CN114956046B - Silicon-based negative electrode material and preparation method and application thereof - Google Patents

Silicon-based negative electrode material and preparation method and application thereof Download PDF

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CN114956046B
CN114956046B CN202210913472.0A CN202210913472A CN114956046B CN 114956046 B CN114956046 B CN 114956046B CN 202210913472 A CN202210913472 A CN 202210913472A CN 114956046 B CN114956046 B CN 114956046B
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porous carbon
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CN114956046A (en
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潘明军
罗飞
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Tianmulake Excellent Anode Materials Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C01B33/021—Preparation
    • C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
    • C01B33/029—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material by decomposition of monosilane
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    • C01B33/02—Silicon
    • C01B33/021—Preparation
    • C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
    • C01B33/03—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material by decomposition of silicon halides or halosilanes or reduction thereof with hydrogen as the only reducing agent
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    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • 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
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • 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
    • 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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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a silicon-based negative electrode material and a preparation method and application thereof. The preparation method comprises the following steps: dissolving a pyridine compound and a metal salt compound in a molar ratio of 1; dropwise adding the pyridine solution into the metal salt water solution, uniformly mixing, stirring, filtering and drying to obtain a crude product, and washing and drying the crude product to obtain a porous carbonaceous substrate; placing the porous carbonaceous substrate in a reaction vessel, introducing silane substances into the reaction vessel, and preparing nano silicon on the porous carbonaceous substrate through a deposition reaction to obtain a nano silicon deposited porous carbon substrate; and (3) placing the porous carbon substrate for nano silicon deposition in a rotary furnace, introducing an organic gas source under a protective atmosphere to carry out chemical vapor deposition, and carrying out soft carbon coating on the porous carbon substrate for nano silicon deposition to obtain the silicon-based negative electrode material. The obtained silicon-based negative electrode material has the performance of long cycle, high capacity and high first efficiency.

Description

Silicon-based negative electrode material and preparation method and application thereof
Technical Field
The invention relates to the technical field of materials, in particular to a silicon-based negative electrode material and a preparation method and application thereof.
Background
The cathode material is one of the most critical materials of the lithium ion battery technology. The graphite negative electrodes currently on the market have reached their technical bottleneck due to their low gram capacity. And silicon is one of the most promising lithium ion negative electrode materials to replace it. The silicon-based negative electrode material has a series of defects of volume expansion effect, poor conductivity and the like, and practical application of the silicon-based negative electrode material is limited. Therefore, how to improve the silicon-based material and to be able to exert its energy density advantage is one of the focuses of the current research.
Disclosure of Invention
The embodiment of the invention provides a silicon-based negative electrode material and a preparation method and application thereof, silane deposition is directionally induced by the high specific surface area of a porous carbon material with a metal-organic framework structure and the catalytic induction effect of metal cations, meanwhile, the metal cations can be bonded with deposited nano-silicon to form partial metal alloy, the bonding capability with the nano-silicon is increased, and volume expansion can be further relieved by coating with soft carbon through vapor deposition, so that the silicon-based negative electrode material with long circulation, high capacity and high first effect is prepared.
In a first aspect, an embodiment of the present invention provides a method for preparing a silicon-based anode material, including:
dissolving a pyridine compound and a metal salt compound in a molar ratio of 1;
dropwise adding the pyridine solution into the metal salt water solution, uniformly mixing, stirring, filtering and drying to obtain a crude product, and washing and drying the crude product to obtain a porous carbonaceous substrate;
placing the porous carbonaceous substrate in a reaction vessel, introducing a silane substance into the reaction vessel, and preparing nano silicon on the porous carbonaceous substrate through a deposition reaction to obtain a nano silicon deposited porous carbon substrate;
and placing the nano silicon deposition porous carbon substrate in a rotary furnace, introducing an organic gas source under a protective atmosphere to carry out chemical vapor deposition, and carrying out soft carbon coating on the nano silicon deposition porous carbon substrate to obtain the silicon-based negative electrode material.
