CN107394176B - Silicon-carbon composite material, preparation method and application thereof, and lithium ion battery cathode material - Google Patents

Silicon-carbon composite material, preparation method and application thereof, and lithium ion battery cathode material Download PDF

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CN107394176B
CN107394176B CN201710646145.2A CN201710646145A CN107394176B CN 107394176 B CN107394176 B CN 107394176B CN 201710646145 A CN201710646145 A CN 201710646145A CN 107394176 B CN107394176 B CN 107394176B
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silicon
electrode
composite material
carbon composite
dimensional carbon
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CN107394176A (en
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符金洲
刘昊
廖立兵
范朋
王振
郝会颖
邢杰
董敬敬
吕国诚
梅乐夫
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China University of Geosciences Beijing
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a silicon-carbon composite material, a preparation method and application thereof, and a lithium ion battery cathode material, and relates to the technical field of cathode materials for lithium ion batteries. The silicon-carbon composite material is used as the negative electrode of the lithium ion battery, so that the technical problem of battery performance reduction caused by separation of a silicon material and a current collector due to volume change of silicon when the silicon is used as the negative electrode material in the prior art is solved, and the service life of the lithium ion battery using the silicon as the negative electrode material is prolonged.

Description

Silicon-carbon composite material, preparation method and application thereof, and lithium ion battery cathode material
Technical Field
The invention relates to the technical field of negative electrode materials for lithium ion batteries, in particular to a silicon-carbon composite material, a preparation method and application thereof and a lithium ion battery negative electrode material.
Background
The lithium ion battery has the outstanding advantages of high energy density, high working voltage, small self-discharge, long cycle life, no memory effect and the like, and is widely applied to various portable electronic products. The flexible/foldable optoelectronic device/wearable equipment is one of the most promising next-generation electronic device products, so that the development of flexible lithium ion batteries with the characteristics of flexibility and bending stability becomes one of the leading-edge hotspots of the research in the energy storage field at present.
Graphite is mostly selected as the current negative electrode material of commercial lithium ion batteries, and is generally covered on a metal current collector by a coating method after being mixed with a conductive agent and a binder, and the electrode is rigid and is not suitable for flexible lithium ion batteries.
Compared with the traditional graphite cathode, silicon has ultrahigh theoretical capacity (up to 4200mAh/g) and lower lithium removal potential (< 0.5V), and the voltage platform of silicon is slightly higher than that of graphite, so that surface lithium precipitation is not easy to occur in the charging process, and the safety performance is good, therefore, silicon becomes one of candidate materials for upgrading and updating of the carbon-based cathode of the lithium ion battery. However, the silicon material itself has disadvantages, for example, silicon is a semiconductor material, the electrical conductivity is low, and during the electrochemical cycling process, the intercalation and deintercalation of lithium ions can cause the silicon material to expand seriously, so that the volume expands and contracts by 300%, the mechanical force generated by the deformation can gradually pulverize the silicon material, the structure collapses, and finally the silicon material and the metal current collector fall off, the electrical contact is lost, and the cycling performance of the battery is greatly reduced. Due to this volume change, it is difficult for silicon to form a stable solid electrolyte interface film in the electrolyte, resulting in corrosion of silicon and capacity degradation.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the present invention is to provide a silicon-carbon composite material to alleviate the technical problem of battery performance degradation caused by separation of silicon material and current collector due to volume change of silicon when silicon is used as a negative electrode material in the prior art.
The second purpose of the invention is to provide an application of the silicon-carbon composite material in a lithium ion battery negative electrode material.
The third purpose of the invention is to provide a lithium ion battery cathode material, which comprises the silicon-carbon composite material.
The fourth purpose of the invention is to provide a preparation method of the silicon-carbon composite material, by which a silicon thin film can be obtained on the surface of the three-dimensional carbon material.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
a silicon-carbon composite material comprises a three-dimensional carbon material, wherein a silicon thin film is coated on the surface of the three-dimensional carbon material.
Further, the thickness of the silicon thin film is 0.01-500 μm.
Further, the three-dimensional carbon material is a flexible three-dimensional carbon material.
Further, the three-dimensional carbon material includes any one of carbon nanotube paper, carbon fiber, graphene foam, graphene aerogel or three-dimensional carbon-metal composite.
Further, a metal layer is arranged between the surface of the three-dimensional carbon material and the silicon film.
Further, the metal layer is a gold layer.
Further, the silicon thin film is doped with p-type silicon or n-type silicon.
An application of the silicon-carbon composite material in a lithium ion battery cathode material.
A lithium ion battery cathode material comprises the silicon-carbon composite material.
The preparation method of the silicon-carbon composite material adopts an electrodeposition method to deposit the silicon film on the surface of the three-dimensional carbon material.
Further, the preparation method of the silicon-carbon composite material comprises the following steps:
and (3) placing the three-dimensional carbon material serving as a working electrode in an electroplating solution containing a silicon source, and performing electrodeposition operation by using a three-electrode system under the environment of protective gas to obtain a silicon film on the surface of the three-dimensional carbon material.
According to the preparation method of the silicon-carbon composite material, the protective gas is argon or nitrogen.
