CN111082006A - Silicon monoxide composite negative electrode material, preparation method thereof and lithium ion battery - Google Patents

Silicon monoxide composite negative electrode material, preparation method thereof and lithium ion battery Download PDF

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CN111082006A
CN111082006A CN201911242759.XA CN201911242759A CN111082006A CN 111082006 A CN111082006 A CN 111082006A CN 201911242759 A CN201911242759 A CN 201911242759A CN 111082006 A CN111082006 A CN 111082006A
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precursor
powder
carbon
silicon
negative electrode
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CN111082006B (en
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夏进阳
李维
潘庆瑞
高红
王亚捷
宋华杰
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Shenzhen Bak Power Battery Co Ltd
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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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • 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 discloses a silicon monoxide composite negative electrode material, a preparation method thereof and a lithium ion battery, which comprises the following steps: s1, providing silicon monoxide powder which is not subjected to disproportionation treatment; s2, performing carbon coating on the silica powder to obtain a first precursor; s3, growing carbon nanofibers on the surface of the first precursor in situ to obtain a second precursor; and S4, carrying out secondary granulation on the second precursor to obtain the silicon monoxide composite negative electrode material. According to the invention, the silica powder is subjected to carbon coating to obtain the first precursor, and the carbon nanofibers grow in situ on the surface of the first precursor, so that the silica powder can be well connected to form a good conductive network, the defect of poor conductivity of the silica is alleviated, the first-time efficiency is further improved, and the volume effect of the silica composite negative electrode material is improved.

Description

Silicon monoxide composite negative electrode material, preparation method thereof and lithium ion battery
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a silicon monoxide composite negative electrode material, a preparation method thereof and a lithium ion battery.
Background
At present, graphite materials are still anode materials used in lithium ion batteries in large quantities, mainly because the graphite materials are rich in raw material sources and have the advantages of high first coulombic efficiency, excellent cycle performance, relatively low cost and the like. However, with the progress of science and technology, in the fields of 3C digital and electric automobiles with the most used lithium ion batteries, higher requirements are provided for the energy density of the lithium ion batteries, but the theoretical gram capacity of the traditional graphite negative electrode material 372mAh/g cannot gradually meet the requirement of high energy density.
The silicon negative electrode is considered as a novel negative electrode material which is very promising and most likely to be industrialized due to the theoretical gram capacity of 4200mAh/g, but the silicon negative electrode has obvious pulverization and shedding during the charging and discharging process due to the huge volume expansion in the lithium releasing process, and the cycle performance is seriously influenced. In order to solve this problem, researchers have made many attempts such as forming a silicon/carbon composite by nano-crystallizing silicon particles and combining them with a carbon material, which may use amorphous carbon, hard and soft carbon, carbon fiber or carbon nanotubes. For example, chinese patent publication No. CN107623110A discloses a method for preparing a silicon-carbon composite material, in which nano-silicon is embedded in hollow through holes of carbon fibers, so that the negative electrode has good structural stability and high electrical conductivity. However, the negative electrode material obtained by the method has high specific surface area, and has negative effects of difficult slurry processing, low coulombic efficiency for the first time and the like. Also, as in chinese patents with publication numbers CN103305965B and CN103311523B, respectively, a method for preparing a silicon-carbon composite material is disclosed, in which nano silicon and carbon fibers are mixed in a solution, a nano composite fiber is obtained by an electrostatic spinning method, and finally a silicon-carbon composite material is obtained by carbonization. However, this method also has the disadvantages of low production efficiency and high cost, and because the nano-silicon and the carbon fiber are simply physically mixed, the binding force is poor, the nano-silicon can not be well dispersed, and the improvement of the cycle performance is limited.
In recent years, a material of silicon monoxide is gradually applied to lithium ion batteries, and the structure of the material is that nano silicon particles are dispersed in a surrounding silicon dioxide matrix, so that silicon dioxide plays a good role in restricting the expansion of silicon, and the total expansion rate (200%) of the material is obviously smaller than that of a pure silicon material (300%) due to the small size of the nano silicon particles. However, the silicon monoxide has the defects of low first efficiency, more side reactions and the like, and is mainly applied to heterogeneous silicon monoxide after disproportionation reaction at present, the distribution uniformity of SiO2 and Si particles formed after disproportionation reaction cannot be strictly controlled, obvious stress difference is formed in the lithium intercalation process of crystalline Si and amorphous SiO2, the polarization in the lithium intercalation process is increased due to the low conductivity and ionic conductivity of SiO2, and the cycle performance of the silicon monoxide-based silicon carbon negative electrode material is influenced.
In view of the above, there is a need to develop a silicon oxide negative electrode material that can effectively improve the kinetics, first-time efficiency and cycle performance of the lithium intercalation process of silicon oxide.
Disclosure of Invention
In order to make up for the defects of the prior art, the invention provides a silicon oxide composite negative electrode material, a preparation method thereof and a lithium ion battery.
The technical problem to be solved by the invention is realized by the following technical scheme:
the preparation method of the silicon oxide composite negative electrode material comprises the following steps:
s1, providing silicon monoxide powder which is not subjected to disproportionation treatment;
s2, performing carbon coating on the silica powder to obtain a first precursor;
s3, growing carbon nanofibers on the surface of the first precursor in situ to obtain a second precursor;
and S4, carrying out secondary granulation on the second precursor to obtain the silicon monoxide composite negative electrode material.
Further, the preparation method of the silicon monoxide powder comprises the following steps: uniformly mixing silicon powder and silicon dioxide powder, heating to generate silicon monoxide gas in an inert atmosphere or a vacuum environment, and cooling to separate out silicon monoxide gas to obtain a silicon monoxide block; and crushing the silicon monoxide block to obtain silicon monoxide powder.
