CN110600720A - Composite silicon-based material, negative electrode material, preparation methods of composite silicon-based material and negative electrode material, and lithium ion battery - Google Patents
Composite silicon-based material, negative electrode material, preparation methods of composite silicon-based material and negative electrode material, and lithium ion battery Download PDFInfo
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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Abstract
The invention relates to the technical field of lithium ion batteries, and discloses a preparation method of a composite silicon-based material, which comprises the following steps: the silica fume is disproportionated to convert a portion of the silica fume particles to silicon and silica. The composite silicon-based material prepared by the method can be used as a negative electrode material after being coated with carbon, and has the advantages of high conductivity, low volume expansion rate and good cycle performance. The invention also discloses a negative electrode material and a preparation method thereof, wherein the preparation method comprises the following steps: the composite silicon-based material provided by the invention is subjected to carbon coating. When the cathode material is applied to a lithium ion battery, excellent electrochemical performance can be shown. The lithium ion battery with the negative electrode material is also disclosed, and the lithium ion battery has good performance.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a composite silicon-based material, a negative electrode material, a preparation method of the composite silicon-based material and the negative electrode material, and a lithium ion battery.
Background
Lithium ion batteries are widely used in portable electronic devices because of their high energy density, long cycle life, and no memory effect. However, the conventional graphite cathode material cannot meet the increasing high-performance storage capacity requirement of the lithium ion battery due to the limited theoretical capacity (372 mAh/g). Currently, silicon is an extremely attractive anode material with a low working voltage and a very high theoretical capacity (4200mAh/g), and is one of the candidates for replacing graphite. However, the severe volume expansion of silicon in the charge-discharge cycle process can lead to the crushing of an electrode structure and the falling of an active material, so that the electrical contact between silicon particles and between an active substance and a current collector is lost, the material capacity is rapidly attenuated, and the cycle performance is poor.
Compared with pure silicon materials, the silicon oxide has the advantage of relatively small volume change, and in the process of first lithium insertion and extraction, the silicon oxide particles react with metallic lithium to generate inert phase Li2O and Li4SiO4The volume expansion generated by the alloying of the lithium and the silicon in the long circulation process is relieved to a certain extent. However, the silica has inherent defects, such as low conductivity, large first irreversible capacity, poor cycle performance and the like, which limits the commercial application of the silica.
In view of this, the invention is particularly proposed.
Disclosure of Invention
An object of the present invention is to provide a composite silicon-based material and a method for preparing the same, which is intended to improve at least one defect of a silicon monoxide material.
The invention further aims to provide a negative electrode material and a preparation method thereof, and aims to provide a negative electrode material with good performance.
Still another object of the present invention is to provide a lithium ion battery having good performance.
The invention is realized by the following steps:
in a first aspect, an embodiment of the present invention provides a method for preparing a composite silicon-based material, including:
the silica fume is disproportionated to convert a portion of the silica fume particles to silicon and silica.
In an alternative embodiment, the disproportionation reaction of the silica fume is: and (3) placing the silica powder in an environment of 950-.
In an alternative embodiment, the silica fume has an average particle size of 3 to 8 μm.
In an alternative embodiment, the inert gas is argon.
In a second aspect, embodiments of the present disclosure provide a composite silicon-based material, which is prepared by the preparation method according to any one of the foregoing embodiments.
In a third aspect, embodiments of the present invention provide an anode material, where particles of the anode material include a carbon coating shell and particles of the composite silicon-based material described above, which are coated in the carbon coating shell.
In an alternative embodiment, the carbon clad outer shell comprises a primary carbon clad layer and a secondary carbon clad layer.
In an alternative embodiment, the primary carbon coating layer is carbonized by a coating agent comprising at least one of glucose, sucrose, styrene butadiene rubber, starch, citric acid, and polyvinylpyrrolidone.
In an alternative embodiment, the secondary carbon coating is obtained by carbonizing an organic carbon source including at least one of phenolic resin, glucose, sucrose, pitch, and polyvinylpyrrolidone.
In a fourth aspect, an embodiment of the present invention provides a method for preparing an anode material, including:
the composite silicon-based material according to the foregoing embodiment is carbon-coated.
In an alternative embodiment, the carbon coating comprises a primary carbon coating, and the primary carbon coating method comprises:
and carbonizing the composite silicon-based material precursor for the first time, wherein the composite silicon-based material precursor is a mixed dispersion body in which a conductive agent, a coating agent and the composite silicon-based material are dispersed.
In an alternative embodiment, before the first carbonization of the composite silicon-based material precursor, the preparation of the composite silicon-based material precursor further comprises:
and uniformly mixing and dispersing the composite silicon-based material, water, the conductive agent and the coating agent to obtain mixed slurry.
Drying the mixed slurry to obtain a composite silicon-based material precursor; more preferably, the water is deionized water.
In an alternative embodiment, the conductive agent includes at least one of graphene, carbon nanotubes, and carbon nanofibers.
In an alternative embodiment, the coating agent comprises at least one of glucose, sucrose, styrene butadiene rubber, starch, citric acid, and polyvinylpyrrolidone.
In an alternative embodiment, the mass ratio of the conductive agent to the composite silicon-based material is 1-8: 100.
In an alternative embodiment, the mass ratio of the capping agent to the composite silicon-based material is 3-10: 100.
In an alternative embodiment, the mass ratio of the deionized water to the composite silicon-based material is as follows: 5.67-11.5:1.
In an alternative embodiment, the drying means is spray drying; more preferably, the spray drying inlet temperature is 140-.
In an alternative embodiment, the first carbonization of the composite silicon-based material precursor is: and (3) pyrolyzing the precursor of the composite silicon-based material for 2-4h in an inert gas protective atmosphere at the temperature of 500-850 ℃.
In an alternative embodiment, the inert gas is argon.
