CN114430041A - Gel type silicon-based negative electrode material, preparation method and application thereof, and lithium ion battery - Google Patents
Gel type silicon-based negative electrode material, preparation method and application thereof, and lithium ion battery Download PDFInfo
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Abstract
The invention discloses a gel type silicon-based negative electrode material, a preparation method and application thereof and a lithium ion battery. The silicon-based negative electrode material comprises conductive polymer gel and a powder silicon source, wherein the conductive polymer gel is of a three-dimensional network structure, and the surface of the powder silicon source is coated by the conductive polymer gel and is dispersed in a skeleton of the three-dimensional network structure of the conductive polymer gel. The preparation method of the silicon-based negative electrode material comprises the step of carrying out in-situ polymerization on a conductive polymer in a powdery silicon source dispersion liquid under an ultrasonic condition. The silicon-based negative electrode material provided by the invention can obviously improve the cycling stability of the silicon-based negative electrode material, and can improve the energy density of a lithium battery when being applied to the lithium ion battery.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a silicon-based negative electrode material, a preparation method thereof and application of the silicon-based negative electrode material in a lithium ion battery.
Background
Silicon has high theoretical specific capacity (4200 mA.h.g) as a promising negative electrode material of lithium battery-1) And a lithium desorption voltage platform (-0.4V vs Li)+Low Li), rich earth crust reserves and the like. However, silicon as a semiconductor has poor conductivity, which seriously affects the performance of the electrical properties of the material, and silicon and Li in the charging and discharging process+Alloying reaction occurs, and serious volume expansion causes the uncontrollable growth of an SEI film, which causes the rapid attenuation of the battery capacity and influences the service life of the battery.
The conductive polymer has the advantages of easy synthesis, high conductivity, good stability, no toxicity to the environment, reversible redox property and the like, and has been widely applied to modification research of the anode material of the lithium ion battery in recent years. CN102185140B adopts polyaniline and other conductive polymers to coat the lithium iron phosphate anode material, thereby remarkably improving the conductivity of the lithium iron phosphate and improving the comprehensive electrical property of the material. CN110854363A discloses a polymer coated electrode material prepared from aniline, thiophene, pyrrole and disulfide, which improves the conductivity and electrochemical performance of the material, but the used dithio diphenylamine and diallyl disulfide are expensive and are not beneficial to mass production.
Therefore, the development of the conductive polymer coated silicon-based negative electrode with excellent electrochemical performance, simple preparation process and low cost belongs to the technical problem in the field.
Disclosure of Invention
The invention aims to solve the problems of poor conductivity and performance deterioration in the repeated charge and discharge process of a silicon-based negative electrode in the prior art, and provides a gel type silicon-based negative electrode material, a preparation method thereof and application of the gel type silicon-based negative electrode material in a lithium ion battery.
The invention provides a gel type silicon-based negative electrode material, which comprises conductive polymer gel and a powder silicon source, wherein the conductive polymer gel is of a three-dimensional network structure, and the surface of the powder silicon source is coated by the conductive polymer gel and is dispersed in a framework of the three-dimensional network structure of the conductive polymer gel.
In the above technical scheme, the conductive polymer is an organic acid-doped conductive polymer. The organic acid is selected from one or more of phytic acid, citric acid, succinic acid and tartaric acid. The doping amount of the organic acid is 1:2-10 of the molar ratio of the organic acid to the monomer used by the conductive polymer.
In the technical scheme, the powder silicon source and the conductive polymer are combined by an R (O) -O-Si bond. Wherein R is P or C.
In the above technical solution, the silicon-based negative electrode material further includes an additive, wherein the additive is selected from any one or more of natural graphite, artificial graphite, carbon nanotubes, and carbon black.
In the above technical scheme, the conductive polymer is one or more of polyaniline, polyaniline derivatives, polythiophene derivatives, polypyrrole, and polypyrrole derivatives.
In the above technical scheme, the powder silicon source is at least one of simple substance silicon, silicon oxide (SiOx, 0.6< x <1.5), and silicon alloy.
In the technical scheme, the total mass of the silicon-based negative electrode material is taken as a reference, the content of the powder silicon source is 5-75%, the content of the conductive polymer gel is 5-95% calculated by the conductive polymer, and the content of the additive is 0-50%. Preferably, the silicon source content is 5% to 50%, the conductive polymer gel content is 5% to 65% and the additive content is 30% to 50% based on the total mass of the silicon-based negative electrode material.
The second aspect of the invention provides a preparation method of a gel type silicon-based negative electrode material, which comprises the following steps:
and carrying out in-situ polymerization on the conductive polymer in the powdered silicon source dispersion liquid under the ultrasonic condition.