Further, the molar ratio of the silicon powder to the silicon dioxide powder is (0.3-0.7): (0.7-0.3); the particle size D50 of the silicon powder is 1-100 mu m, and the particle size D50 of the silicon dioxide powder is 0.01-1 mu m; the heating temperature is 900-1600 ℃; the chemical formula of the silicon monoxide powder is SiOx, wherein the value of x is 0.8-1.3; the particle size D50 of the silicon oxide powder is 0.1-1 μm.
Further, the carbon coating adopts a method comprising solid phase coating, liquid phase coating or gas phase coating.
Further, the liquid phase coating comprises the following specific steps: dispersing the silica powder in a first organic solvent, gradually adding a soft carbon precursor, fully and uniformly mixing to obtain a first mixed solution, then carrying out spray drying granulation to obtain a compound, and carrying out heat treatment on the compound to obtain a first precursor; the gas phase coating comprises the following specific steps: and (2) introducing the silica powder into a fluidized bed type atmosphere furnace, heating to 600-800 ℃ under the protection of inert gas, introducing a carbon source gas, preserving heat for 0.5-10h, closing the carbon source gas, and cooling to room temperature to obtain a first precursor.
Further, in the liquid phase coating, the first organic solvent is one or more of ethanol, propanol, isopropanol and tetrahydrofuran; the mass ratio of the soft carbon precursor to the silicon monoxide powder is (0.5-5): 1; the soft carbon precursor is one or more of asphalt, citric acid and polyvinylpyrrolidone; the solid content of the first mixed solution is 10-50%; the heat treatment method comprises the following steps: placing the compound in inert gas, and heating at a constant temperature of 500-800 ℃ for 1-10 hours at a heating rate of 0.5-15 ℃/min; in the gas phase coating, the volume ratio of the carbon source gas to the inert gas is (0.1-5): (10-30); the carbon source gas is one or more of acetylene, ethylene, methane and ethane, and the inert gas is one or more of nitrogen, argon and helium.
Further, the in-situ growth of the carbon nanofibers on the surface of the first precursor comprises the following specific steps: dispersing the first precursor in a second organic solvent, gradually adding a catalyst, fully and uniformly mixing to obtain a second mixed solution, and then drying to obtain catalyst-loaded carbon-coated silicon monoxide powder; and placing the obtained catalyst-loaded carbon-coated silica powder in a reactor, heating to 600-850 ℃ under the protection of inert gas, introducing mixed gas of hydrogen and carbon source gas, preserving heat for 0.5-10h, closing the carbon source gas, and cooling to room temperature to obtain a second precursor.
Further, the second organic solvent is one or more of ethanol, methanol, propanol, isopropanol, ethylene glycol and glycerol, and the catalyst is Fe (NO)3)3•9H2O、FeSO4•7H2O、FeCl3•6H2O、Co(NO3)2•6H2O、Ni(NO3)2•6H2One or more of O; the mass ratio of the catalyst to the first precursor is 1 (1-1000); the solid content of the second mixed solution is 10-50%; the volume ratio of the carbon source gas, the hydrogen and the inert gas is (0.1-5) to 1 (10-30), the carbon source gas is one or more of acetylene, ethylene, methane and ethane, and the inert gas is one or more of nitrogen, argon and helium; the length of the nano carbon fiber is 0.01-100 μm, and the diameter is 0.1-20 nm.
Further, the second precursor is granulated for the second time, which comprises the following specific steps: and dispersing the second precursor in a third organic solvent, gradually adding the soft carbon precursor, fully and uniformly mixing to obtain a third mixed solution, and then carrying out spray drying granulation to obtain the secondary granulated silicon oxide composite negative electrode material.
Further, the third organic solvent is one or more of ethanol, propanol, isopropanol and tetrahydrofuran; the soft carbon precursor is one or more of asphalt, citric acid and polyvinylpyrrolidone; the mass ratio of the soft carbon precursor to the second precursor is (0.5-5): 1; the solid content of the third mixed solution is 10-50%; the particle size D50 of the silicon oxide composite negative electrode material is 5-10 μm; the carbon content of the silicon monoxide composite negative electrode material is 5-20%.
The invention also provides a silicon monoxide composite negative electrode material which is prepared by the preparation method.
The invention also provides a lithium ion battery which comprises the silicon monoxide composite negative electrode material.
The invention has the following beneficial effects:
according to the invention, the silica powder is subjected to carbon coating to obtain the first precursor, and the carbon nanofibers grow in situ on the surface of the first precursor, so that the silica powder can be well connected to form a good conductive network, the defect of poor conductivity of the silica is alleviated, the first-time efficiency is further improved, and the volume effect of the silica composite negative electrode material is improved.
In the invention, the non-disproportionated silicon monoxide powder is used as a raw material, and the disproportionation degree of the silicon monoxide is controlled while the carbon nanofibers are generated on the surface by adjusting the reaction temperature in the subsequent processes of carbon coating and surface in-situ growth of the carbon nanofibers, thereby ensuring that the silicon particles in the silicon monoxide material are not obviously grown, reducing SO2The generation of the silicon oxide material can reduce the impedance of the silicon oxide material and improve the dynamic performance of the silicon oxide material.
In the invention, by adopting secondary granulation, the silicon monoxide composite negative electrode material is designed into a structural form of secondary particles, so that the electronic contact inactivation caused by particle pulverization due to volume change in the later cycle process of the silicon monoxide can be relieved better, and the cycle performance of the silicon monoxide can be greatly improved by the interconnection of surface carbon fibers.
The preparation method has simple and convenient process and low cost, and is easy for industrial production.
Drawings
FIG. 1 is a schematic structural diagram of a silicon monoxide composite negative electrode material of the present invention;
fig. 2 is an XRD pattern of example 1 of the present invention and comparative example 4.