Further, the plating solution includes a silicon source, an electrolyte, and an organic solvent.
Further, the silicon source comprises any one of silicon tetrachloride, trichlorosilane, tetraethoxysilane, trimethoxy silane, dimethylamine silane, silicon bromide or potassium silicofluoride or a combination of at least two of the silicon tetrachloride, the trichlorosilane, the tetraethoxysilane, the trimethoxy silane, the dimethylamine silane, the silicon bromide or the potassium silicofluoride.
Further, the concentration of the silicon source in the plating liquid is 0.01 to 2 mol/L.
Further, the electrolyte comprises any one of tetrabutylammonium chloride, tetrabutylammonium perchlorate, lithium perchlorate or tetrabutylammonium bromide or a combination of at least two of the tetrabutylammonium chloride, the tetrabutylammonium perchlorate, the lithium perchlorate or the tetrabutylammonium bromide.
Further, the concentration of the electrolyte in the plating solution is 0.01 to 2 mol/L.
Further, the organic solvent comprises any one of propylene carbonate, tetrahydrofuran, acetonitrile, dimethyl sulfate or acetone or a combination of at least two of the propylene carbonate, the tetrahydrofuran, the acetonitrile, the dimethyl sulfate and the acetone.
Further, the preparation method of the electroplating solution comprises the following steps: heating the electrolyte in a protective gas environment, stirring at 120-250 ℃, adding the cooled electrolyte into an organic solvent for dissolving, and then adding a silicon source for stirring to obtain the electroplating solution.
Further, the protective gas is argon or nitrogen.
Further, the electroplating solution also comprises any one or a combination of at least two of phosphorus trichloride, phosphorus pentachloride or triethyl phosphate;
or the electroplating solution also comprises triethyl borate and/or aluminum trichloride.
Further, the electrodeposition method includes any one of a galvanostatic method, a constant voltage method, a square wave amperometry, a square wave voltagemethod or a cyclic voltammetry method or a combination of at least two methods.
Furthermore, in the electrodeposition process, the current density is-0.1 to-10 mA/cm2The voltage range is-1.5 to-3.5V.
Further, the counter electrode in the three-electrode system comprises a platinum sheet electrode or a titanium sheet electrode.
Furthermore, the reference electrode in the three-electrode system comprises a platinum wire electrode, a silver chloride electrode, a calomel electrode, a mercury oxidized mercury electrode, a mercury mercuric sulfate electrode or a copper sulfate electrode.
Further, the method also comprises the steps of washing, soaking, drying and annealing the obtained silicon-carbon composite material after the electrodeposition is finished.
Further, the annealing conditions are as follows: annealing is carried out for 30-40 min under the condition of 330-370 ℃.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the silicon film is covered on the surface of the three-dimensional carbon material, so that the problems of silicon material expansion and easy falling of the silicon material and a current collector can be relieved to a certain extent. The three-dimensional carbon material can buffer the volume expansion and contraction of the silicon material in the charging and discharging processes, and avoids the silicon material from being separated from the three-dimensional carbon material, so that the prepared silicon-carbon composite material is not easy to be separated from a current collector, and the cycle life of the battery is prolonged.
In addition, the three-dimensional carbon material has a porous structure, so that the three-dimensional carbon material can provide an excellent conductive network, and the rapid charge and discharge capacity and the rate capability of the silicon-carbon composite material are improved.
In addition, the three-dimensional carbon material has high specific surface area, good conductivity, excellent flexibility and excellent mechanical properties, so that the three-dimensional carbon material has a three-dimensional conductive network structure, and a silicon-carbon composite material obtained by combining the three-dimensional carbon material and a silicon material has excellent flexibility and electrochemical properties, and can be used as a lithium ion battery negative electrode material.
In addition, the three-dimensional carbon material has a porous structure and the surface has higher roughness, so the invention utilizes the electrodeposition method to electroplate and deposit silicon on the surface of the three-dimensional carbon material, thereby coating a layer of silicon film on the surface of the three-dimensional carbon material. The electro-deposition method adopted by the invention has simple process and easy realization, does not need to add other binders and conductive agents in the preparation process, reduces the influence of inactive material factors on the electrode performance, and simultaneously does not add inactive materials, thereby being beneficial to improving the capacity of the electrode. In addition, the silicon film is prepared by the electrodeposition method, so that the surface of the three-dimensional carbon material can be covered with a layer of silicon film, and silicon can enter the internal structure of the three-dimensional carbon material, so that the electrical property of the silicon-carbon composite material is further improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a scanning electron microscope image of three-dimensional carbon nanotube paper before and after gold evaporation, wherein a) is a scanning electron microscope image of three-dimensional carbon nanotube paper without gold evaporation, and b) is a scanning electron microscope image of three-dimensional carbon nanotube paper with gold evaporation;
FIG. 2 is a schematic view of the connection structure of the three-electrode system;
FIG. 3 is a scanning electron microscope photograph of the silicon carbon composite of example 1;
FIG. 4 is a flexibility test chart of the three-dimensional carbon nanotube paper after steaming gold in example 1;
FIG. 5 is a specific capacity diagram of a lithium ion battery using the silicon-carbon composite material of example 1 as a negative electrode under different charge and discharge current density conditions;
FIG. 6 is a graph of the first charge-discharge specific capacity at 0.02C for a lithium ion battery using the silicon-carbon composite material of example 1 as the negative electrode;
FIG. 7 is a cycle test chart of a lithium ion battery using the silicon-carbon composite material of example 1 as a negative electrode at a current density of 0.2C;
fig. 8 is a specific capacity diagram of a lithium ion battery (6 h of electroplating) using the silicon-carbon composite material of the present example as a negative electrode under different charge and discharge current density conditions.