In an optional embodiment, the mixing and dispersing uniformly of the composite silicon-based material, the deionized water, the conductive agent and the coating agent to obtain the mixed slurry is as follows:
and mixing the composite silicon-based material with deionized water, and performing ball milling to obtain dispersed slurry.
And mixing and stirring the dispersed slurry, the conductive agent and the coating agent uniformly to obtain mixed slurry.
In an alternative embodiment, the mixing and ball milling time is 3 to 10 hours.
In an alternative embodiment, the step of mixing and stirring the dispersion slurry, the conductive agent and the coating agent uniformly is as follows: mixing the dispersion slurry with the conductive agent and the coating agent, and then stirring in vacuum at the rotation speed of 800-1100rpm for 20-90 min.
In an alternative embodiment, the carbon coating further comprises a secondary carbon coating; the secondary carbon coating method comprises the following steps: and uniformly mixing the primary carbon-coated product with an organic carbon source, and then carrying out secondary carbonization.
In an alternative embodiment, the mass ratio of the primary carbon-coated product to the organic carbon source is: 7-9:1-3.
In an alternative embodiment, the organic carbon source comprises at least one of phenolic resin, glucose, sucrose, pitch, and polyvinylpyrrolidone.
In alternative embodiments, the secondary carbonation is: mixing the primary carbon-coated product with an organic carbon source, and then pyrolyzing the mixture for 2-4h in an inert gas protective atmosphere at the temperature of 700-900 ℃.
In an alternative embodiment, the inert gas is argon.
In a fourth aspect, embodiments of the present disclosure provide an anode material prepared by the preparation method according to any one of the foregoing embodiments.
In a fifth aspect, an embodiment of the present invention provides a lithium ion battery, and a material for preparing a negative electrode of the lithium ion battery includes the negative electrode material provided by the present invention or the negative electrode material prepared by the preparation method of the present invention. The invention has the following beneficial effects:
according to the composite silicon-based material obtained by the design, because the silica fume is placed at high temperature and part of the silica fume is subjected to disproportionation reaction, the particles in the silica fume are converted into silicon, silica and silicon dioxide composite silicon-based particles. Crystalline silicon and silicon dioxide are generated by reaction on original silicon oxide particles, the crystalline silicon increases the capacity of the composite material, the first coulombic efficiency of the material is improved, the silicon dioxide serving as an inert substance can buffer the volume change in the process of lithium intercalation and deintercalation of silicon to a certain extent in the particles, and the cycle performance of the material is improved. Compared with a mixed silicon-based material obtained by directly and physically mixing simple substance silicon, silicon dioxide and silicon monoxide, the composite silicon-based material provided by the application can effectively relieve the volume expansion of the material from the inside of the material and even on the basis of nano particles, and has a certain effect on the improvement of the first coulombic efficiency. Therefore, when the composite silicon-based particles are applied to the negative electrode material, the negative electrode material has the advantages of high conductivity, low volume expansion rate, good cycle performance and small first irreversible capacity.
The composite silicon-based material obtained by the design is prepared by the preparation method of the composite silicon-based material provided by the invention, so that the composite silicon-based material is used as a negative electrode material of a lithium ion battery after being coated by carbon.
According to the negative electrode material obtained through the design, the carbon coating layer is coated with the particles of the composite silicon-based material provided by the embodiment of the invention. Therefore, the cathode material has the advantages of high conductivity, low volume expansion rate, high first coulombic efficiency and good cycle performance.
According to the preparation method of the cathode material obtained through the design, the composite silicon-based material is subjected to carbon coating, so that the prepared cathode material has the advantages of high conductivity, low volume expansion rate and good cycle performance.
According to the lithium ion battery obtained through the design, the material for preparing the negative electrode of the lithium ion battery comprises the negative electrode material provided by the invention or the negative electrode material prepared by the preparation method, so that the lithium ion battery has good performance.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a SiO solid provided in example 1xA cycle charge-discharge curve diagram of the/C composite negative electrode material;
FIG. 2 is the SiO solid provided in example 3xA cycle charge-discharge curve diagram of the/C composite negative electrode material;
FIG. 3 is the SiO solid provided in example 4xA cycle charge-discharge curve diagram of the/C composite negative electrode material;
FIG. 4 is the SiO solid provided in example 5xA cycle charge-discharge curve diagram of the/C composite negative electrode material;
FIG. 5 is a SiO solid provided in example 7xA cycle charge-discharge curve diagram of the/C composite negative electrode material;
FIG. 6 is a SiO solid provided in example 8xA cycle charge-discharge curve diagram of the/C composite negative electrode material;
FIG. 7 is SiO that provided in comparative example 1xA cycle charge-discharge curve diagram of the/C composite negative electrode material;
FIG. 8 is SiO as provided in comparative example 2xA cycle charge-discharge curve diagram of the/C composite negative electrode material;
FIG. 9 is SiO that provided in comparative example 3xA cycle charge-discharge curve diagram of the/C composite negative electrode material;
FIG. 10 is the SiO solid provided in example 3xXRD pattern of the/C composite negative electrode material;
FIG. 11 is the SiO solid provided in example 3xFTIR profile of/C composite anode material;
FIG. 12 is the SiO solid provided in example 3xSEM image of/C composite cathode material;
FIG. 13 is a SiO solid provided in example 6xSEM image of/C composite cathode material.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The composite silicon-based material, the negative electrode material, the preparation method and the application thereof provided by the embodiment of the invention are described in detail below.
The preparation method of the composite silicon-based material provided by the embodiment of the invention comprises the following steps:
carrying out disproportionation reaction on the silica powder to convert the silica particles in the silica powder into composite silicon-based particles containing silica, silicon and silicon dioxide.