Preferably, the silicon-based anode material comprises porous carbon, nano silicon and soft carbon; wherein, nanometer silicon is deposited inside the porous carbon, and soft carbon is coated outside the porous carbon; the porous carbon is a metal-organic framework (MOFs) material.
Preferably, the pyridine compound comprises: 4, one or more of 4 '-bipyridine, 2,4, 6-trimethylpyridine, 4-ethylpyridine, 2' -bipyridine, terpyridine, 1, 2-di (4-pyridyl) ethylene, phenanthroline, 2 '-bipyridine-3, 3' -dicarboxylic acid, 2 '-bipyridine-4, 4' -dicarboxylic acid, 2 '-bipyridine-5, 5' -dicarboxylic acid, and 2,2 '-bipyridine-6, 6' -dicarboxylic acid;
the metalThe salt compound comprises: one or more of nitrate, acetate or tetrafluoroborate of metal cations; wherein the metal cations comprise: fe 3+ 、Fe 2+ 、Co 3+ 、Pt 4+ 、Al 3+ 、Cu 2+ 、Zn 2+ 、Hg 2+ 、Cd 2+ 、Ag + 、Cu + Or Au + One or more of them.
Preferably, the silane-based species includes: one or more of tri (trimethylsilyl) silane, monosilane, disilane, tetrafluorosilane, silicon trichloride, chlorosilane, hexamethyldisilane, methylvinyldichlorosilane, dimethylvinylchlorosilane or vinyltrichlorosilane.
Preferably, the deposition reaction comprises vapor deposition or plasma deposition.
Preferably, the temperature of the chemical vapor deposition is 500-800 ℃, and the time is 2-4 hours;
the organic gas source comprises: one or more of methane, acetylene, propylene or propane.
In a second aspect, an embodiment of the present invention provides a silicon-based anode material prepared by the preparation method in the first aspect.
In a third aspect, an embodiment of the present invention provides a lithium battery pole piece, including the silicon-based negative electrode material described in the second aspect.
In a fourth aspect, an embodiment of the present invention provides a lithium battery, including the lithium battery pole piece described in the third aspect.
According to the preparation method of the silicon-based negative electrode material, silane deposition is directionally induced by the high specific surface area of the porous carbon material with the metal-organic framework structure, and meanwhile, metal cations contained in the metal-organic framework material can also catalyze silane to deposit in porous carbon. In addition, metal cations can be bonded with deposited nano silicon to form a partial metal alloy, so that the binding capacity with the nano silicon is increased. Furthermore, the porous carbon skeleton of the metal-organic framework material can provide space for the volume expansion of the silicon-based material and can provide different channels for the transmission of lithium ions. The soft carbon coating is carried out through vapor deposition, so that more complete carbon coating on the surface of the nano silicon is realized, secondary constraint is carried out on porous carbon, and good cycle performance of the silicon-based negative electrode material is ensured. The preparation method is simple, is suitable for application of large-scale industrial production, and has potential market value.
Drawings
The technical solutions of the embodiments of the present invention are further described in detail with reference to the accompanying drawings and embodiments.
Fig. 1 is a flowchart of a method for preparing a silicon-based anode material according to an embodiment of the present invention.
Detailed Description
The invention is further illustrated by the following figures and specific examples, but it should be understood that these examples are for the purpose of illustration only and are not to be construed as in any way limiting the present invention, i.e., as in no way limiting its scope.