In the figure: 1. amorphous carbon formed by secondary granulation, 2 nano carbon fiber grown in situ, 3 silicon oxide powder, 4 amorphous carbon formed by carbon coating.
Detailed Description
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
In a first aspect, the present invention provides a method for preparing a silica composite anode material, comprising the steps of:
s1, providing silicon monoxide powder which is not subjected to disproportionation treatment;
s2, performing carbon coating on the silica powder to obtain a first precursor;
s3, growing carbon nanofibers on the surface of the first precursor in situ to obtain a second precursor;
and S4, carrying out secondary granulation on the second precursor to obtain the silicon monoxide composite negative electrode material.
In step S1, the preparation method of the silica powder includes: uniformly mixing silicon powder and silicon dioxide powder, heating to generate silicon monoxide gas in an inert atmosphere or a vacuum environment, and cooling to separate out silicon monoxide gas to obtain a silicon monoxide block; and crushing the silicon monoxide block to obtain silicon monoxide powder.
Specifically, the molar ratio of the silicon powder to the silicon dioxide powder is (0.3-0.7): (0.7-0.3), for example, it may be 0.3:0.7, 0.4:0.6, 0.5:0.5, 0.6:0.4, 0.7: 0.3. The particle size D50 of the silicon powder is 1-100 μm, and the particle size D50 of the silicon dioxide powder is 0.01-1 μm. The heating temperature is 900-1600 ℃, for example, 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃, 1400 ℃, 1500 ℃, 1600 ℃; the chemical formula of the silicon oxide powder is SiOx, wherein the value of x is 0.8-1.3, and can be 0.8, 0.9, 1, 1.1, 1.2 and 1.3; the particle size D50 of the silicon oxide powder is 0.1-1 μm.
In the invention, silicon vapor and silicon dioxide vapor are generated by the silicon powder and the silicon dioxide powder through heating, and the silicon vapor and the silicon dioxide vapor are subjected to chemical reaction to generate silicon monoxide gas.
The crushing in the present invention is preferably carried out by crushing the silica agglomerates with a jaw crusher to particles having an average particle size of 0.5 to 8mm, and it is understood that the crushing apparatus in the present invention includes, but is not limited to, the above-mentioned crushing apparatus, and other crushing apparatus which are not listed in the present embodiment but are well known to those skilled in the art.
In the present invention, the pulverizing device is preferably a jet mill, and it is understood that the pulverizing device in the present invention includes, but is not limited to, the above-mentioned devices, and other devices which are not listed in the present embodiment but are well known to those skilled in the art, such as a planetary ball mill, a roller mill, a Raymond mill, a mechanical pulverizer, an ultra-low temperature pulverizer, and a superheated steam pulverizer.
In the prior art, the preparation method of the silicon monoxide powder comprises the following steps: heating the mixture of silicon dioxide and silicon to generate silicon monoxide gas, and cooling and precipitating to obtain a silicon monoxide block; carrying out heat treatment at 900-1150 ℃ in an inert environment to carry out disproportionation reaction; then, crushing and crushing are carried out to obtain the silicon oxide powder. The silica powder obtained by this method is heterogeneous silica after disproportionation reaction, and a composite negative electrode material using this as a raw material has a problem of high resistance. In the present invention, oxygen without disproportionation treatment is usedThe method is characterized in that the silicon oxide powder is used as a raw material, the reaction temperature in the subsequent carbon coating and surface in-situ growth carbon nanofiber process is adjusted, the disproportionation degree of silicon oxide is controlled while carbon nanofibers are generated on the surface, the silicon particles in the silicon oxide material are ensured not to grow obviously, and SO is reduced2The generation of the silicon oxide material can reduce the impedance of the silicon oxide material and improve the dynamic performance of the silicon oxide material.
In step S2, the carbon coating is performed by a method including solid phase coating, liquid phase coating, or gas phase coating.
Preferably, the carbon coating adopts a liquid phase coating method, and comprises the following specific steps: the preparation method comprises the steps of dispersing silica powder in a first organic solvent, gradually adding a soft carbon precursor, fully and uniformly mixing to obtain a first mixed solution, then carrying out spray drying granulation to obtain a compound, and carrying out heat treatment on the compound to obtain a first precursor. Specifically, in the liquid phase coating, the first organic solvent is one or more of ethanol, propanol, isopropanol and tetrahydrofuran. The mass ratio of the soft carbon precursor to the silicon monoxide powder is (0.5-5): 1, for example, can be 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5: 1. The soft carbon precursor is one or more of asphalt, citric acid and polyvinylpyrrolidone, and it is understood that the soft carbon precursor in the present invention includes, but is not limited to, the foregoing materials, and other materials that are not listed in this embodiment but are well known to those skilled in the art. The solids content of the first mixed solution is 10 to 50%, for example, 10%, 20%, 30%, 40%, 50%; the solid content of the first mixed solution is not selected to be too high, the aim of spray drying is to uniformly coat a layer of amorphous carbon on the surface of the silicon oxide, and the particle size D50 obtained after spray drying in the step is not used for secondary granulation and is ensured to be basically unchanged compared with the particle size before coating. The heat treatment method comprises the following steps: placing the compound in inert gas, and heating at a constant temperature of 500-800 ℃ for 1-10 hours at a heating rate of 0.5-15 ℃/min. The inert gas is not particularly limited, and may be one or more of nitrogen, argon and helium.
It should be noted that, in order to make the components in the composite obtained by spray drying uniformly distributed, the first mixed solution needs to be fully and uniformly mixed before spray drying, and mechanical stirring can be adopted, wherein the stirring speed is 300-2000 r/min, and the time is 2-8 hours.