Icon: 10-a working electrode; 20-pair of electrodes; 30-reference electrode.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a silicon-carbon composite material, which comprises a three-dimensional carbon material, wherein the surface of the three-dimensional carbon material is coated with a silicon thin film.
According to the invention, the silicon film is covered on the surface of the three-dimensional carbon material, so that the problems of silicon material expansion and easy falling of the silicon material and a current collector can be relieved to a certain extent. The three-dimensional carbon material can buffer the volume expansion and contraction of the silicon material in the charging and discharging processes, and avoids the silicon material from being separated from the three-dimensional carbon material, so that the prepared silicon-carbon composite material is not easy to be separated from a current collector, and the cycle life of the battery is prolonged.
In addition, the three-dimensional carbon material has a porous structure, so that the three-dimensional carbon material can provide an excellent conductive network, and the rapid charge and discharge capacity and the rate capability of the silicon-carbon composite material are improved.
In a preferred embodiment of the present invention, the thickness of the silicon thin film is 0.01 to 500. mu.m. In the above preferred embodiments, the silicon thin film typically has, but not limited to, a thickness of, for example, 0.01 μm, 0.1 μm, 0.5 μm, 1 μm, 10 μm, 50 μm, 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 350 μm, 400 μm, 450 μm or 500 μm.
The thickness of silicon film is undersize, and silicon carbon composite's electric capacity can receive the influence, and the thickness of silicon film is too big, and silicon does not have sufficient accommodation space when taking place the volume expansion in charge-discharge process, consequently can cause the destruction of silicon structure, influences the electrical property.
In a preferred embodiment of the present invention, the three-dimensional carbon material is a flexible three-dimensional carbon material. The flexibility of the silicon-carbon composite material can be improved by adopting the flexible three-dimensional carbon material, so that the prepared silicon-carbon composite material has more excellent flexibility, and can be bent and folded for multiple times at different angles to meet the use requirements of the flexible lithium ion battery.
As a preferred embodiment of the present invention, the flexible three-dimensional carbon material includes any one of carbon nanotube paper, carbon fiber, graphene foam, graphene aerogel or three-dimensional carbon-metal composite.
The carbon nanotube paper is composed of disordered carbon nanotubes with a certain length, has the specific surface area far larger than that of the carbon fiber paper, the strength similar to that of a heat-conducting graphite sheet, and good electric and thermal conductivity and chemical stability.
Carbon Fiber (CF) is a new fiber material of high-strength and high-modulus fiber with carbon content above 95%. It is made up by stacking organic fibres of flake graphite microcrystals along the axial direction of fibre, and making carbonization and graphitization treatment so as to obtain the invented microcrystal graphite material. The carbon fiber is 'soft outside and rigid inside', is lighter than metal aluminum in mass, but higher than steel in strength, and has the characteristics of corrosion resistance and high modulus.
The graphene foam has good performance, and also has good self-supporting capability and structural stability.
The graphene aerogel is a high-strength oxide aerogel and has the characteristics of high elasticity and strong adsorption.
The three-dimensional carbon-metal composite material is a composite material of a three-dimensional carbon material and metal, and the electrical property of the three-dimensional carbon material can be improved after the three-dimensional carbon material and the metal material are compounded.
In a preferred embodiment of the present invention, a metal layer is disposed between the surface of the three-dimensional carbon material and the silicon thin film.
As a preferred embodiment of the present invention, the metal layer is a gold layer.
A metal layer, particularly a gold layer, is additionally arranged between the surface of the three-dimensional carbon material and the silicon thin film, so that the conductivity of the three-dimensional carbon material can be further improved.
In a preferred embodiment of the present invention, the silicon thin film is doped with p-type silicon or n-type silicon.
The conductivity of the silicon-carbon composite material can be further improved by doping p-type silicon or n-type silicon in the silicon thin film.
The second aspect of the invention provides an application of the silicon-carbon composite material in a lithium ion battery negative electrode material.
The three-dimensional carbon material has high specific surface area, good conductivity, excellent flexibility and excellent mechanical properties, so that the three-dimensional carbon material has a three-dimensional conductive network structure, and a silicon-carbon composite material obtained by combining the three-dimensional carbon material and a silicon material has excellent flexibility and electrochemical properties and can be used as a lithium ion battery cathode material.
The invention also provides a lithium ion battery anode material which comprises the silicon-carbon composite material.
The fourth aspect of the invention provides a preparation method of the silicon-carbon composite material, wherein an electrodeposition method is adopted to deposit the silicon film on the surface of the three-dimensional carbon material.