The invention provides a preparation method of a silicon-based anode material, which mainly comprises the following steps of:
step 110, dissolving a pyridine compound and a metal salt compound with a molar ratio of 1;
the pyridine compounds comprise: 4.4 '-bipyridine, 2,4, 6-trimethylpyridine, 4-ethylpyridine, 2' -bipyridine, terpyridine, 1, 2-di (4-pyridyl) ethylene, phenanthroline, 2 '-bipyridine-3, 3' -dicarboxylic acid, 2 '-bipyridine-4, 4' -dicarboxylic acid, 2 '-bipyridine-5, 5' -dicarboxylic acid, 2 '-bipyridine-6, 6' -dicarboxylic acid;
the metal salt compound includes: one or more of nitrate, acetate or tetrafluoroborate of metal cations; among them, the metal cations preferably may include: fe 3+ 、Fe 2+ 、Co 3+ 、Pt 4+ 、Al 3+ 、Cu 2+ 、Zn 2+ 、Hg 2+ 、Cd 2+ 、Ag + 、Cu + Or Au + One or more of them.
The pyridine ligand and the metal element are coordinated to generate a two-dimensional crystal structure, and the pyridine compound and the metal salt compound are subjected to coordination reaction under the catalytic action of methanol to form the porous carbonaceous substrate with a metal-organic framework (MOFs) structure.
In the process, the pyridine solution and the metal salt solution are slowly mixed, metal cations are gradually coordinated with the pyridine ligand, and the metal organic framework material is generated through self-assembly crystallization. Specifically, pyridine and copper salt are taken as examples, and pyridine can be coordinated with copper ions mainly through coordination bonding with nitrogen atoms on pyridine molecules. 1mol of copper ions can be coordinated to 4N atoms, i.e. 2mol of pyridine, so the molar ratio is pyridine: metal salt =2:1. the coordination bonding varies from metal salt compound to metal salt compound, and therefore the molar ratio varies accordingly.
Step 120, placing the porous carbonaceous substrate in a reaction vessel, introducing a silane substance into the reaction vessel, and preparing nano silicon on the porous carbonaceous substrate through a deposition reaction to obtain a nano silicon deposited porous carbon substrate;
specifically, the silane-based substance includes: one or more of tri (trimethylsilyl) silane, monosilane, disilane, tetrafluorosilane, silicon trichloride, chlorosilane, hexamethyldisilane, methylvinyldichlorosilane, dimethylvinylchlorosilane or vinyltrichlorosilane.
And introducing protective gas argon while introducing silane substances into the reaction vessel so as to isolate the environment of air or oxygen. When the silane substance is liquid, the protective gas can be used as a carrier gas to carry the liquid silane substance into the reaction vessel.
The deposition reaction may include vapor deposition or plasma deposition.
And step 130, placing the nano silicon deposition porous carbon substrate in a rotary furnace, introducing an organic gas source under a protective atmosphere to perform chemical vapor deposition, and performing soft carbon coating on the nano silicon deposition porous carbon substrate to obtain the silicon-based negative electrode material.
The protective atmosphere is preferably argon, and the organic gas source introduced may be selected from: one or more of methane, acetylene, propylene or propane.
The temperature of the chemical vapor deposition is 500-800 ℃, and the heat preservation time is 2-4 hours. And after heat preservation, closing an organic gas source and cooling to obtain the silicon-based negative electrode material.
The silicon-based negative electrode material comprises porous carbon, nano silicon and soft carbon; depositing nano-silicon inside the porous carbon, and coating soft carbon outside the porous carbon; the porous carbon in the silicon-based negative electrode material is a metal-organic framework (MOFs) material, is an organic-inorganic hybrid material with intramolecular pores formed by self-assembling an organic ligand and metal ions or clusters through coordination bonds, and has the advantages of high specific surface area, highly ordered structure, adjustable pore channel surface and the like.
According to the silicon-based negative electrode material, the gram capacity of the negative electrode active substance can be remarkably improved by the nano silicon, so that an electrochemical device such as a lithium battery using the silicon-based negative electrode material has higher energy density. According to the preparation method, the expansion of the nano silicon can be effectively inhibited through the porous carbon metal-organic frame material, and the high first effect of the cathode material can be ensured.
