-natural graphite silicon-carbon composite negative electrode material is assembled into a lithium battery according to example 1, the first specific discharge capacity is 1050mAh/g, and the specific capacity of 463mAh/g is still obtained after 50 cycles.
Example 3
1. Weighing 50g of graphite powder and 2g of cobalt nitrate, mixing in an aqueous solution, drying at 80 ℃ for 12h in a forced air drying oven, grinding, and sieving by a 200-mesh sieve. And placing the sample in a chemical vapor deposition furnace, depositing for 0.5h at 800 ℃ and normal pressure by taking propylene as a carbon source, then placing the sample in a high-temperature furnace for heat treatment for 0.5h at 1500 ℃, and removing trace elements to prepare the carbon nanofiber-natural graphite composite negative electrode material.
2. And (2) putting 5g of the sample in the step (1) into a specific tool, placing the specific tool in a chemical vapor deposition furnace, depositing for 2 hours at 900 ℃ by using dichlorodimethylsilane as a silicon source and argon as a carrier gas, grinding the deposited sample, washing with deionized water for three times, performing suction filtration and drying to prepare the silicon-carbon nanofiber-natural graphite composite negative electrode material.
3. And (3) putting the 2 pilot samples into a chemical vapor deposition furnace, carrying out carbon coating deposition for 1h at the temperature of 600 ℃ under the normal pressure condition with the flow ratio of nitrogen to hydrogen to acetylene of 0.8:0.1:0.1, and preparing the amorphous carbon-silicon-carbon nanofiber-natural graphite silicon-carbon composite negative electrode material.
The prepared amorphous carbon-silicon-carbon nanofiber-natural graphite silicon-carbon composite negative electrode material is assembled into a lithium battery according to example 1, the first specific discharge capacity is 980mAh/g, and the specific capacity of 460mAh/g is still obtained after 50 cycles.
Claims (9)
1. A preparation method of an amorphous carbon-silicon-carbon nanofiber-graphite composite material is characterized by comprising the following steps: comprises the following steps:
1) uniformly mixing a metal catalyst and natural graphite, depositing carbon nanofibers on the surface of the graphite through chemical vapor deposition, and removing the metal catalyst through high-temperature volatilization to obtain a carbon nanofiber-graphite composite material; the metal catalyst is a metal compound containing at least one of iron, nickel, copper and cobalt;
2) depositing silicon on the surface of the carbon nanofiber-graphite composite material through chemical vapor deposition to obtain a silicon-carbon nanofiber-graphite composite material;
3) and (3) depositing amorphous carbon on the surface of the silicon-carbon nanofiber-graphite composite material through chemical vapor deposition to obtain the amorphous carbon-silicon-carbon nanofiber-graphite composite material.
2. The method for preparing an amorphous carbon-silicon-carbon nanofiber-graphite composite material as claimed in claim 1, wherein: the metal catalyst and the natural graphite are mixed by a dry method or a wet method.
3. The method for preparing an amorphous carbon-silicon-carbon nanofiber-graphite composite material as claimed in claim 1, wherein: the mass of the metal catalyst is 0.01-10% of the total mass of the metal catalyst and the natural graphite.
4. The method for preparing an amorphous carbon-silicon-carbon nanofiber-graphite composite material as claimed in claim 1, wherein: the conditions of the chemical vapor deposition of the carbon nanofiber are as follows: aliphatic hydrocarbon is used as a carbon source, the pressure is normal pressure, the temperature is 500-1100 ℃, and the time is 0.5-3 hours.
5. The method for preparing an amorphous carbon-silicon-carbon nanofiber-graphite composite material as claimed in claim 1, wherein: the conditions for volatilizing and removing the metal catalyst at high temperature are as follows: the temperature is 1500-2500 ℃, and the time is 0.5-2 hours.
6. The method for preparing an amorphous carbon-silicon-carbon nanofiber-graphite composite material as claimed in claim 1, wherein: the conditions for chemical vapor deposition of silicon are as follows: silane and/or chlorosilane are/is used as a silicon source, the pressure is normal pressure, the temperature is 500-1100 ℃, and the time is 1-3 hours.
7. The method for preparing an amorphous carbon-silicon-carbon nanofiber-graphite composite material as claimed in claim 1, wherein: the conditions for the chemical vapor deposition of amorphous carbon are as follows: aliphatic hydrocarbon or aromatic hydrocarbon is used as a carbon source, the pressure is negative pressure or positive pressure, the temperature is 500-1100 ℃, and the time is 1-3 hours.
8. An amorphous carbon-silicon-carbon nanofiber-graphite composite material, characterized in that: the preparation method of any one of claims 1 to 7.
9. Use of an amorphous carbon-silicon-carbon nanofiber-graphite composite material according to claim 8, characterized in that: the material is applied as a negative electrode material of a lithium ion battery.
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