In the composite silicon-based particles obtained after the disproportionation reaction of the silica fume powder, the silica fume powder is placed at a high temperature to cause a part of the silica fume powder to undergo the disproportionation reaction, so that the particles in the silica fume powder are converted into silicon, silica and silicon dioxide composite silicon-based particles. Crystalline silicon and silicon dioxide are generated on the original silicon monoxide particles through reaction, the crystalline silicon increases the capacity of the composite material, the first coulombic efficiency of the material is improved, the silicon dioxide serving as an inert substance can buffer the volume change in the process of lithium intercalation and deintercalation of silicon to a certain extent in the particles, and the cycle performance of the material is improved. Compared with a mixed silicon-based material obtained by directly and physically mixing simple substance silicon, silicon dioxide and silicon monoxide, the composite silicon-based material provided by the application can effectively relieve the volume expansion of the material from the inside of the material and even on the basis of nano particles, and has a certain effect on the improvement of the first coulombic efficiency.
Preferably, in order to further improve the performance of the composite silicon-based material, the average particle size of the silica particles in the silica powder is 3-8 μm.
Preferably, the disproportionation reaction is: and (3) placing the silica powder in an environment of 950-. In the heating temperature and the reaction time, the ratio of the generated silicon and the silicon dioxide in the generated composite silicon-based particles is in a proper range, so that the composite silicon-based particles have more excellent performance when being applied to a negative electrode material. Preferably, the inert gas is argon gas commonly used.
The composite silicon-based material provided by the embodiment of the invention is prepared by adopting the preparation method of the composite silicon-based material provided by the embodiment of the invention. The composite silicon-based material is coated by carbon, so that the lithium ion battery cathode material is high in conductivity, low in volume expansion rate and good in cycle performance.
The negative electrode material provided by the embodiment of the invention comprises a carbon coating shell and composite silicon-based material particles coated in the carbon coating shell.
The particles of the cathode material are the particles of the composite silicon-based material coated in the carbon coating shell. Therefore, the cathode material has the advantages of high conductivity, low volume expansion rate, good cycle performance and small first irreversible capacity.
Preferably, the carbon clad outer shell comprises a primary carbon clad layer and a secondary carbon clad layer. Specifically, the primary carbon coating layer is obtained by carbonizing a coating agent, and the coating agent comprises at least one of glucose, sucrose, styrene butadiene rubber, starch, citric acid and polyvinylpyrrolidone. The secondary carbon coating layer is obtained by carbonizing an organic carbon source, wherein the organic carbon source comprises at least one of phenolic resin, glucose, sucrose, asphalt and polyvinylpyrrolidone.
The cathode material is coated by carbon twice, the surface is uniform and compact, the direct contact between silicon-based particles and electrolyte can be effectively avoided, the probability of side reaction is reduced, the stress effect generated in the charging and discharging process can be buffered, and the stability of the cathode material structure is ensured.
The preparation method of the negative electrode material provided by the embodiment of the invention comprises the following steps:
the composite silicon-based material provided by the invention is subjected to carbon coating.
The method specifically comprises the following steps:
s1, primary carbon coating
And placing the composite silicon-based material and deionized water in a mechanical ball milling device for ball milling. So that the particle size of the composite silicon-based particles is reduced to below 5 mu m, and the mechanical ball milling time is 3-10h, and the dispersion slurry is obtained after uniform dispersion. Feeding the composite silicon-based material and the deionized water according to the mass ratio of 1: 5.67-11.5.
And adding the conductive agent and the coating agent into the dispersion slurry for vacuum stirring at the rotation speed of 800-1100rpm for 20-90min, so as to ensure that the mixed slurry is obtained after uniform mixing and dispersion.
In order to ensure good conductivity of the finished product, the conductive agent preferably comprises at least one of graphene, carbon nanotubes and carbon nanofibers. In order to ensure that the conductivity is better and the addition amount of the conductive agent is not too much to influence the performance of the cathode material, the mass ratio of the conductive agent to the composite silicon-based material is preferably 1-8: 100. In order to ensure that the carbon layer formed after the primary coating has good structural characteristics, the coating agent preferably comprises at least one of glucose, sucrose, styrene butadiene rubber, starch, citric acid and polyvinylpyrrolidone. In order to fully coat the particles in the composite silicon-based material and not to make the coating amount too large to cause the carbon layer to be too thick to influence the performance of the cathode material, the mass ratio of the coating agent to the composite silicon-based material is preferably 3-10: 100.
And carrying out spray drying on the mixed slurry, wherein the inlet temperature of the spray drying is 140-300 ℃, and the outlet temperature of the spray drying is 80-160 ℃ so as to obtain the composite silicon-based material precursor. The drying mode adopts spray drying, so that the particle size distribution of the particles in the obtained precursor of the composite silicon-based material is more uniform.
And carrying out primary carbonization on the composite silicon-based material precursor to obtain a primary carbon-coated product. The primary carbonization method comprises the following steps: and putting the precursor of the composite silicon-based material in a tubular furnace under the protective atmosphere of inert gas, and pyrolyzing for 1-3h in the environment of 500-850 ℃, wherein the heating rate in the pyrolysis process is 5 ℃/min. Preferably, the inert gas is argon.
S2, secondary carbon coating
And uniformly mixing the primary carbon-coated product with an organic carbon source, and then carrying out secondary carbonization. The secondary carbonization method comprises the following specific steps:
and mixing the primary carbon-coated product with an organic carbon source, placing the mixture in a tubular furnace under the protection of inert gas, raising the temperature of the tubular furnace to 700-900 ℃, and pyrolyzing for 2-4h to obtain the secondary carbon-coated composite silicon-based negative electrode material. The temperature is raised in a tube furnace at a rate of 10 ℃/min. Preferably, the inert gas is argon.
The pyrolysis temperature of the organic carbon source in the tubular furnace is not too high, and the temperature is not too highToo high SiOxThe crystal Si in the particles reacts with carbon to generate SiC, and the generated SiC serves as an inert phase in the process of lithium intercalation and deintercalation of the composite material, so that the charge and discharge capacity of the composite material is reduced, and the electrochemical performance of the composite material is influenced.
Preferably, the organic carbon source comprises at least one of phenolic resin, glucose, sucrose, pitch and polyvinylpyrrolidone.