More preferably, the carbon coating adopts a gas phase coating method, and the method comprises the following specific steps: and (2) introducing the silica powder into a fluidized bed type atmosphere furnace, heating to 600-800 ℃ under the protection of inert gas, introducing a carbon source gas, preserving heat for 0.5-10h, closing the carbon source gas, and cooling to room temperature to obtain a first precursor. Specifically, in the gas phase cladding, the volume ratio of the carbon source gas to the inert gas is (0.1-5): (10-30), for example, may be 0.1:10, 2:10, 3:10, 4:10, 5:10, 0.1:20, 2:20, 3:20, 4:20, 5:20, 0.1:30, 2:30, 3:30, 4:30, 5: 30; the carbon source gas is one or more of acetylene, ethylene, methane and ethane, and the inert gas is one or more of nitrogen, argon and helium.
It should be noted that, in the gas phase coating, inert gas needs to be introduced in the whole process to ensure that the silicon monoxide powder is not oxidized. Only when the temperature reaches the required temperature, the carbon source gas is introduced in time, and when the required time is reached, the carbon source gas is closed immediately.
When the silicon monoxide is used as a composite negative electrode material, the initial coulomb efficiency is low. According to the invention, the problem of low initial coulombic efficiency is solved by uniformly coating amorphous carbon on the surface of the silica powder through carbon coating of the silica powder, and meanwhile, in the process of preparing the negative pole piece, conductive carbon black is added to form a conductive network combined by point lines, so that the cycle performance is obviously improved.
In step S3, the in-situ growth of the filamentous nanocarbon on the surface of the first precursor specifically includes: dispersing the first precursor in a second organic solvent, gradually adding a catalyst, fully and uniformly mixing to obtain a second mixed solution, and then drying to obtain catalyst-loaded carbon-coated silicon monoxide powder; and placing the obtained catalyst-loaded carbon-coated silica powder in a reactor, heating to 600-850 ℃ under the protection of inert gas, introducing mixed gas of hydrogen and carbon source gas, preserving heat for 0.5-10h, closing the carbon source gas, and cooling to room temperature to obtain a second precursor.
Specifically, the second organic solvent is one or more of ethanol, methanol, propanol, isopropanol, ethylene glycol and glycerol, and the catalyst is Fe (NO)3)3•9H2O、FeSO4•7H2O、FeCl3•6H2O、Co(NO3)2•6H2O、Ni(NO3)2•6H2One or more of O; the mass ratio of the catalyst to the first precursor is 1 (1-1000), and can be, for example, 1:1, 1:10, 1:50, 1:100, 1:200, 1:300, 1:400, 1:500, 1:600, 1:700, 1:800, 1:900, 1: 1000.
The solid content of the second mixed solution is 10 to 50%, for example, 10%, 20%, 30%, 40%, 50%, and in the present invention, the purpose of spray drying is to uniformly distribute the catalyst on the surface of the carbon-coated silica, not for secondary granulation.
The volume ratio of the carbon source gas, the hydrogen gas and the inert gas is (0.1-5): 1: (10-30), and may be, for example, 0.1:1:10, 0.1:1:20, 0.1:1:30, 1:1:10, 1:1:20, 1:1:30, 3:1:10, 3:1:20, 3:1:30, 5:1:10, 5:1:20, 5:1: 30.
The carbon source gas is one or more of acetylene, ethylene, methane and ethane, and the inert gas is one or more of nitrogen, argon and helium; the length of the nano carbon fiber is 0.01-100 μm, and the diameter is 0.1-20 nm.
The drying is preferably, but not limited to, spray drying.
In order to enable the catalyst to be uniformly loaded on the surface of the silica powder, the second mixed solution needs to be sufficiently and uniformly mixed before drying, and mechanical stirring can be adopted, wherein the stirring speed is 300-2000 r/min, and the time is 2-8 hours.
It should be noted that, when the carbon nanofibers are grown in situ on the surface of the first precursor, inert gas needs to be introduced in the whole process to ensure that the silicon monoxide powder is not oxidized. Only when the temperature reaches the required temperature, the carbon source gas is introduced in time, and when the required time is reached, the carbon source gas is closed immediately.
According to the invention, the carbon nanofibers are grown in situ on the surface of the first precursor, so that the bonding force between the carbon nanofibers and the silica powder is stronger, the separation of the silica powder from the carbon fibers in the expansion and contraction processes is prevented, and the defect of poor electron conductivity of the silica is overcome.
In step S4, the second precursor is granulated for the second time specifically by: and dispersing the second precursor in a third organic solvent, gradually adding the soft carbon precursor, fully and uniformly mixing to obtain a third mixed solution, and then carrying out spray drying granulation to obtain the secondary granulated silicon oxide composite negative electrode material.
Specifically, the third organic solvent is one or more of ethanol, propanol, isopropanol and tetrahydrofuran; the soft carbon precursor is one or more of asphalt, citric acid and polyvinylpyrrolidone, and it is understood that the soft carbon precursor in the present invention includes, but is not limited to, the foregoing materials, and other materials that are not listed in this embodiment but are well known to those skilled in the art. The mass ratio of the soft carbon precursor to the second precursor is (0.5-5): 1, for example, can be 0.5:1, 1:1, 2:1, 3:1, 4:1, 5: 1; the solids content of the third mixed solution is 10 to 50%, for example, 10%, 20%, 30%, 40%, 50%; since the purpose of spray drying in this step is secondary granulation, the solid content of the third mixed solution cannot be too low, which would result in failure to form secondary particles. The particle size D50 of the silicon oxide composite negative electrode material is 5-10 μm; the carbon content of the silicon monoxide composite negative electrode material is 5-20%.
According to the invention, by adopting secondary granulation, the volume change of the silicon monoxide in the circulation process can be better relieved, the electronic contact inactivation caused by particle crushing is prevented, and the circulation performance of the silicon monoxide can be greatly improved due to the interconnection of the surface carbon fibers.