In the above technical scheme, the conductive polymer is one or more of polyaniline, polyaniline derivatives, polythiophene derivatives, polypyrrole, and polypyrrole derivatives.
In the above technical scheme, the powder silicon source is at least one of simple substance silicon, silicon oxide (SiOx, 0.6< x <1.5), and silicon alloy.
In the above technical scheme, the powder silicon source dispersion liquid contains an organic acid, and the organic acid is selected from any one or more of phytic acid, citric acid, succinic acid and tartaric acid.
In the above technical scheme, the polymerization reaction temperature is 20-40 ℃, for example, 20 ℃, 30 ℃, 40 ℃ and the like. The ultrasonic conditions were as follows: the ultrasonic frequency is 20KHz-40KHz, and the ultrasonic time is 1min-60min, such as 1min, 3min, 20min, 40min, 60min, etc.
In the above technical scheme, the polymerization reaction does not need stirring.
The third aspect of the invention provides the silicon-based negative electrode material prepared by the preparation method.
The fourth aspect of the invention provides an application of the silicon-based negative electrode material in a lithium ion battery.
The invention provides a lithium ion battery, which comprises the silicon-based negative electrode material, a positive electrode material containing lithium element, a diaphragm and electrolyte.
In the silicon-based negative electrode material provided by the invention, the active substance (silicon) is combined with the organic acid-doped conductive polymer through an R (O) -O-Si bond, and the rivet is arranged on a gel skeleton of the conductive polymer, so that the problem of peeling between the silicon and the polymer caused by volume expansion in the charging and discharging processes is solved, and the cycle stability of the material is obviously improved.
The inventor finds that in the preparation process of the silicon-based negative electrode material, the raw materials are subjected to polymerization reaction under a specific ultrasonic condition, the formation of polymer gel with a three-dimensional network structure can be promoted, and the abundant pore structure can store more electrolyte and is beneficial to Li+The migration and diffusion of the material can improve the electrical property of the material. In addition, no template agent (graphene oxide and the like) is required to be added in the whole preparation process, so that the content of inert substances is reduced, and the gram volume of the material is favorably improved. The gel-type silicon negative electrode material has certain adhesiveness, can be directly coated on the surface of a current collector without adding an adhesive, and can improve the energy density of a lithium battery when being applied to the lithium ion battery.
The silicon-based negative electrode material provided by the invention is used in a lithium ion battery, and under the constant current discharge rate of 0.2C, after 400 cycles, the capacity retention rate can reach more than 70%, and further can reach more than 80%.
Drawings
Fig. 1 is an SEM image of the conductive polymer coated silicon-based negative electrode of example 1, in which a is a powder silicon source coated with polyaniline, and B is polyaniline;
FIG. 2 is a TEM image of conductive polymer-coated silicon of example 1, wherein C is a powdery silicon source and D is polyaniline;
FIG. 3 is a schematic representation of a silicon-based negative electrode obtained in example 1;
fig. 4 is a cycle stability test curve of the silicon-based anode obtained in example 1;
fig. 5 is an X-ray photoelectron spectrum of the silicon-based negative electrode obtained in example 1.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present specification, the median diameter refers to a diameter corresponding to a cumulative particle size distribution percentage of 50%, and is generally used to indicate an average particle size of a powder. In the invention, the median particle diameter of the silicon-based anode material can be obtained by dynamic light scattering characterization without special indication.
The invention provides a gel type silicon-based negative electrode material, which comprises conductive polymer gel and a powder silicon source, wherein the conductive polymer gel is of a three-dimensional network structure, and the surface of the powder silicon source is coated by the conductive polymer gel and is dispersed in a framework of the three-dimensional network structure of the conductive polymer gel.
According to the silicon-based negative electrode material provided by the invention, the conductive polymer is an organic acid-doped conductive polymer. The organic acid is selected from one or more of phytic acid, citric acid, succinic acid and tartaric acid. The doping amount of the organic acid is 1:2-10 of the molar ratio of the organic acid to the monomer used by the conductive polymer.
According to the silicon-based anode material provided by the invention, the powder silicon source and the conductive polymer are combined by an R (O) -O-Si bond.
According to the silicon-based anode material provided by the invention, preferably, the silicon-based anode material further comprises an additive, wherein the additive is selected from any one or more of natural graphite, artificial graphite, carbon nanotubes and carbon black.
According to the silicon-based negative electrode material provided by the invention, preferably, based on the total mass of the silicon-based negative electrode material, the content of the powder silicon source is 5% -75%, the content of the conductive polymer gel is 5% -95% calculated by the conductive polymer, and the content of the additive is 0-50%. Preferably, the silicon source content is 5% to 50%, the conductive polymer gel content is 5% to 65% and the additive content is 30% to 50% based on the total mass of the silicon-based negative electrode material.