Because the three-dimensional carbon material has a porous structure and the surface has higher roughness, the invention utilizes the electrodeposition method to electroplate and deposit silicon on the surface of the three-dimensional carbon material, thereby coating a layer of silicon film on the surface of the three-dimensional carbon material. The electro-deposition method adopted by the invention has simple process and easy realization, does not need to add other binders and conductive agents in the preparation process, reduces the influence of inactive material factors on the electrode performance, and simultaneously does not add inactive materials, thereby being beneficial to improving the capacity of the electrode. In addition, the silicon film is prepared by the electrodeposition method, so that the surface of the three-dimensional carbon material can be covered with a layer of silicon film, and silicon can enter the internal structure of the three-dimensional carbon material, so that the electrical property of the silicon-carbon composite material is further improved.
As a preferred embodiment of the present invention, the method for preparing the silicon-carbon composite material comprises the following steps:
and (3) placing the three-dimensional carbon material serving as a working electrode in an electroplating solution containing a silicon source, and performing electrodeposition operation by using a three-electrode system under the environment of protective gas to obtain a silicon film on the surface of the three-dimensional carbon material.
In a preferred embodiment of the present invention, the protective gas in the above method for producing a silicon-carbon composite material is argon or nitrogen. Inert gases such as protective argon or nitrogen are used for protection, so that the electroplating solution can be prevented from undergoing redox reaction in the electrodeposition process, and the reaction of a silicon source with water and oxygen is avoided, so that the utilization rate of the electroplating solution is reduced.
As a preferred embodiment of the present invention, the plating solution includes a silicon source, an electrolyte, and an organic solvent. Optionally, the silicon source comprises any one of silicon tetrachloride, trichlorosilane, tetraethoxysilane, trimethoxy silane, dimethylamine silane, silicon bromide or potassium silicofluoride or a combination of at least two of the above.
In a preferred embodiment of the present invention, the concentration of the silicon source in the plating solution is 0.01 to 2 mol/L. in the preferred embodiment, typical but non-limiting concentrations of the silicon source are, for example, 0.01 mol/L, 0.1 mol/L, 0.3 mol/L, 0.5 mol/L, 0.7 mol/L, 1 mol/L, 1.5 mol/L, or 2 mol/L.
Optionally, the electrolyte comprises any one of tetrabutylammonium chloride, tetrabutylammonium perchlorate, lithium perchlorate, or tetrabutylammonium bromide, or a combination of at least two thereof.
In the preferred embodiment of the present invention, the electrolyte is present in the plating solution at a concentration of 0.01 to 2 mol/L. the conductivity of the plating solution can be enhanced by optimizing the concentration of the electrolyte in the plating solution, and typical but non-limiting concentrations of the electrolyte are, for example, 0.01 mol/L, 0.1 mol/L, 0.3 mol/L, 0.5 mol/L, 0.7 mol/L, 1 mol/L, 1.5 mol/L, or 2 mol/L.
Optionally, the organic solvent comprises any one of propylene carbonate, tetrahydrofuran, acetonitrile, dimethyl sulfate, or acetone, or a combination of at least two thereof.
As a preferred embodiment of the present invention, the method for preparing the plating solution comprises the steps of: heating the electrolyte in a protective gas environment, stirring at 120-250 ℃, adding the cooled electrolyte into an organic solvent for dissolving, and then adding a silicon source for stirring to obtain the electroplating solution.
Heating and stirring the electrolyte to fully melt the electrolyte, cooling the electrolyte to room temperature (generally 20-35 ℃) and adding the electrolyte into the organic solvent to fully dissolve the electrolyte in the organic solvent, then adding a silicon source into the mixed solution, and stirring to obtain the electroplating solution.
In a preferred embodiment of the present invention, the protective gas is argon or nitrogen, and may be an inert gas. Inert gases such as protective argon and nitrogen are used for protection, so that the electroplating solution can be prevented from undergoing redox reaction in the electrodeposition process, and the reaction of a silicon source with water and oxygen is avoided, so that the utilization rate of the electroplating solution is reduced.
As a preferred embodiment of the invention, the electroplating solution also comprises any one or a combination of at least two of phosphorus trichloride, phosphorus pentachloride or triethyl phosphate;
or the electroplating solution also comprises triethyl borate and/or aluminum trichloride.
Adding phosphorus trichloride, phosphorus pentachloride or triethyl phosphate into the electroplating solution to form n-type silicon in the deposited silicon film; triethyl borate or aluminum trichloride or a mixture of triethyl borate and aluminum trichloride is added into the electroplating solution to form p-type silicon in the deposited silicon film. P-type silicon or n-type silicon is formed in the silicon thin film to improve the conductivity of the silicon thin film.
As a preferred embodiment of the present invention, the electrodeposition method includes any one of a galvanostatic method, a constant voltage method, a square wave amperometry, a square wave voltagemethod, or a cyclic voltammetry method, or a combination of at least two methods.
As a preferred embodiment of the present invention, the current density during electrodeposition is from-0.1 to-10 mA/cm2The voltage range is-1.5 to-3.5V, and different current and voltage values are selected according to the concentration of a silicon source in the electroplating solution so as to improve the electrodeposition effect.