The application proposes that the temperature of the carbon coating is 500-800 ℃. For example, the temperature may be 500 ℃, 550 ℃,600 ℃, 650 ℃,700 ℃,750 ℃,800 ℃ or any temperature within the range. The applicant finds that if the carbon coating temperature is lower than 500 ℃, the organic gas source is difficult to carbonize completely, the gas source utilization rate is low, and the surface carbon formation contains a large amount of redundant functional groups such as hydroxyl groups, and the like, so that the integrity of the surface coating is influenced. If the carbon coating temperature is higher than 800 ℃, silicon crystal grains are easy to grow, are easy to crack in the circulating process and influence the circulating stability, and inert substances such as silicon carbide and the like are easy to generate at higher temperature to influence the de-intercalation performance of lithium ions; and the formed porous carbon material skeleton is easy to collapse due to overhigh temperature.
The application proposes that the carbon coating time is 2-4 hours. For example, it may be 2 hours, 2.4 hours, 2.8 hours, 3.2 hours, 3.6 hours, 4 hours, or any value therebetween. The applicant has found that if the carbon coating time is less than 2 hours, the carbon content of the matrix is lower, which affects the coating uniformity. If the carbon coating time is longer than 4 hours, the carbon coating time is too long, the carbon content of the substrate is too high, and the carbon layer is easily broken.
The silicon-based negative electrode material prepared by the method can be used as a negative electrode material active substance for a lithium battery negative electrode material and used for preparing a lithium battery negative electrode piece. The negative electrode sheet of the present application further includes a negative current collector, and the present application does not particularly limit the negative current collector as long as the object of the present application can be achieved, and for example, may include, but is not limited to, a copper foil, a copper alloy foil, a nickel foil, a stainless steel foil, a nickel foam, a copper foam, a composite current collector, or the like.
In the present application, a conductive agent may be further included in the lithium battery negative electrode material, and the present application is not particularly limited as long as the object of the present application can be achieved.
The silicon-based negative electrode material can be applied to electrochemical devices such as secondary batteries or ion capacitors and the like. In one specific application, lithium batteries that may employ the silicon-based materials of the present invention as negative electrode materials for lithium batteries may include, but are not limited to: a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery, a lithium ion polymer secondary battery, or the like. By adopting the silicon-based anode material, the electrochemical device has good cycle performance and safety performance.
In order to better understand the technical solutions provided by the present invention, the following specific examples are respectively described as follows, which illustrate specific processes for preparing silicon-based negative electrode materials by using the methods provided by the above embodiments of the present invention, and methods and characteristics for applying the silicon-based negative electrode materials to lithium batteries.
Example 1
Dissolving 4,4' -bipyridine and copper tetrafluoroborate in a molar ratio of 2. Introducing dimethylvinylchlorosilane and protective gas argon into a reactor, depositing in a vapor deposition mode, naturally cooling to obtain a nano silicon deposited porous carbon substrate, namely forming a coating structure of a metal-organic framework material coating a nano silicon material. And then placing the obtained material in a rotary furnace, introducing propylene under the protection of argon atmosphere, preserving the heat at 680 ℃ for 3 hours, and naturally cooling to obtain the silicon-based negative electrode material.
The mass ratio of the obtained silicon-based negative electrode material as a negative electrode active material to carbon black as a conductive additive to an adhesive is 1:1, sodium carboxymethylcellulose and styrene butadiene rubber, in a mass ratio of 95%:2%:3% of the slurry is weighed and put into a beater at room temperature for preparing the slurry. And uniformly coating the prepared slurry on a copper foil. After drying for 2 hours at 50 ℃ in a forced air drying oven, cutting into pole pieces with the size of 8 multiplied by 8mm, and then vacuumizing and drying for 10 hours at 100 ℃ in a vacuum drying oven. And transferring the dried pole piece into a glove box for standby use to assemble a battery.