In a second aspect, the invention also provides a silicon monoxide composite negative electrode material, which is prepared by the preparation method.
In a third aspect, the invention also provides a lithium ion battery, which comprises the above-mentioned silica composite negative electrode material. The silicon monoxide containing the lithium ion battery conforms to the negative electrode material, so that the lithium ion battery has better dynamic performance, first efficiency and cycle performance.
The present invention will be described in detail with reference to examples, which are only preferred embodiments of the present invention and are not intended to limit the present invention.
Example 1
The preparation method of the silicon oxide composite negative electrode material comprises the following steps:
s1, providing silicon monoxide powder which is not subjected to disproportionation treatment; the preparation method of the silicon monoxide powder comprises the following steps: uniformly mixing silicon powder and silicon dioxide powder, heating to 1400 ℃ in an inert atmosphere or vacuum environment to generate silicon monoxide gas, and cooling and separating out on a deposition plate to obtain a silicon monoxide block; crushing the silicon monoxide block into particles with the average particle size of 0.5-8mm by a jaw crusher, and then crushing and crushing by airflow to obtain silicon monoxide powder with the particle size D50 of 0.1-1 mu m; wherein the molar ratio of the silicon powder to the silicon dioxide powder is 0.5: 0.5; the particle size D50 of the silicon powder is 1-100 mu m, and the particle size D50 of the silicon dioxide powder is 0.01-1 mu m; the chemical formula of the silicon monoxide powder is SiOx, wherein the value of x is 0.8-1.3;
s2, performing carbon coating on the silica powder to obtain a first precursor; the carbon coating adopts a gas phase coating method; the gas phase coating comprises the following specific steps: introducing the silica fume into a fluidized bed type atmosphere furnace, heating to 750 ℃ under the protection of inert gas, introducing a carbon source gas, preserving heat for 6 hours, closing the carbon source gas, and cooling to room temperature to obtain a first precursor; wherein the volume ratio of the carbon source gas to the inert gas is 3: 20; the carbon source gas is acetylene; the inert gas is nitrogen;
s3, preparing a precursor on the surface of the first precursorGrowing carbon nanofibers in situ to obtain a second precursor; the method specifically comprises the following steps: dispersing the first precursor in methanol, gradually adding a catalyst, fully and uniformly mixing to obtain a second mixed solution, and then drying to obtain catalyst-loaded carbon-coated silicon monoxide powder; placing the obtained catalyst-loaded carbon-coated silica powder in a fluidized bed type atmosphere furnace, heating to 800 ℃ under the protection of nitrogen, introducing a mixed gas of hydrogen and a carbon source gas, preserving heat for 6 hours, closing the carbon source gas, and cooling to room temperature to obtain a second precursor; wherein the catalyst is Fe (NO)3)3•9H2O; the mass ratio of the catalyst to the first precursor is 1: 400; the solid content of the second mixed solution was 30%; the volume ratio of the carbon source gas to the hydrogen to the nitrogen is 3:1:2, the carbon source gas is acetylene, the length of the carbon nanofiber is 0.01-100 mu m, and the diameter of the carbon nanofiber is 0.1-20 nm;
s4, carrying out secondary granulation on the second precursor to obtain the silicon monoxide composite negative electrode material, and specifically comprising the following steps: dispersing the second precursor in ethanol, gradually adding citric acid, fully and uniformly mixing to obtain a third mixed solution, and then carrying out spray drying granulation to obtain a secondary granulated silicon oxide composite negative electrode material; wherein the mass ratio of the citric acid to the second precursor is 3: 1; the solid content of the third mixed solution was 30%; the particle size D50 of the silicon oxide composite negative electrode material is 5-10 μm.
Example 2
The preparation method of the silicon oxide composite negative electrode material comprises the following steps:
s1, providing silicon monoxide powder which is not subjected to disproportionation treatment; the preparation method of the silicon monoxide powder comprises the following steps: uniformly mixing silicon powder and silicon dioxide powder, heating to 900 ℃ in an inert atmosphere or vacuum environment to generate silicon monoxide gas, and cooling and separating out on a deposition plate to obtain a silicon monoxide block; crushing the silicon monoxide block into particles with the average particle size of 0.5-8mm by a jaw crusher, and then crushing and crushing by airflow to obtain silicon monoxide powder with the particle size D50 of 0.1-1 mu m; wherein the molar ratio of the silicon powder to the silicon dioxide powder is 0.6: 0.4; the particle size D50 of the silicon powder is 1-100 mu m, and the particle size D50 of the silicon dioxide powder is 0.01-1 mu m; the chemical formula of the silicon monoxide powder is SiOx, wherein the value of x is 0.8-1.3;
s2, performing carbon coating on the silica powder to obtain a first precursor; the carbon coating adopts a liquid phase coating method; the liquid phase coating comprises the following specific steps: dispersing silica fume in ethanol, gradually adding asphalt, fully and uniformly mixing to obtain a first mixed solution, then carrying out spray drying granulation to obtain a compound, and carrying out heat treatment on the compound to obtain a first precursor; the mass ratio of the asphalt to the silicon monoxide powder is 2: 1; the solid content of the first mixed solution was 30%; the heat treatment method comprises the following steps: placing the compound in inert gas, and heating at a constant temperature of 800 ℃ for 6 hours at a heating rate of 5 ℃/min;
s3, growing carbon nanofibers on the surface of the first precursor in situ to obtain a second precursor; the method specifically comprises the following steps: dispersing the first precursor in ethylene glycol, gradually adding a catalyst, fully and uniformly mixing to obtain a second mixed solution, and then drying to obtain catalyst-loaded carbon-coated silicon monoxide powder; placing the obtained catalyst-loaded carbon-coated silica powder in a reactor, heating to 850 ℃ under the protection of helium, introducing a mixed gas of hydrogen and a carbon source gas, preserving heat for 10 hours, closing the carbon source gas, and cooling to room temperature to obtain a second precursor; wherein the catalyst is FeCl3•6H2O; the mass ratio of the catalyst to the first precursor is 1: 1000; the solid content of the second mixed solution is 50%; the volume ratio of the carbon source gas to the hydrogen gas to the helium gas is 5:1:30, the carbon source gas is methane, the length of the carbon nanofiber is 0.01-100 mu m, and the diameter of the carbon nanofiber is 0.1-20 nm;
s4, carrying out secondary granulation on the second precursor to obtain the silicon monoxide composite negative electrode material, and specifically comprising the following steps: dispersing the second precursor in propanol, gradually adding polyvinylpyrrolidone, fully and uniformly mixing to obtain a third mixed solution, and then carrying out spray drying granulation to obtain a secondary granulated silicon oxide composite negative electrode material; wherein the mass ratio of the polyvinylpyrrolidone to the second precursor is 0.5: 1; the solid content of the third mixed solution was 10%; the particle size D50 of the silicon oxide composite negative electrode material is 5-10 μm.