As a preferred embodiment of the present invention, the counter electrode in the three-electrode system comprises a platinum sheet electrode or a titanium sheet electrode. Optionally, the reference electrode in the three-electrode system comprises a platinum wire electrode, a silver chloride electrode, a calomel electrode, a mercury oxidized mercury electrode, a mercury mercurous sulfate electrode, or a copper sulfate electrode.
As a preferred embodiment of the invention, the method also comprises the steps of washing, soaking, drying and annealing the obtained silicon-carbon composite material after the electrodeposition.
As a preferred embodiment of the present invention, the annealing conditions are: annealing is carried out for 30-40 min under the condition of 330-370 ℃. Impurities which can be attached to the substrate in the electroplating process are removed through annealing, so that the performance of the silicon-carbon composite material is improved.
The silicon carbon composite material of the present invention will be described in further detail with reference to examples.
Example 1
The embodiment is a preparation method of a silicon-carbon composite material, wherein the three-dimensional carbon material in the embodiment is three-dimensional carbon nanotube paper, and the preparation method comprises the following steps:
step a) cutting to 18 × 10mm2The three-dimensional carbon nanotube paper is ultrasonically cleaned for 15min by deionized water and absolute ethyl alcohol respectively, and then is dried for 12h in a vacuum drying oven at the temperature of 60 ℃;
step b): in order to further improve the conductivity of the three-dimensional carbon nanotube paper, a thin layer of gold is evaporated on the surface of the three-dimensional carbon nanotube paper to form a gold layer, and the specific operation comprises the following steps: placing the three-dimensional carbon nanotube paper after vacuum drying in a film steaming machine, steaming gold at 200 ℃, wherein the current is 210A, and the duration is 15 min; then taking out the carbon nanotube paper, replacing one surface of the carbon nanotube paper, and repeating the steps to ensure that two surfaces of the three-dimensional carbon nanotube paper are steamed with gold under the same condition;
fig. 1 shows scanning electron microscope pictures of three-dimensional carbon nanotube paper before and after gold evaporation, in fig. 1, a) is a scanning electron microscope picture of three-dimensional carbon nanotube paper without gold evaporation, and b) is a scanning electron microscope picture of three-dimensional carbon nanotube paper with gold evaporation, and it can be observed from the two pictures that the structure of the three-dimensional carbon nanotube paper is not damaged after a layer of gold is evaporated on the three-dimensional carbon nanotube paper; the conductivity of the three-dimensional carbon nanotube paper after gold evaporation is better, so that the three-dimensional carbon nanotube paper has better cycle performance as a negative electrode;
step c), under the protection of argon in a glove box, putting 0.555g of tetrabutylammonium chloride into a three-electrode bottle, wherein the three-electrode bottle selected in the embodiment is a Teflon bottle, stirring for 4 hours at 130 ℃ on a magnetic stirrer, cooling to room temperature, then adding 20m of L propylene carbonate, dropwise adding 1.2m of L of silicon tetrachloride after dissolving, then stirring for 30min by magnetic force to prepare colorless and transparent silicon-containing electroplating solution, wherein the molar concentration of the tetrabutylammonium chloride is 0.1 mol/L, and the molar concentration of the silicon tetrachloride is 0.5 mol/L;
step d) as shown in FIG. 2, the three-dimensional carbon nanotube paper was sandwiched by the working electrode 10 under the protection of argon gas in a glove box, and the plating work area was 10 × 10mm2And ensuring that the three-dimensional carbon nanotube paper is vertically immersed in the electroplating solution; the counter electrode 20 adopts a high-purity platinum sheet electrode, the reference electrode 30 adopts a high-purity platinum wire electrode, the working electrode 10, the counter electrode 20 and the reference electrode 30 are arranged in an equilateral triangle, the three-dimensional carbon nanotube paper clamped by the working electrode 10, the high-purity platinum sheet electrode of the counter electrode 20 and the platinum wire electrode of the reference electrode 30 are not completely immersed into the electroplating solution, the three-dimensional carbon nanotube paper clamped by the working electrode 10 and the high-purity platinum sheet electrode of the counter electrode 20 are vertically symmetrical, the platinum wire electrode of the reference electrode 30 is close to the three-dimensional carbon nanotube paper as much as possible, and then the wiring of a three-electrode system is connected with an electrochemical workstation outside a glove box; electroplating silicon by constant current method with current density of-3 mA/cm2The electrodeposition time is 4 hours;
step e): and taking out the working electrode several seconds before the electroplating is finished, washing and soaking the working electrode by using propylene carbonate, transferring the working electrode into a transition bin of a glove box, vacuumizing and drying for 20min, then placing the working electrode on a heating table, heating the working electrode to 350 ℃, annealing for 30min, and cooling the working electrode to room temperature to obtain the silicon-carbon composite material capable of being used as the negative electrode material of the flexible lithium ion battery.
After the preparation, the prepared silicon-carbon composite material is weighed and characterized, and the mass of the silicon film electrodeposited on the three-dimensional carbon nanotube paper is about 1.1-2mg through determination, and the thickness of the silicon film is 500 mu m.
Fig. 3 is a picture of a scanning electron microscope of a silicon carbon composite.
Fig. 4 shows the flexibility of the three-dimensional carbon nanotube paper after gold evaporation.