Preferably, in order to ensure that the secondary carbon coating reaches a sufficient coating amount without affecting the overall performance of the material, the mass ratio of the primary carbon coating product to the organic carbon source is as follows: 7-9:1-3.
In the primary carbon coating process, the coating agent is pyrolyzed on the surfaces of the composite silicon-based particles at high temperature to form a carbon layer, and the carbon layer can be formed to prevent the composite material particles from being in direct contact with electrolyte to a certain extent, so that the probability of side reaction is reduced.
After the secondary carbonization, the organic carbon source forms an amorphous carbon layer on the surface of the primary carbon-coated product again, the amorphous carbon layer is uniformly coated on the surface of the particles, so that the full coating can be further fully ensured, the surface of the carbon layer is uniform and compact, and the phenomenon of nonuniform coating possibly caused by the primary coating is compensated.
In the preferred embodiment of the present invention, when the primary carbon-coated coating agent is selected from the above-mentioned materials, and the secondary carbon-coated organic carbon source is selected from the above-mentioned materials, the electrochemical performance of the prepared anode material can be optimized.
On one hand, the lithium oxide, the lithium silicate and the SEI film generated in the first circulation process are irreversible processes and are the main reasons for generating irreversible capacity, the carbon coating layer formed by carbon coating has uniform and compact surface and reduced specific surface area, the irreversible process for generating the SEI film is relatively reduced, and meanwhile, the carbon coating also avoids the direct contact of a silicon-based material and electrolyte, reduces the probability of side reaction, reduces the first irreversible capacity and improves the first coulombic efficiency of the composite material. On the other hand, the amorphous carbon layer not only improves the conductivity of the material, but also plays a role in buffering the volume expansion of the material in the process of lithium intercalation and deintercalation, improves the electrochemical performance of the composite material and prolongs the cycle life of the composite material. Furthermore, the conductive agent added in the carbon coating process is used as a transmission channel of ions and electrons, so that the conductivity of the prepared material can be further remarkably increased.
The negative electrode material provided by the embodiment of the invention is prepared by the preparation method of the negative electrode material provided by the embodiment of the invention. The cathode material has the characteristics of high conductivity, low volume expansion rate and good cycle performance.
The embodiment of the invention also provides a lithium ion battery, and the material for preparing the negative electrode of the lithium ion battery comprises the negative electrode material provided by the invention or the negative electrode material prepared by the preparation method provided by the invention, so that the lithium ion battery has good performance. The lithium ion battery provided by the embodiment of the invention particularly comprises a button type lithium ion battery.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The composite silicon-based material, the negative electrode material and the preparation method thereof provided by the embodiment are as follows:
the preparation method of the composite silicon-based material comprises the following steps: heating the silicon monoxide with the average grain diameter of 8 mu m to 1000 ℃ under the protection of argon, and preserving the heat for 3h, wherein the heating rate is 10 ℃/min to obtain the composite silicon-based material.
The preparation method of the cathode material comprises the following steps:
putting 400g of the composite silicon-based material and deionized water into a ball mill according to the proportion of 1:9 for ball milling for 5 hours to obtain uniform dispersed slurry; adding 40g of glucose and 8g of carbon nano tube into the obtained dispersed slurry, stirring in vacuum at the rotating speed of 1000rpm for 20min, uniformly mixing, and spray-drying to obtain a composite silicon-based material precursor, wherein the inlet temperature of the spray-drying is 280 ℃, and the outlet temperature is 120 ℃; putting the composite silicon-based material precursor into a tubular furnace, heating to 700 ℃ under the protection of argon, keeping the temperature for 2h at the heating speed of 5 ℃/min to obtain a primary carbon-coated product, mixing the primary carbon-coated product with asphalt according to the mass ratio of 9:1, putting the mixture into the tubular furnace, heating to 850 ℃ at the temperature of 10 ℃/min, keeping the temperature for 3h, and cooling to room temperature along with the furnace to obtain the secondary carbon-coated cathode material.
Example 2
The composite silicon-based material, the negative electrode material and the preparation method thereof provided by the embodiment are as follows:
the preparation method of the composite silicon-based material comprises the following steps: heating the silicon monoxide with the average grain diameter of 3 mu m to 950 ℃ under the protection of argon, and preserving the heat for 4h, wherein the heating rate is 25 ℃/min to obtain the composite silicon-based material.
The preparation method of the cathode material comprises the following steps:
putting 300g of the composite silicon-based material and deionized water into a ball mill according to the proportion of 1:9 for ball milling for 1h to obtain uniform dispersed slurry; adding 15g of sucrose and 3g of graphene into the obtained dispersed slurry, stirring in vacuum at the rotating speed of 800rpm for 90min, uniformly mixing, and performing spray drying to obtain a composite silicon-based material precursor, wherein the inlet temperature of the spray drying is 280 ℃, and the outlet temperature is 120 ℃; putting the composite silicon-based material precursor into a tubular furnace, heating to 750 ℃ under the protection of argon, keeping the temperature for 3h at the heating speed of 10 ℃/min to obtain a primary carbon-coated product, mixing the primary carbon-coated product with asphalt according to the mass ratio of 9:1, putting the mixture into the tubular furnace, heating to 850 ℃ at the temperature of 5 ℃/min, keeping the temperature for 3h, and cooling to room temperature along with the furnace to obtain the secondary carbon-coated cathode material.
Example 3
The composite silicon-based material, the negative electrode material and the preparation method thereof provided by the embodiment are as follows:
the preparation method of the composite silicon-based material comprises the following steps: heating the silicon monoxide with the average grain diameter of 5 mu m to 1000 ℃ under the protection of argon, and preserving the heat for 3h, wherein the heating rate is 20 ℃/min to obtain the composite silicon-based material.