Example 3
The preparation method of the silicon oxide composite negative electrode material comprises the following steps:
s1, providing silicon monoxide powder which is not subjected to disproportionation treatment; the preparation method of the silicon monoxide powder comprises the following steps: uniformly mixing silicon powder and silicon dioxide powder, heating to 1600 ℃ in an inert atmosphere or vacuum environment to generate silicon monoxide gas, and cooling and separating out on a deposition plate to obtain a silicon monoxide block; crushing the silicon monoxide block into particles with the average particle size of 0.5-8mm by a jaw crusher, and then crushing and crushing by airflow to obtain silicon monoxide powder with the particle size D50 of 0.1-1 mu m; wherein the molar ratio of the silicon powder to the silicon dioxide powder is 0.7: 0.3; the particle size D50 of the silicon powder is 1-100 mu m, and the particle size D50 of the silicon dioxide powder is 0.01-1 mu m; the chemical formula of the silicon monoxide powder is SiOx, wherein the value of x is 0.8-1.3;
s2, performing carbon coating on the silica powder to obtain a first precursor; the carbon coating adopts a liquid phase coating method; the liquid phase coating comprises the following specific steps: dispersing silica powder in propanol, gradually adding citric acid, fully and uniformly mixing to obtain a first mixed solution, then carrying out spray drying granulation to obtain a compound, and carrying out heat treatment on the compound to obtain a first precursor; wherein the mass ratio of the citric acid to the silicon monoxide powder is 0.5: 1; the solid content of the first mixed solution is 10-50%; the heat treatment method comprises the following steps: placing the compound in inert gas, and heating at a constant temperature of 500 ℃ for 10 hours at a heating rate of 0.5 ℃/min;
s3, growing carbon nanofibers on the surface of the first precursor in situ to obtain a second precursor; the method specifically comprises the following steps: dispersing the first precursor in propanol, and gradually adding catalystFully and uniformly mixing the agents to obtain a second mixed solution, and then drying to obtain catalyst-loaded carbon-coated silicon monoxide powder; placing the obtained catalyst-loaded carbon-coated silica powder in a reactor, heating to 600 ℃ under the protection of argon, introducing a mixed gas of hydrogen and a carbon source gas, preserving heat for 0.5h, closing the carbon source gas, and cooling to room temperature to obtain a second precursor; wherein the catalyst is FeSO4•7H2O; the mass ratio of the catalyst to the first precursor is 1: 1; the solid content of the second mixed solution was 10%; the volume ratio of the carbon source gas, the hydrogen and the argon is 0.1:1:10, the carbon source gas is ethylene, the length of the carbon nanofiber is 0.01-100 mu m, and the diameter of the carbon nanofiber is 0.1-20 nm;
s4, carrying out secondary granulation on the second precursor to obtain the silicon monoxide composite negative electrode material, and specifically comprising the following steps: dispersing the second precursor in isopropanol, gradually adding asphalt, fully and uniformly mixing to obtain a third mixed solution, and then carrying out spray drying granulation to obtain a secondary granulated silicon oxide composite negative electrode material; wherein the mass ratio of the asphalt to the second precursor is 5: 1; the solid content of the third mixed solution is 10-0%; the particle size D50 of the silicon oxide composite negative electrode material is 5-10 μm.