Fig. 5 is a specific capacity diagram of a lithium ion battery using a silicon carbon composite material as a negative electrode under different charge and discharge current density conditions. The data in fig. 5 show that the battery has a higher specific capacity under low current conditions and still has a certain capacity under high current conditions.
FIG. 6 is a diagram of the first charge-discharge specific capacity of a lithium ion battery using a silicon-carbon composite material as a negative electrode under the condition of 0.02C, wherein the first discharge (lithium intercalation) capacity can reach 4434mAh/g, the first charge (lithium deintercalation) capacity can reach 2084mAh/g, the first charge-discharge efficiency is 47%, and test results show that an SEI layer is formed after the first discharge (lithium intercalation).
Fig. 7 is a cycle test chart of a lithium ion battery using a silicon carbon composite material as a negative electrode under a condition that a current density is 0.2C. After 100 cycles, the specific capacity is about 600 mAh/g.
Example 2
The embodiment is a preparation method of a silicon-carbon composite material, wherein the three-dimensional carbon material in the embodiment is three-dimensional carbon nanotube paper, and the preparation method comprises the following steps:
step a) cutting to 18 × 10mm2The three-dimensional carbon nanotube paper is ultrasonically cleaned for 15min by deionized water and absolute ethyl alcohol respectively, and then is dried for 12h in a vacuum drying oven at the temperature of 60 ℃;
b) putting 0.555g of tetrabutylammonium chloride into a three-electrode bottle under the protection of argon in a glove box, wherein the three-electrode bottle selected in the example is a Teflon bottle, stirring for 4 hours at 130 ℃ on a magnetic stirrer, cooling to room temperature, then adding 20m of L propylene carbonate, dropwise adding 1.2m of L silicon tetrachloride after dissolving, and then magnetically stirring for 30min to prepare a colorless and transparent silicon-containing electroplating solution, wherein the molar concentration of the tetrabutylammonium chloride is 0.1 mol/L, and the molar concentration of the silicon tetrachloride is 0.5 mol/L;
c) clamping the three-dimensional carbon nanotube paper by using a working electrode under the protection of argon in a glove box, wherein the working area of electroplating is 10 × 10mm2The counter electrode adopts a high-purity platinum sheet electrode, and the reference electrode adopts a high-purity platinum wire electrode; by usingElectroplating silicon by constant current method with current density of-3 mA/cm2The electrodeposition time is 4 hours;
step d): and taking out the working electrode several seconds before the electroplating is finished, washing and soaking the working electrode by using propylene carbonate, transferring the working electrode into a transition bin of a glove box, vacuumizing and drying for 20min, then placing the working electrode on a heating table, heating the working electrode to 350 ℃, annealing for 30min, and cooling the working electrode to room temperature to obtain the silicon-carbon composite material capable of being used as the negative electrode material of the flexible lithium ion battery.
Example 3
The embodiment is a preparation method of a silicon-carbon composite material, wherein the three-dimensional carbon material in the embodiment is three-dimensional carbon nanotube paper, and the preparation method comprises the following steps:
step a) cutting to 18 × 10mm2The three-dimensional carbon nanotube paper is ultrasonically cleaned for 15min by deionized water and absolute ethyl alcohol respectively, and then is dried for 12h in a vacuum drying oven at the temperature of 60 ℃;
step b): placing the three-dimensional carbon nanotube paper after vacuum drying in a film steaming machine, and carrying out gold steaming treatment at the temperature of 200 ℃, wherein the current is 210A, and the duration is 15 min; then taking out the carbon nanotube paper, replacing one surface of the carbon nanotube paper, and repeating the steps to ensure that gold is evaporated on two surfaces of the carbon nanotube paper under the same condition;
step c), under the protection of argon in a glove box, putting 1.11g of tetrabutylammonium chloride into a three-electrode bottle, stirring for 6 hours at 130 ℃ on a magnetic stirrer, cooling to room temperature, then adding 20m of L propylene carbonate, dropwise adding 1.8m of L silicon tetrachloride after dissolving, and then stirring for 30 minutes by magnetic force to prepare colorless and transparent silicon-containing electroplating solution, wherein the molar concentration of the tetrabutylammonium chloride is 0.2 mol/L, and the molar concentration of the silicon tetrachloride is 0.75 mol/L;
and d) clamping the three-dimensional carbon nanotube paper by using a working electrode under the protection of argon in a glove box, wherein the working area of electroplating is 10 × 10mm2The counter electrode adopts a high-purity platinum sheet electrode, and the reference electrode adopts a high-purity platinum wire electrode; the silicon is electroplated by adopting a constant current method, and the current density is-4 mA/cm2The electrodeposition time is 6 hours;
step e): and taking out the working electrode several seconds before the electroplating is finished, washing and soaking the working electrode by using propylene carbonate, transferring the working electrode into a transition bin of a glove box, vacuumizing and drying for 20min, then placing the working electrode on a heating table, heating the working electrode to 350 ℃, annealing for 30min, and cooling the working electrode to room temperature to obtain the silicon-carbon composite material capable of being used as the negative electrode material of the flexible lithium ion battery.