The simulated cell was assembled in a glove box containing a high purity Ar atmosphere using lithium metal as the counter electrode and 1 mole of LiPF 6 A solution in Ethylene Carbonate (EC)/dimethyl carbonate (DMC) (v: v = 1) was used as an electrolyte to assemble a battery. And (3) carrying out a constant-current charge-discharge mode test by using a charge-discharge instrument, wherein the discharge cut-off voltage is 0.005V, the charge cut-off voltage is 1.5V, the first-week charge-discharge test is carried out at a current density of C/10, and the second-week discharge test is carried out at a current density of C/10.
Under the above conditions, the cycle test was carried out, and the 100-cycle capacity retention ratio was 98%.
Example 2
Dissolving 2,2 '-bipyridine-4, 4' -dicarboxylic acid and zinc nitrate in a molar ratio of 2. Introducing chlorosilane and protective gas argon into a reactor, depositing in a plasma deposition mode, naturally cooling to obtain a nano silicon deposited porous carbon substrate, namely forming a coating structure of a metal-organic framework material coating a nano silicon material. And then placing the obtained material in a rotary furnace, introducing acetylene under the protection of argon atmosphere, keeping the temperature at 600 ℃ for 3 hours, and naturally cooling to obtain the silicon-based negative electrode material.
The battery assembly and cycling tests were performed according to the parameters and test conditions described above in example 1, and the 100-week cycle capacity retention was 97%.
Example 3
Dissolving 1, 2-di (4-pyridyl) ethylene and ferric tetrafluoroborate with a molar ratio of 3. Introducing chlorosilane and protective gas argon into a reactor, depositing in a vapor deposition mode, naturally cooling to obtain a nano silicon deposition porous carbon substrate, namely forming a coating structure of a metal-organic framework material coated nano silicon material. And then placing the obtained material in a rotary furnace, introducing acetylene and propane under the protection of argon atmosphere, preserving the temperature for 2.5 hours at 700 ℃, and naturally cooling to obtain the silicon-based negative electrode material.
The battery assembly and cycling tests were performed according to the parameters and test conditions described above in example 1, and the 100-week cycle capacity retention was 97%.
Example 4
Dissolving 2,2 '-bipyridine-3, 3' -dicarboxylic acid and aluminum nitrate in a molar ratio of 3. Introducing hexamethyldisilane and argon as protective gas into a reactor, depositing in a vapor deposition mode, naturally cooling and cooling to obtain the nano silicon deposition porous carbon substrate, namely forming a coating structure of the nano silicon material wrapped by the metal-organic framework material. And then placing the obtained material in a rotary furnace, introducing propane under the protection of argon atmosphere, preserving the heat at 750 ℃ for 3 hours, and naturally cooling to obtain the silicon-based negative electrode material.
The battery assembly and cycling tests were performed according to the parameters and test conditions described in example 1 above, and the 100-cycle capacity retention rate was 96%.
Example 5
Dissolving phenanthroline and cobalt acetate with a molar ratio of 3. Introducing chlorosilane and protective gas argon into a reactor, depositing in a plasma deposition mode, naturally cooling to obtain the nano silicon deposition porous carbon substrate, namely forming a coating structure of a metal-organic framework material coated nano silicon material. And then placing the obtained material in a rotary furnace, introducing acetylene and propane under the protection of argon atmosphere, preserving the heat of 700 ℃ for 2.5 hours, and naturally cooling to obtain the silicon-based negative electrode material.
The battery assembly and cycling tests were performed according to the parameters and test conditions described above in example 1, and the 100-cycle capacity retention rate was 96%.
Example 6
Dissolving phenanthroline and ferrous nitrate in a molar ratio of 3. Introducing tri (trimethylsilyl) silane and argon as protective gas into a reactor, depositing in a vapor deposition mode, naturally cooling to obtain the nano silicon deposition porous carbon substrate, and forming a coating structure of the nano silicon material wrapped by the metal-organic framework material. And then placing the obtained material in a rotary furnace, introducing acetylene and methane under the protection of argon atmosphere, preserving the heat at 800 ℃ for 2 hours, and naturally cooling to obtain the silicon-based negative electrode material.