Example 4
The preparation method of the silicon oxide composite negative electrode material comprises the following steps:
s1, providing silicon monoxide powder which is not subjected to disproportionation treatment; the preparation method of the silicon monoxide powder comprises the following steps: uniformly mixing silicon powder and silicon dioxide powder, heating to 1500 ℃ in an inert atmosphere or vacuum environment to generate silicon monoxide gas, and cooling and separating out on a deposition plate to obtain a silicon monoxide block; crushing the silicon monoxide block into particles with the average particle size of 0.5-8mm by a jaw crusher, and then crushing and crushing by airflow to obtain silicon monoxide powder with the particle size D50 of 0.1-1 mu m; wherein the molar ratio of the silicon powder to the silicon dioxide powder is 0.4: 0.6; the particle size D50 of the silicon powder is 1-100 mu m, and the particle size D50 of the silicon dioxide powder is 0.01-1 mu m; the chemical formula of the silicon monoxide powder is SiOx, wherein the value of x is 0.8-1.3;
s2, performing carbon coating on the silica powder to obtain a first precursor; the carbon coating adopts a gas phase coating method; the gas phase coating comprises the following specific steps: introducing the silica fume into a fluidized bed type atmosphere furnace, heating to 850 ℃ under the protection of inert gas, introducing a carbon source gas, preserving heat for 10 hours, closing the carbon source gas, and cooling to room temperature to obtain a first precursor; wherein the volume ratio of the carbon source gas to the inert gas is 0.1: 10; the carbon source gas is ethylene, and the inert gas is argon;
s3, growing carbon nanofibers on the surface of the first precursor in situ to obtain a second precursor; the method specifically comprises the following steps: dispersing the first precursor in glycerol and methanol, gradually adding a catalyst, fully and uniformly mixing to obtain a second mixed solution, and then drying to obtain catalyst-loaded carbon-coated silica powder; placing the obtained catalyst-loaded carbon-coated silica powder in a reactor, heating to 700 ℃ under the protection of nitrogen, introducing a mixed gas of hydrogen and a carbon source gas, preserving heat for 5 hours, closing the carbon source gas, and cooling to room temperature to obtain a second precursor; wherein the catalyst is Fe (NO)3)3•9H2O and Ni (NO)3)2•6H2O; the mass ratio of the catalyst to the first precursor is 1: 300; the solid content of the second mixed solution was 25%; the volume ratio of the carbon source gas, the hydrogen and the nitrogen is 3:1:10, the carbon source gas is acetylene and ethane, the length of the carbon nanofiber is 0.01-100 mu m, and the diameter of the carbon nanofiber is 0.1-20 nm;
s4, carrying out secondary granulation on the second precursor to obtain the silicon monoxide composite negative electrode material, and specifically comprising the following steps: dispersing the second precursor in tetrahydrofuran, gradually adding the soft carbon precursor, fully and uniformly mixing to obtain a third mixed solution, and then carrying out spray drying granulation to obtain a secondary granulated silicon oxide composite negative electrode material; wherein the third organic solvent is one or more of ethanol, propanol, isopropanol and tetrahydrofuran; the soft carbon precursor is asphalt and polyvinylpyrrolidone; the mass ratio of the soft carbon precursor to the second precursor is 2: 1; the solid content of the third mixed solution was 40%; the particle size D50 of the silicon oxide composite negative electrode material is 5-10 μm.
Comparative example 1
Based on example 1, the difference is only that: step S2 is omitted in this comparative example 1.
Comparative example 2
Based on example 1, the difference is only that: step S3 is omitted in this comparative example 2.
Comparative example 3
Based on example 1, the difference is only that: step S4 is omitted in this comparative example 3.
Comparative example 4
Based on example 1, the difference is only that: the preparation method of the silica powder in the comparative example 4 comprises the following steps: uniformly mixing silicon powder and silicon dioxide powder, heating to 1400 ℃ in an inert atmosphere or vacuum environment to generate silicon monoxide gas, and cooling and separating out on a deposition plate to obtain a silicon monoxide block; carrying out heat treatment at 900-1150 ℃ in an inert environment to carry out disproportionation reaction, crushing the reaction product into particles with the average particle size of 0.5-8mm by a jaw crusher, and then carrying out jet milling and crushing to obtain silicon monoxide powder with the particle size D50 of 0.1-1 mu m; wherein the molar ratio of the silicon powder to the silicon dioxide powder is 0.5: 0.5; the particle size D50 of the silicon powder is 1-100 μm, and the particle size D50 of the silicon dioxide powder is 0.01-1 μm.
Test examples
The materials prepared in examples 1 to 4 and comparative examples 1 to 4 were mixed with graphite in a ratio (after mixing, a gram volume of 500 mAh/g) as a composite negative electrode material, and mixed with a binder of sodium carboxymethylcellulose (CMC), a conductive agent (conductive carbon black), and a binder of styrene-butadiene rubber (SBR) in a ratio of 94:1.5: 2: 2.5, adding a proper amount of deionized water as a dispersing agent, mixing into slurry, coating on a copper foil, and preparing into the negative plate through vacuum drying and rolling. A CR2025 type cell was assembled in a glove box (M Braun) using a pure Li sheet as the negative electrode, Celgard 2300 as the separator, EC: DMC (1: 1 volume ratio, 1 mol/L LiPF6, Samsung) as the electrolyte.
And (3) normal-temperature cycle test: charging at constant temperature of 25 deg.C with 0.1C current at constant current and constant voltage until voltage is 5mV, then discharging at 0.1C current to 1.5V, and repeating charge-discharge cycle for 50 times; and recording the discharge capacity of the battery in the circulation process, and taking the percentage of the 50 th discharge capacity to the first discharge capacity as a capacity retention rate.
Figure DEST_PATH_IMAGE002
In the XRD pattern: the peak at 2 θ =28.4 ° represents the <111> plane diffraction peak of Si. As can be seen from FIG. 2, the peak intensity of example 1 is weaker, which indicates that the disproportionation degree is lower, and the disproportionation degree is lower, which indicates that the nano-silicon particle size is very small, which is beneficial to improving the cycle performance. In contrast, comparative example 4 has a higher peak-to-peak intensity at this point, indicating that the disproportionation degree is larger, and the cycle performance is deteriorated due to the larger size of the nano-silicon particles.
In the invention, in the preparation of the silicon oxide composite negative electrode material, (1) the silicon oxide powder is coated with carbon; (2) growing nano carbon fiber in situ; (3) secondary granulation; (4) controlling the disproportionation degree of the silicon monoxide; the four processes are correlated and inseparable, the four processes influence the dynamic performance of the lithium ion battery together, the technical effect is not the simple superposition of the four processes, the dynamic performance, the first efficiency and the cycle performance are greatly improved, the technical effect of '1 +1+1+ 4' is realized, and the unexpected technical effect is obtained. Absent any of these four processes, none of the cells combines good kinetic, first-time efficiency, and cycling performance.