Fig. 8 is a specific capacity diagram of a lithium ion battery (6 h of electroplating) using the silicon-carbon composite material of the present example as a negative electrode under different charge and discharge current density conditions.
Example 4
The embodiment is a preparation method of a silicon-carbon composite material, wherein a three-dimensional carbon material in the embodiment is a three-dimensional carbon fiber, and the preparation method comprises the following steps:
step a) cutting to 18 × 10mm2The three-dimensional carbon fiber is respectively ultrasonically cleaned for 15min by deionized water and absolute ethyl alcohol, and then is vacuum-dried for 12h by a vacuum drying oven at the temperature of 60 ℃;
b) under the protection of argon in a glove box, putting 0.644g of tetrabutylammonium bromide into a three-electrode bottle, stirring for 6 hours at 150 ℃ on a magnetic stirrer, cooling to room temperature, then adding 20m of L tetrahydrofuran, dropwise adding 1.8m of L silicon tetrachloride after dissolving, and then magnetically stirring for 30 minutes to prepare silicon electroplating solution, wherein the molar concentration of the tetrabutylammonium bromide is 0.1 mol/L, and the molar concentration of the silicon tetrachloride is 0.75 mol/L;
step c) clamping the three-dimensional carbon fiber by using a working electrode under the protection of argon in a glove box, wherein the electroplated working area is 10 × 10mm2The counter electrode adopts a high-purity platinum sheet electrode, and the reference electrode adopts a high-purity platinum wire electrode; electroplating silicon by a constant voltage method, wherein the voltage is-2.3V, and the electrodeposition time is 8 h;
step d): and taking out the working electrode several seconds before the electroplating is finished, washing and soaking the working electrode by using propylene carbonate, transferring the working electrode into a transition bin of a glove box, vacuumizing and drying for 20min, then placing the working electrode on a heating table, heating the working electrode to 350 ℃, annealing for 30min, and cooling the working electrode to room temperature to obtain the silicon-carbon composite material capable of being used as the negative electrode material of the flexible lithium ion battery.
Example 5
The embodiment is a preparation method of a silicon-carbon composite material, wherein the graphene foam is selected as the three-dimensional carbon material in the embodiment, and the preparation method comprises the following steps:
step a) cutting to 18 × 10mm2Respectively ultrasonically cleaning the graphene foam for 20min by using deionized water and absolute ethyl alcohol, and then carrying out vacuum drying for 20h by using a vacuum drying oven at the temperature of 60 ℃;
b) under the protection of argon in a glove box, putting 1.36g of tetrabutylammonium perchlorate into a three-electrode bottle, stirring for 6 hours at 230 ℃ on a magnetic stirrer, cooling to room temperature, then adding 20m of L propylene carbonate, dropwise adding 2.4m of L silicon tetrachloride after dissolving, then stirring for 30 minutes under magnetic force to prepare silicon electroplating solution, and then adding a certain amount of phosphorus trichloride into the electroplating solution, wherein the molar concentration of the tetrabutylammonium perchlorate is 0.2 mol/L, and the molar concentration of the silicon tetrachloride is 1 mol/L;
step c), clamping the graphene foam by using a working electrode under the protection of argon in a glove box, wherein the working area of electroplating is 10 × 10mm2The counter electrode adopts a high-purity platinum sheet electrode, and the reference electrode adopts a high-purity platinum wire electrode; electroplating silicon by square wave current method (one square wave with low current of-3 mA for 0.5s and high current of 0mA for 1s) for 28800 times;
step d): taking out the working electrode several seconds before the electroplating is finished, then washing and soaking the working electrode by using propylene carbonate, then transferring the working electrode into a transition bin of a glove box for vacuumizing and drying for 20min, then placing the working electrode on a heating table, heating the working electrode to 350 ℃ for annealing for 30min, and cooling the working electrode to room temperature to obtain the silicon-carbon composite material which can be used as the negative electrode material of the flexible lithium ion battery, and realizing the p-type doping of the silicon film.