The preparation method of the cathode material comprises the following steps:
putting 200g of the composite silicon-based material and deionized water into a ball mill according to the proportion of 1:9 for ball milling for 4 hours to obtain uniform dispersed slurry; adding 15g of styrene butadiene rubber and 8g of carbon nano tubes into the obtained dispersed slurry, stirring in vacuum at the rotating speed of 1000rpm for 30min, uniformly mixing, and performing spray drying to obtain a composite silicon-based material precursor, wherein the inlet temperature of the spray drying is 320 ℃, and the outlet temperature is 150 ℃; putting the composite silicon-based material precursor into a tubular furnace, heating to 850 ℃ under the protection of argon, keeping the temperature for 1h at the heating speed of 5 ℃/min to obtain a primary carbon-coated product, mixing the primary carbon-coated product with asphalt according to the mass ratio of 9:1, putting the mixture into the tubular furnace, heating to 800 ℃ at the temperature of 10 ℃/min, keeping the temperature for 3h, and cooling to room temperature along with the furnace to obtain the secondary carbon-coated cathode material.
Example 4
The composite silicon-based material, the negative electrode material and the preparation method thereof provided by the embodiment are as follows:
the preparation method of the composite silicon-based material comprises the following steps: heating the silicon monoxide with the average grain diameter of 5 mu m to 1000 ℃ under the protection of argon, and preserving the heat for 3h, wherein the heating rate is 30 ℃/min to obtain the composite silicon-based material.
The preparation method of the cathode material comprises the following steps:
putting 300g of the composite silicon-based material and deionized water into a ball mill according to the proportion of 1:9 for ball milling for 3 hours to obtain uniform dispersed slurry; adding 90g of phenolic resin and 12g of graphene into the obtained dispersed slurry, stirring in vacuum at the rotating speed of 800rpm for 50min, uniformly mixing, and spray-drying to obtain a composite silicon-based material precursor, wherein the inlet temperature of the spray-drying is 260 ℃ and the outlet temperature is 120 ℃; putting the composite silicon-based material precursor into a tubular furnace, heating to 800 ℃ under the protection of argon, keeping the temperature for 2h at the heating speed of 10 ℃/min to obtain a primary carbon-coated product, mixing the primary carbon-coated product with asphalt according to the mass ratio of 8:1, putting the mixture into the tubular furnace, heating to 800 ℃ at the temperature of 10 ℃/min, keeping the temperature for 3h, and cooling to room temperature along with the furnace to obtain the secondary carbon-coated cathode material.
Example 5
The composite silicon-based material, the negative electrode material and the preparation method thereof provided by the embodiment are as follows:
the preparation method of the composite silicon-based material comprises the following steps: heating the silicon monoxide with the average grain diameter of 5 mu m to 980 ℃ under the protection of argon, and preserving the heat for 3h, wherein the heating rate is 30 ℃/min to obtain the composite silicon-based material.
The preparation method of the cathode material comprises the following steps:
putting 300g of the composite silicon-based material and deionized water into a ball mill according to the proportion of 1:9 for ball milling for 2 hours to obtain uniform dispersed slurry; adding 15g of citric acid and 9g of graphene into the obtained dispersed slurry, stirring in vacuum at the rotation speed of 900rpm for 70min, uniformly mixing, and spray-drying to obtain a composite silicon-based material precursor, wherein the inlet temperature of the spray-drying is 290 ℃, and the outlet temperature is 130 ℃; putting the composite silicon-based material precursor into a tubular furnace, heating to 750 ℃ under the protection of argon, keeping the temperature for 3h at the heating speed of 5 ℃/min to obtain a primary carbon-coated product, mixing the primary carbon-coated product with asphalt according to the mass ratio of 7:3, putting the mixture into the tubular furnace, heating to 750 ℃ at the temperature of 5 ℃/min, keeping the temperature for 3h, and cooling to room temperature along with the furnace to obtain the secondary carbon-coated cathode material.
Example 6
The composite silicon-based material, the negative electrode material and the preparation method thereof provided by the embodiment are as follows:
the preparation method of the composite silicon-based material comprises the following steps: and heating the silicon monoxide with the average grain diameter of 3 mu m to 1050 ℃ under the protection of argon, and preserving the heat for 3 hours at the heating rate of 25/min to obtain the composite silicon-based material.
The preparation method of the cathode material comprises the following steps:
putting 200g of the composite silicon-based material and deionized water into a ball mill according to the proportion of 1:9 for ball milling for 4 hours to obtain uniform dispersed slurry; adding 20g of styrene butadiene rubber and 8g of carbon nano tubes into the obtained dispersed slurry, stirring in vacuum at the rotating speed of 1000m for 40min, uniformly mixing, and performing spray drying to obtain a composite silicon-based material precursor, wherein the inlet temperature of the spray drying is 300 ℃, and the outlet temperature is 140 ℃; putting the composite silicon-based material precursor into a tubular furnace, heating to 800 ℃ under the protection of argon, keeping the temperature for 3h at the heating speed of 5 ℃/min to obtain a primary carbon-coated product, mixing the primary carbon-coated product with asphalt according to the mass ratio of 8:2, putting the mixture into the tubular furnace, heating to 800 ℃ at the temperature of 5 ℃/min, keeping the temperature for 3h, and cooling to room temperature along with the furnace to obtain the secondary carbon-coated cathode material.
Example 7
The composite silicon-based material, the negative electrode material and the preparation method thereof provided by the embodiment are as follows:
the preparation method of the composite silicon-based material comprises the following steps: heating the silicon monoxide with the average grain diameter of 3 mu m to 990 ℃ under the protection of argon, and preserving the heat for 3 hours at the heating rate of 35/min to obtain the composite silicon-based material.