The battery assembly and cycling tests were performed according to the parameters and test conditions described in example 1 above, and the 100-cycle capacity retention rate was 96%.
Example 7
Dissolving terpyridine and zinc acetate in a molar ratio of 2. Introducing disilane and protective gas argon into a reactor, depositing in a plasma deposition mode, naturally cooling to obtain the nano silicon deposition porous carbon substrate, namely forming a coating structure of the nano silicon material wrapped by the metal-organic framework material. And then placing the obtained material in a rotary furnace, introducing methane under the protection of argon atmosphere, preserving the heat at 800 ℃ for 3 hours, and naturally cooling to obtain the silicon-based negative electrode material.
The battery assembly and cycling tests were performed according to the parameters and test conditions described in example 1 above, and the 100-cycle capacity retention was 98%.
Example 8
Dissolving 2,2 '-bipyridine-6, 6' -dicarboxylic acid and copper tetrafluoroborate in a molar ratio of 2. Introducing chlorosilane and protective gas argon into a reactor, depositing in a plasma deposition mode, naturally cooling to obtain the nano silicon deposition porous carbon substrate, namely forming a coating structure of a metal-organic framework material coated nano silicon material. And then placing the obtained material in a rotary furnace, introducing acetylene under the protection of argon atmosphere, keeping the temperature at 600 ℃ for 3 hours, and naturally cooling to obtain the silicon-based negative electrode material.
The battery assembly and cycling tests were performed according to the parameters and test conditions described in example 1 above, and the 100-cycle capacity retention was 97%.
The invention also provides comparative examples which are intended to be compared with the examples described above.
Comparative example 1
Introducing dimethylvinylchlorosilane and protective gas argon into a reactor, depositing in a vapor deposition mode, and naturally cooling to obtain the deposited nano silicon material. And then placing the silicon substrate in a rotary furnace, introducing acetylene under the protection of argon atmosphere, preserving heat for 3 hours at 680 ℃, and naturally cooling to obtain the silicon substrate cathode material.
The battery assembly and cycling tests were performed according to the parameters and test conditions described in example 1 above, and the 100-cycle capacity retention was 5%.
Comparative example 2
Dissolving 4,4' -bipyridine and copper tetrafluoroborate in a molar ratio of 2. Introducing dimethylvinylchlorosilane and protective gas argon into a reactor, depositing in a vapor deposition mode, naturally cooling to obtain a nano silicon deposition porous carbon substrate, namely forming a coating structure of a metal-organic framework material coated nano silicon material. And then placing the obtained material in a rotary furnace, introducing propylene under the protection of argon atmosphere, preserving the heat for 2 hours at 950 ℃, and naturally cooling to obtain the silicon-based negative electrode material.
The battery assembly and cycling tests were performed according to the parameters and test conditions described above in example 1, and the 100-week cycle capacity retention was 80%.
As can be seen from examples 1-8, we obtained porous carbon metal-organic framework materials by selecting appropriate pyridine ligands and metal cations for coordination reactions. And then, performing silane deposition by using a plasma method or a vapor deposition method to obtain the porous carbon-coated nano silicon material. And then through effective vapor deposition carbon coating, double coating of porous carbon and soft carbon is formed, and the volume expansion of the nano silicon can be effectively inhibited. Meanwhile, a buffer space is reserved for the expansion of the nano-silicon by the porous structure in the porous carbon metal-organic frame material, so that the cycle performance of the cathode material is very excellent.
Comparative example 1 does not use a metal organic framework material as a substrate and has poor cycle performance.
Comparative example 2 adopts 950 ℃ as the temperature of carbon coating, the metal-organic framework material is damaged by heat and collapses, and an inert substance silicon carbide is generated in the system, thus causing the cycle performance to be reduced sharply.