Example 6
The embodiment is a preparation method of a silicon-carbon composite material, wherein the graphene aerogel is selected as the three-dimensional carbon material in the embodiment, and the preparation method comprises the following steps:
step a) cutting to 18 × 10mm2The graphene aerogel is ultrasonically cleaned for 20min by deionized water and absolute ethyl alcohol respectively, and then is dried in a vacuum drying oven at the temperature of 60 DEG CDrying for 20 h;
b) under the protection of argon in a glove box, putting 1.36g of tetrabutylammonium perchlorate into a three-electrode bottle, stirring for 6 hours at 230 ℃ on a magnetic stirrer, cooling to room temperature, then adding 20m of L propylene carbonate, dropwise adding 2.4m of L silicon tetrachloride after dissolving, then stirring for 30 minutes under magnetic force to prepare silicon electroplating solution, and then adding a certain amount of triethyl borate into the electroplating solution, wherein the molar concentration of the tetrabutylammonium perchlorate is 0.2 mol/L, and the molar concentration of the silicon tetrachloride is 1 mol/L;
and c) clamping the graphene aerogel by using a working electrode under the protection of argon in a glove box, wherein the electroplated working area is 10 × 10mm2The counter electrode adopts a high-purity platinum sheet electrode, and the reference electrode adopts a high-purity platinum wire electrode; electroplating silicon by square wave voltage method (one square wave with low voltage of-2.5V and duration of 0.5s and high voltage of 0V and duration of 1s) for 28800 times;
step d): taking out the working electrode several seconds before the electroplating is finished, then washing and soaking the working electrode by using propylene carbonate, then transferring the working electrode into a transition bin of a glove box for vacuumizing and drying for 20min, then placing the working electrode on a heating table, heating the working electrode to 350 ℃ for annealing for 30min, and cooling the working electrode to room temperature to obtain the n-type doped silicon-carbon composite material which can be used as the negative electrode material of the flexible lithium ion battery and realize the n-type doping of the silicon film.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (23)

1. The preparation method of the silicon-carbon composite material is characterized in that the silicon-carbon composite material comprises a three-dimensional carbon material, and a silicon thin film is coated on the surface of the three-dimensional carbon material;
the three-dimensional carbon material is a flexible three-dimensional carbon material and comprises any one of carbon nanotube paper, carbon fiber, graphene foam, graphene aerogel or a three-dimensional carbon-metal composite material;
depositing the silicon film on the surface of the three-dimensional carbon material by adopting an electrodeposition method, comprising the following steps:
and (3) placing the three-dimensional carbon material serving as a working electrode in an electroplating solution containing a silicon source, and performing electrodeposition operation by using a three-electrode system under the environment of protective gas to obtain a silicon film on the surface of the three-dimensional carbon material.
2. The method of claim 1, wherein the silicon thin film has a thickness of 0.01 to 500 μm.
3. The method according to claim 1, wherein a metal layer is disposed between the surface of the three-dimensional carbon material and the silicon thin film.
4. The method according to claim 3, wherein the metal layer is a gold layer.
5. The method of any one of claims 1 to 4, wherein the silicon thin film is doped with p-type silicon or n-type silicon.
6. The method according to claim 1, wherein the protective gas is argon or nitrogen.
7. The method of claim 1, wherein the plating solution comprises a silicon source, an electrolyte, and an organic solvent.
8. The method of claim 7, wherein the silicon source comprises any one or a combination of at least two of silicon tetrachloride, trichlorosilane, tetraethoxysilane, trimethoxymonosilane, dimethylamine silane, silicon bromide, or potassium silicofluoride.
9. The method for producing a silicon-carbon composite material according to claim 7, wherein the concentration of the silicon source in the plating solution is 0.01 to 2 mol/L.
10. The method of claim 7, wherein the electrolyte comprises any one of or a combination of at least two of tetrabutylammonium chloride, tetrabutylammonium perchlorate, lithium perchlorate, or tetrabutylammonium bromide.
11. The method for producing a silicon-carbon composite material according to claim 7, wherein the concentration of the electrolyte in the plating solution is 0.01 to 2 mol/L.
12. The method of claim 7, wherein the organic solvent comprises any one of propylene carbonate, tetrahydrofuran, acetonitrile, dimethyl sulfate, or acetone, or a combination of at least two thereof.
13. The method for preparing a silicon-carbon composite material according to claim 7, wherein the method for preparing the plating solution comprises the steps of: heating the electrolyte in a protective gas environment, stirring at 120-250 ℃, adding the cooled electrolyte into an organic solvent for dissolving, and then adding a silicon source for stirring to obtain the electroplating solution.
14. The method of claim 13, wherein the shielding gas is argon or nitrogen.
15. The method for preparing silicon-carbon composite material according to claim 1, wherein the electroplating solution further comprises any one or a combination of at least two of phosphorus trichloride, phosphorus pentachloride and triethyl phosphate;
or the electroplating solution also comprises triethyl borate and/or aluminum trichloride.
16. The method of any one of claims 6 to 15, wherein the electrodeposition method comprises any one of a galvanostatic method, a potentiostatic method, a square wave amperometry, a square wave voltageometry or a cyclic voltammetry or a combination of at least two methods.
17. The method for preparing a silicon-carbon composite material according to claim 1, wherein the current density is-0.1 to-10 mA/cm during the electrodeposition2The voltage range is-1.5 to-3.5V.
18. The method of claim 1, wherein the counter electrode in the three-electrode system comprises a platinum sheet electrode or a titanium sheet electrode.
19. The method of claim 1, wherein the reference electrode in the three-electrode system comprises a platinum wire electrode, a silver-silver chloride electrode, a calomel electrode, a mercury oxide electrode, a mercury mercuric sulfate electrode, or a copper sulfate electrode.
20. The method for preparing the silicon-carbon composite material according to claim 1, wherein the method further comprises the steps of washing, soaking, drying and annealing the obtained silicon-carbon composite material after the electrodeposition is finished.
21. The method of claim 20, wherein the annealing conditions are as follows: annealing is carried out for 30-40 min under the condition of 330-370 ℃.
22. The application of the silicon-carbon composite material prepared by the preparation method of the silicon-carbon composite material according to any one of claims 1 to 5 in a lithium ion battery negative electrode material.
23. A lithium ion battery negative electrode material, which is characterized by comprising the silicon-carbon composite material prepared by the preparation method of the silicon-carbon composite material according to any one of claims 1 to 5.
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