The above-mentioned embodiments only express the embodiments of the present invention, and the description is more specific and detailed, but not understood as the limitation of the patent scope of the present invention, but all the technical solutions obtained by using the equivalent substitution or the equivalent transformation should fall within the protection scope of the present invention.

Claims (10)

1. The preparation method of the silicon oxide composite negative electrode material is characterized by comprising the following steps of:
s1, providing silicon monoxide powder which is not subjected to disproportionation treatment;
s2, performing carbon coating on the silica powder to obtain a first precursor;
s3, growing carbon nanofibers on the surface of the first precursor in situ to obtain a second precursor;
and S4, carrying out secondary granulation on the second precursor to obtain the silicon monoxide composite negative electrode material.
2. The method for preparing the silica composite negative electrode material according to claim 1, wherein the method for preparing the silica powder comprises: uniformly mixing silicon powder and silicon dioxide powder, heating to generate silicon monoxide gas in an inert atmosphere or a vacuum environment, and cooling to separate out silicon monoxide gas to obtain a silicon monoxide block; and crushing the silicon monoxide block to obtain silicon monoxide powder.
3. The method for preparing the silica composite anode material according to claim 2, wherein the molar ratio of the silicon powder to the silica powder is (0.3-0.7): (0.7-0.3); the particle size D50 of the silicon powder is 1-100 mu m, and the particle size D50 of the silicon dioxide powder is 0.01-1 mu m; the heating temperature is 900-1600 ℃; the chemical formula of the silicon monoxide powder is SiOx, wherein the value of x is 0.8-1.3; the particle size D50 of the silicon oxide powder is 0.1-1 μm.
4. The method for preparing the silica composite anode material according to claim 1, wherein the carbon coating is performed by a method including solid phase coating, liquid phase coating, or vapor phase coating; the liquid phase coating comprises the following specific steps: dispersing the silica powder in a first organic solvent, gradually adding a soft carbon precursor, fully and uniformly mixing to obtain a first mixed solution, then carrying out spray drying granulation to obtain a compound, and carrying out heat treatment on the compound to obtain a first precursor; the gas phase coating comprises the following specific steps: and (2) introducing the silica powder into a fluidized bed type atmosphere furnace, heating to 600-800 ℃ under the protection of inert gas, introducing a carbon source gas, preserving heat for 0.5-10h, closing the carbon source gas, and cooling to room temperature to obtain a first precursor.
5. The preparation method of the silicon monoxide composite negative electrode material as claimed in claim 4, wherein in the liquid phase coating, the first organic solvent is one or more of ethanol, propanol, isopropanol and tetrahydrofuran; the mass ratio of the soft carbon precursor to the silicon monoxide powder is (0.5-5): 1; the soft carbon precursor is one or more of asphalt, citric acid and polyvinylpyrrolidone; the solid content of the first mixed solution is 10-50%; the heat treatment method comprises the following steps: placing the compound in inert gas, and heating at a constant temperature of 500-800 ℃ for 1-10 hours at a heating rate of 0.5-15 ℃/min; in the gas phase coating, the volume ratio of the carbon source gas to the inert gas is (0.1-5): (10-30); the carbon source gas is one or more of acetylene, ethylene, methane and ethane, and the inert gas is one or more of nitrogen, argon and helium.
6. The preparation method of the silicon monoxide composite negative electrode material as claimed in claim 1, wherein the specific steps of growing the carbon nanofibers in situ on the surface of the first precursor are as follows: dispersing the first precursor in a second organic solvent, gradually adding a catalyst, fully and uniformly mixing to obtain a second mixed solution, and then drying to obtain catalyst-loaded carbon-coated silicon monoxide powder; and placing the obtained catalyst-loaded carbon-coated silica powder in a reactor, heating to 600-850 ℃ under the protection of inert gas, introducing mixed gas of hydrogen and carbon source gas, preserving heat for 0.5-10h, closing the carbon source gas, and cooling to room temperature to obtain a second precursor.
7. The method for producing the silica composite negative electrode material according to claim 6, wherein the method comprises a step of forming a porous layer on the surface of the porous layerThe second organic solvent is one or more of ethanol, methanol, propanol, isopropanol, ethylene glycol and glycerol, and the catalyst is Fe (NO)3)3•9H2O、FeSO4•7H2O、FeCl3•6H2O、Co(NO3)2•6H2O、Ni(NO3)2•6H2One or more of O; the mass ratio of the catalyst to the first precursor is 1 (1-1000); the solid content of the second mixed solution is 10-50%; the volume ratio of the carbon source gas, the hydrogen and the inert gas is (0.1-5) to 1 (10-30), the carbon source gas is one or more of acetylene, ethylene, methane and ethane, and the inert gas is one or more of nitrogen, argon and helium; the length of the nano carbon fiber is 0.01-100 μm, and the diameter is 0.1-20 nm.
8. The method for preparing the silicon monoxide composite negative electrode material as claimed in claim 1, wherein the secondary granulation of the second precursor comprises the following specific steps: dispersing the second precursor in a third organic solvent, gradually adding the soft carbon precursor, fully and uniformly mixing to obtain a third mixed solution, and then carrying out spray drying granulation to obtain a secondary granulated silicon oxide composite negative electrode material; wherein the third organic solvent is one or more of ethanol, propanol, isopropanol and tetrahydrofuran; the soft carbon precursor is one or more of asphalt, citric acid and polyvinylpyrrolidone; the mass ratio of the soft carbon precursor to the second precursor is (0.5-5): 1; the solid content of the third mixed solution is 10-50%; the particle size D50 of the silicon oxide composite negative electrode material is 5-10 μm; the carbon content of the silicon monoxide composite negative electrode material is 5-20%.
9. A silica composite negative electrode material characterized by being produced by the production method according to any one of claims 1 to 8.
10. A lithium ion battery comprising the negative electrode material of claim 9.
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