The preparation method of the silicon-based negative electrode material provided by the invention has the advantages that silane deposition is directionally induced by the high specific surface area of the porous carbon material with the metal-organic framework structure, meanwhile, metal cations contained in the metal-organic framework material can also catalyze silane to deposit in porous carbon to form nano silicon, a buffer zone is provided for the expansion of the nano silicon by gaps of the nano silicon, meanwhile, cracked nano silicon is bound by the metal-organic framework material to provide a space for the volume expansion of the silicon-based material, in addition, the metal cations can be bonded with the deposited nano silicon to form a part of metal alloy, and the binding capacity with the nano silicon is increased. Moreover, the porous carbon skeleton of the metal organic framework material can provide different channels for the transmission of lithium ions, thereby being more beneficial to the transmission of the lithium ions. The carbon coating on the surface of the nano silicon is more complete by vapor deposition of soft carbon coating, the nano silicon deposited on the surface of the porous carbon can be effectively coated, the porous carbon is secondarily bound, and the good cycle performance of the silicon-based cathode material is ensured. Moreover, the preparation method is simple, is suitable for application of large-scale industrial production, and has potential market value.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (8)

1. A preparation method of a silicon-based anode material is characterized by comprising the following steps:
dissolving a pyridine compound and a metal salt compound in a molar ratio of 1;
dropwise adding the pyridine solution into the metal salt water solution, uniformly mixing, stirring, filtering and drying to obtain a crude product, and washing and drying the crude product to obtain a porous carbonaceous substrate;
placing the porous carbonaceous substrate in a reaction vessel, introducing silane substances into the reaction vessel, and preparing nano silicon on the porous carbonaceous substrate through a deposition reaction to obtain a nano silicon deposited porous carbon substrate;
placing the nano silicon deposition porous carbon substrate in a rotary furnace, introducing an organic gas source under a protective atmosphere to carry out chemical vapor deposition, and carrying out soft carbon coating on the nano silicon deposition porous carbon substrate to obtain the silicon-based negative electrode material;
the pyridine compounds comprise: 4, one or more of 4 '-bipyridine, 2,4, 6-trimethylpyridine, 4-ethylpyridine, 2' -bipyridine, terpyridine, 1, 2-di (4-pyridyl) ethylene, phenanthroline, 2 '-bipyridine-3, 3' -dicarboxylic acid, 2 '-bipyridine-4, 4' -dicarboxylic acid, 2 '-bipyridine-5, 5' -dicarboxylic acid, and 2,2 '-bipyridine-6, 6' -dicarboxylic acid;
the metal salt compound includes: one or more of nitrate, acetate or tetrafluoroborate of metal cations; wherein the metal cations comprise: fe 3+ 、Fe 2+ 、Co 3+ 、Pt 4+ 、Al 3+ 、Cu 2+ 、Zn 2+ 、Hg 2+ 、Cd 2+ 、Ag + 、Cu + Or Au + One or more of them.
2. The preparation method according to claim 1, wherein the composition of the silicon-based anode material comprises porous carbon, nano silicon and soft carbon; wherein, nanometer silicon is deposited inside the porous carbon, and soft carbon is coated outside the porous carbon; the porous carbon is a metal-organic framework (MOFs) material.
3. The production method according to claim 1, characterized in that the silane-based substance includes: one or more of tri (trimethylsilyl) silane, monosilane, disilane, tetrafluorosilane, silicon trichloride, chlorosilane, hexamethyldisilane, methylvinyldichlorosilane, dimethylvinylchlorosilane or vinyltrichlorosilane.
4. A method of manufacturing as claimed in claim 1, wherein the deposition reaction comprises vapor deposition or plasma deposition.
5. The method of claim 1, wherein the chemical vapor deposition is carried out at a temperature of 500 to 800 ℃ for 2 to 4 hours;
the organic gas source comprises: one or more of methane, acetylene, propylene or propane.
6. A silicon-based negative electrode material prepared by the preparation method of any one of claims 1 to 5.
7. A lithium battery pole piece, characterized in that the lithium battery pole piece comprises the silicon-based negative electrode material of claim 6.
8. A lithium battery comprising the lithium battery electrode sheet of claim 7.
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