The preparation method of the cathode material comprises the following steps:
putting 200g of the composite silicon-based material and deionized water into a ball mill according to the proportion of 1:9 for ball milling for 4 hours to obtain uniform dispersed slurry; adding 6g of citric acid and 4g of carbon nano tubes into the obtained dispersion slurry, stirring in vacuum at the rotation speed of 900rpm for 60min, uniformly mixing, and spray-drying to obtain a composite silicon-based material precursor, wherein the inlet temperature of the spray-drying is 290 ℃, and the outlet temperature is 130 ℃; putting the composite silicon-based material precursor into a tubular furnace, heating to 750 ℃ under the protection of argon, keeping the temperature for 3h at the heating speed of 5 ℃/min to obtain a primary carbon-coated product, mixing the primary carbon-coated product with asphalt according to the mass ratio of 85:15, putting the mixture into the tubular furnace, heating to 850 ℃ at the temperature of 5 ℃/min, keeping the temperature for 3h, and cooling to room temperature along with the furnace to obtain the secondary carbon-coated cathode material.
Example 8
The composite silicon-based material, the negative electrode material and the preparation method thereof provided by the embodiment are as follows:
the preparation method of the composite silicon-based material comprises the following steps: and heating the silicon monoxide with the average grain diameter of 5 mu m to 1050 ℃ under the protection of argon, and preserving the heat for 3 hours at the heating rate of 30/min to obtain the composite silicon-based material.
The preparation method of the cathode material comprises the following steps:
putting 400g of the composite silicon-based material and deionized water into a ball mill according to the proportion of 1:9 for ball milling for 2 hours to obtain uniform dispersed slurry; adding 80g of styrene butadiene rubber and 8g of carbon nano tubes into the obtained dispersed slurry, stirring in vacuum at the rotating speed of 1100rpm for 30min, uniformly mixing, and performing spray drying to obtain a composite silicon-based material precursor, wherein the inlet temperature of the spray drying is 300 ℃, and the outlet temperature is 150 ℃; putting the composite silicon-based material precursor into a tubular furnace, heating to 800 ℃ under the protection of argon, keeping the temperature for 3h at the heating speed of 5 ℃/min to obtain a primary carbon-coated product, mixing the primary carbon-coated product with asphalt according to the mass ratio of 8:2, putting the mixture into the tubular furnace, heating to 850 ℃ at the temperature of 5 ℃/min, keeping the temperature for 3h, and cooling to room temperature along with the furnace to obtain the secondary carbon-coated cathode material.
Example 9
This embodiment is substantially the same as embodiment 1 except that:
in the preparation process of the composite silicon-based material, the disproportionation reaction temperature is 1200 ℃, and the reaction time is 1 h.
The preparation process of the anode material comprises the following steps: putting the composite silicon-based material and deionized water into a ball mill according to the proportion of 1:5.67 for ball milling for 6 hours; in the primary carbon coating process, the adding amount of the carbon nano tube is 32 g; the inlet temperature of spray drying is 140 ℃, and the outlet temperature is 80 ℃; putting the primary carbonization process into a tubular furnace, wherein the pyrolysis temperature is 500 ℃, and the pyrolysis time is 3 h; the secondary carbonization process is put into a tube furnace, the pyrolysis temperature is 700 ℃, and the pyrolysis time is 4 h.
Example 10
This embodiment is substantially the same as embodiment 1 except that:
in the preparation process of the composite silicon-based material, the disproportionation reaction temperature is 950 ℃, and the reaction time is 6 hours.
The preparation process of the anode material comprises the following steps: putting the composite silicon-based material and deionized water into a ball mill according to the proportion of 1:11.5 for ball milling; the inlet temperature of spray drying is 200 ℃, and the outlet temperature is 100 ℃; putting the primary carbonization process into a tubular furnace, wherein the pyrolysis temperature is 600 ℃, and the pyrolysis time is 1 h; the secondary carbonization process is put into a tubular furnace, the pyrolysis temperature is 900 ℃, and the pyrolysis time is 2 hours.
Comparative example 1
This comparative example is essentially the same as example 3, except that the disproportionation reaction time was 8 h.
Comparative example 2
This comparative example is essentially the same as example 3 except that the disproportionation reaction time was 30 min.
Comparative example 3
This comparative example is substantially the same as example 3 except that the primary carbon coating was performed only by the primary carbon coating method and the secondary carbon coating was not performed.
Experimental example 1
A2032 button-type analog cell was prepared from the negative electrode materials obtained in some of examples 1 to 10 and comparative examples 1 to 3The electrochemical performance was tested. The preparation method comprises the following specific steps: mixing SiOxUniformly mixing a/C composite material, a conductive agent acetylene black, a thickening agent sodium carboxymethyl cellulose and a binder styrene butadiene rubber according to a mass ratio of 80:10:5:5, taking deionized water as a solvent, uniformly stirring by using a magnetic stirrer to prepare slurry, uniformly coating the slurry on a copper foil at a stirring speed of 800rpm, putting an electrode plate into a vacuum drying oven, and drying at 80 ℃ for 12 hours to remove water; in a glove box filled with argon, a dried pole piece is taken as a positive electrode, a lithium piece is taken as a negative electrode, Celgard2500 is taken as a diaphragm, 1mol/L LiPF6 is dissolved in a solution of Ethylene Carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC) (the volume ratio is 1:1:1) to be taken as an electrolyte, a 2032 type button half cell is assembled, and a constant current charge-discharge performance test is carried out on a cell test system (LAND CTR 2001A). The current density of 100mA/g is adopted for testing in the first 10 times of circulation, and the current density of 200mA/g is adopted for testing in the subsequent circulation. The experimental results were plotted as shown in fig. 1 to 9, in which fig. 1 to 6 are the cyclic discharge curves of examples 1, 3, 4, 5, 7 and 8, respectively, and fig. 7 to 9 are the cyclic discharge curves of comparative examples 1 to 3, respectively.
As can be seen from fig. 1, the button cell made of the negative electrode material provided in example 1 has a first discharge capacity of 1910.3mAh/g and a charge capacity of 1031.5mAh/g after 100 cycles, and as can be seen from fig. 2, at a current of 200mA/g, the button cell made of example 3 still has an effective capacity of over 1000mAh/g after 140 cycles, and has small capacity fading and good cycle stability. Fig. 3 is a button cell prepared from the negative electrode material provided in example 4, wherein the first discharge capacity of the button cell is 1800.6mAh/g, the first coulombic efficiency is 70.0%, and the effective capacity after 110 weeks of cycling is above 700mAh/g, fig. 4 and 5 are respectively a cycle curve diagram of the button cell prepared in example 5 and example 7, fig. 6 is a charge-discharge curve diagram of the button cell assembled from the negative electrode material prepared in example 8, wherein the first discharge capacity of the button cell is 1857.0mAh/g, the first coulombic efficiency is 70.5%, and the charge capacity after 110 weeks of cycling is above 1100 mAh/g. FIG. 7 is a charge-discharge curve diagram of a button cell assembled by the negative electrode material prepared in comparative example 1, wherein the first discharge capacity is 1016.3mAh/g, the first coulombic efficiency is 67.5%, and the charge capacity after 60 weeks of circulation is 903.4 mAh/g; fig. 8 is a charge-discharge curve chart of a button cell assembled by the negative electrode material prepared in comparative example 2, wherein the initial coulombic efficiency is 48.9%, and the capacity retention rate after 80 weeks of circulation is 79.8%; fig. 9 is a charge-discharge curve diagram of a button cell assembled by the negative electrode material prepared in comparative example 3, in which the first discharge capacity is 1719.4mAh/g, the first charge capacity is 1160.2mAh/g, and the first coulombic efficiency is 67.4%.
Experimental example 2
The anode materials provided in some of examples 1-10 and the anode materials provided in comparative examples 1-3 were fabricated into 2032 type button half cells in the manner provided in experimental example 1. The number of cycles at a current density of 200mA/g was tested. And recorded in the table below.
TABLE 1 Cyclic Charge and discharge data for the examples
As can be seen from the above table, the charge capacity after 112 weeks of cycle in example 1 was 1031.5mAh/g, and the capacity retention rate was 77.6%; the first charge capacity of the capacitor in the embodiment 3 is 1301.5mAh/g, the charge capacity is still 1089.5mAh/g after 144 weeks of circulation, the capacity decay is slow, and the circulation stability is good; the first coulombic efficiency of example 8 was 70.5%. After 118 weeks of circulation, the effective capacity is still 1108.6mAh/g, the capacity retention rate is 84.7%, the circulation stability is good, and the table shows that the first charge-discharge capacity of comparative example 1 is lower, the first coulombic efficiency of comparative example 2 is lower, and the first coulombic efficiency of comparative example 3 is also lower than that of example 3.
Experimental example 3
The negative electrode material obtained in example 3 was subjected to X-ray diffraction and fourier transform infrared spectroscopy, respectively, to obtain fig. 10 to 11.
As can be seen from the XRD pattern of fig. 10, the negative electrode material of example 3 has a steamed peak in the range of 20 to 25 ° 2 θ, which corresponds to the characteristic peak of amorphous silica. Diffraction peaks at 2 θ of 28.4 °, 47.3 °, 56.1 °, 76.2 °, and 88.2 ° respectively correspond to the crystalline silicon (111), (220), and (311),(400) And (331) a characteristic peak of a crystal face, a diffraction peak of silica appears at 2 θ ═ 30.1 °, which is due to disproportionation reaction of the silicon monoxide under high temperature conditions to produce crystalline silicon and silica. FIG. 11 is an infrared spectrum at 1098cm of a composite silicon-based material of example 3-1、809cm-1And 479cm-1Similar absorption peaks are respectively corresponding to an antisymmetric stretching vibration absorption peak of a Si-O-Si bond, a symmetric stretching vibration absorption peak of a Si-O bond and a bending vibration absorption peak of a Si-O bond, which shows that SiOxIs present.
Experimental example 4
Scanning electron micrographs of the composite silicon-based materials obtained in examples 3 and 6 were taken. As shown in fig. 12 and 13, the composite silicon-based material is better in morphology.
In summary, according to the preparation method of the composite silicon-based material provided by the invention, the silica powder is placed at a high temperature, so that a part of the silica powder is subjected to disproportionation reaction, and particles in the silica powder are converted into silicon, silica and silicon dioxide composite silicon-based particles. Crystalline silicon and silicon dioxide are generated by reaction on original silicon oxide particles, the crystalline silicon increases the capacity of the composite material, the first coulombic efficiency of the material is improved, the silicon dioxide serving as an inert substance can buffer the volume change in the process of lithium intercalation and deintercalation of silicon to a certain extent in the particles, and the cycle performance of the material is improved. Compared with a mixed silicon-based material obtained by directly and physically mixing simple substance silicon, silicon dioxide and silicon monoxide, the composite silicon-based material provided by the application can effectively relieve the volume expansion of the material from the inside of the material and even on the basis of nano particles, and has a certain effect on the improvement of the first coulombic efficiency. Therefore, when the composite silicon-based particles are applied to the negative electrode material, the negative electrode material has the advantages of high conductivity, low volume expansion rate, good cycle performance and small first irreversible capacity.
The composite silicon-based material provided by the invention is prepared by the preparation method of the composite silicon-based material provided by the invention, so that the composite silicon-based material is used as a negative electrode material of a lithium ion battery after being coated by carbon.
The negative electrode material provided by the invention is formed by coating the particles of the composite silicon-based material provided by the embodiment of the invention in the shell of the carbon coating layer. Therefore, the cathode material has the advantages of high conductivity, low volume expansion rate, high first coulombic efficiency and good cycle performance.
According to the preparation method of the cathode material, the composite silicon-based material is subjected to carbon coating, so that the prepared cathode material has the advantages of high conductivity, low volume expansion rate and good cycle performance. The carbon layer formed by primary carbon coating can isolate the composite silicon-based particles from the external electrolyte to a certain extent, and the probability of side reaction is reduced. The added conductive agent is used as a transmission channel of ions and electrons, and the conductivity of the prepared material can be increased. And the secondary carbon is coated on the surface of the primary carbon coated product to form an amorphous carbon layer, the amorphous carbon layer on the surface of the particle is uniform and compact, on one hand, the stress effect generated in the charging and discharging process is buffered, the volume expansion in the charging and discharging process of the material is relieved, the stability of the material structure is kept, on the other hand, the direct contact between the composite silicon-based material in the carbon layer and the electrolyte can be further avoided, the probability of generating side reaction is further reduced, the initial irreversible capacity is reduced, and therefore the initial coulomb efficiency of the composite material is improved. And the amorphous carbon layer and the conductive agent generate synergistic action, so that the conductivity of the material is obviously improved, the volume expansion of the material in the lithium intercalation and deintercalation process is further effectively relieved, the electrochemical performance of the composite material is improved, and the cycle life of the composite material is prolonged.
According to the lithium ion battery provided by the invention, the material for preparing the negative electrode of the lithium ion battery comprises the negative electrode material provided by the invention or the negative electrode material prepared by the preparation method provided by the invention, so that the lithium ion battery has good performance.
In the lithium ion battery provided by the invention, the material for preparing the negative electrode of the lithium ion battery comprises the negative electrode material provided by the invention or the negative electrode material prepared by the preparation method provided by the invention. Therefore, the lithium ion battery has good performance.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a composite silicon-based material is characterized by comprising the following steps:
carrying out disproportionation reaction on the silica powder to convert the silica particles in the silica powder into composite silicon-based particles containing silica, silicon and silicon dioxide.
2. The method for preparing a composite silicon-based material according to claim 1, wherein the disproportionation reaction of the silica fume is: placing the silica powder in an environment of 950-1200 ℃ under the protection of inert gas, and reacting for 3-10 h;
preferably, the average particle size of the silica powder is 3-8 μm;
preferably, the inert gas is argon.
3. A composite silicon-based material, characterized by being produced by the production method according to claim 1 or 2.
4. A negative electrode material, wherein the particles of the negative electrode material comprise a carbon-coated shell and the particles of the composite silicon-based material according to claim 3 coated in the carbon-coated shell.
5. The anode material of claim 4, wherein the carbon clad outer shell comprises a primary carbon clad layer and a secondary carbon clad layer;
preferably, the primary carbon coating layer is obtained by carbonizing a coating agent, wherein the coating agent comprises at least one of glucose, sucrose, styrene butadiene rubber, starch, citric acid and polyvinylpyrrolidone;
preferably, the secondary carbon coating layer is obtained by carbonizing an organic carbon source, wherein the organic carbon source comprises at least one of phenolic resin, glucose, sucrose, asphalt and polyvinylpyrrolidone.
6. A method for preparing an anode material, comprising:
carbon coating a composite silicon-based material according to claim 3.
7. The method for preparing the anode material according to claim 6, wherein the carbon coating comprises a primary carbon coating, and the method for performing the primary carbon coating comprises:
carrying out primary carbonization on a composite silicon-based material precursor, wherein the composite silicon-based material precursor is a mixed dispersion body in which a conductive agent, a coating agent and the composite silicon-based material are dispersed; preferably, before the primary carbonization of the composite silicon-based material precursor, the preparation of the composite silicon-based material precursor further comprises:
uniformly mixing and dispersing the composite silicon-based material, water, the conductive agent and the coating agent to obtain mixed slurry;
drying the mixed slurry to obtain a composite silicon-based material precursor; more preferably, the water is deionized water;
preferably, the conductive agent includes at least one of graphene, carbon nanotubes, and carbon nanofibers;
preferably, the coating agent comprises at least one of glucose, sucrose, styrene butadiene rubber and starch;
preferably, the mass ratio of the conductive agent to the composite silicon-based material is 1-8: 100;
preferably, the mass ratio of the coating agent to the composite silicon-based material is 3-10: 100;
preferably, the mass ratio of the deionized water to the composite silicon-based material is as follows: 5.67-11.5: 1;
preferably, the drying means is spray drying; more preferably, the spray drying inlet temperature is 140-320 ℃ and the outlet temperature is 80-160 ℃;
preferably, the primary carbonization of the composite silicon-based material precursor is as follows: pyrolyzing the composite silicon-based material precursor for 2-4h in an inert gas protective atmosphere at the temperature of 500-850 ℃;
preferably, the inert gas is argon.
8. The preparation method of the anode material according to claim 7, wherein the mixing and dispersing of the composite silicon-based material, water, the conductive agent and the coating agent to obtain the mixed slurry is as follows:
mixing the composite silicon-based material with the water, and performing ball milling to obtain dispersed slurry;
uniformly mixing and stirring the dispersed slurry, the conductive agent and the coating agent to obtain mixed slurry;
preferably, the mixing and ball milling time is 3-10 h;
preferably, the mixing and stirring of the dispersion slurry, the conductive agent and the coating agent are as follows: and mixing the dispersion slurry, the conductive agent and the coating agent, and then stirring in vacuum at the rotation speed of 800-1100rpm for 20-90 min.
9. The method for producing an anode material according to claim 7, wherein the carbon coating further comprises a secondary carbon coating; the method for performing secondary carbon coating comprises the following steps: uniformly mixing the primary carbon-coated product with an organic carbon source, and then carrying out secondary carbonization;
preferably, the mass ratio of the primary carbon-coated product to the organic carbon source is: 7-9: 1-3;
preferably, the organic carbon source comprises at least one of phenolic resin, glucose, sucrose and pitch;
preferably, the secondary carbonation is: mixing the primary carbon-coated product with an organic carbon source, and then pyrolyzing the mixture for 2-4h in an inert gas protective atmosphere at the temperature of 700-900 ℃;
more preferably, the inert gas is argon.
10. A lithium ion battery, characterized in that the material for preparing the negative electrode of the lithium ion battery comprises the negative electrode material according to claim 4 or the negative electrode material prepared by the method for preparing the negative electrode material according to any one of claims 5 to 9.
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