According to the silicon-based anode material provided by the invention, preferably, the median particle diameter of the powdered silicon source is 0.05-5.0 μm, for example, 0.1 μm, 0.2 μm, 0.5 μm, 1.0 μm, 2.0 μm, and any value in the range formed by any two of these values.
The second aspect of the invention provides a preparation method of a silicon-based anode material, which comprises the following steps:
and carrying out in-situ polymerization on the conductive polymer in the powdered silicon source dispersion liquid under the ultrasonic condition.
According to the present invention, preferably, the preparation method of the silicon-based anode material specifically comprises:
(1) mixing a monomer for synthesizing a conductive polymer, an organic acid and a powdery silicon source to obtain a mixture A;
(2) preparing a catalyst into a solution B;
(3) and uniformly mixing the mixture A and the solution B, carrying out polymerization reaction under the ultrasonic condition to obtain viscous slurry, and drying to obtain the gel type silicon-based negative electrode material.
According to the present invention, preferably, in the step (3), the dried material may be subjected to a washing step. The washing can be deionized water washing, and the washing can be carried out for multiple times. And drying the washed materials to obtain the gel type silicon-based negative electrode material. The drying conditions were as follows: drying at 60-80 deg.c for 4-6 hr. The drying is preferably carried out under vacuum. According to the present invention, preferably, the conductive polymer is any one or more of polyaniline, polyaniline derivatives, polythiophene derivatives, polypyrrole, and polypyrrole derivatives. The monomer is at least one of aniline, aniline derivatives (including but not limited to 3-methylaniline, p-methylaniline, diphenylamine, etc.), thiophene derivatives (including but not limited to 2-hexylthiophene, 3, 4-ethylenedioxythiophene, etc.), pyrrole derivatives (including but not limited to 3-methylpyrrole, N-ethylpyrrole, etc.).
According to the invention, preferably, the powdered silicon source is at least one of simple substance silicon, silicon oxide compound (SiOx, 0.6< x <1.5) and silicon alloy.
According to the invention, the organic acid is selected from any one or more of phytic acid, citric acid, succinic acid and tartaric acid.
According to the invention, the molar ratio of organic acid to polymer monomer is from 1:2 to 10, for example 1:2, 1:3, 1:4, 1:5, 1:7, 1:10 and any value in the range between any two of these values.
According to the invention, step (1) can be added with a reaction cosolvent, wherein the reaction cosolvent is selected from any one or more of water, alcohols, amides, ketones and ethers. The alcohol may be at least one of methanol, ethanol, and isopropanol. The amide may be at least one of N 'N-dimethylformamide and N' N-dimethylacetamide. The ketone may be at least one of acetone and N-methylpyrrolidone. The ether may be at least one of diethyl ether and tetrahydrofuran. The dosage of the reaction cosolvent can be 2-3 times of the total mass of the conductive polymer monomer and the powder silicon source.
According to the present invention, the catalyst in step (2) is a catalyst for in situ polymerization, including but not limited to at least one of ammonium persulfate, hydrogen peroxide, ferric trichloride, benzoyl peroxide, ammonium cerium sulfate, sodium persulfate, and cerium sulfate. The catalyst may be used in an amount of 0.1 to 0.5 times the molar amount of the monomer of the conductive polymer.
According to the present invention, the polymerization reaction temperature in the step (3) is 20 to 40 ℃, for example, 20 ℃, 30 ℃, 40 ℃ and the like.
According to the present invention, preferably, the ultrasonic conditions in step (3) are as follows: the ultrasonic frequency is 20KHz-40KHz, and the ultrasonic time is 1min-60min, such as 1min, 3min, 20min, 40min, 60min, etc.
According to the present invention, the polymerization reaction in step (3) does not require stirring.
According to the invention, the drying conditions of step (3) are as follows: drying at 60-80 deg.c for 4-6 hr. The drying is preferably carried out under vacuum.
The third aspect of the invention provides the silicon-based negative electrode material prepared by the preparation method. The structural and composition characteristics of the silicon-based anode material are as described above, and are not described in detail herein.
The fourth aspect of the invention provides an application of the silicon-based negative electrode material in a lithium ion battery. In the research process, the inventor of the invention finds that the energy density of a lithium battery can be improved by using the silicon-based negative electrode material provided by the invention in the lithium ion battery.
The invention provides a lithium ion battery, which comprises the silicon-based negative electrode material, a positive electrode material containing lithium element, a diaphragm and electrolyte.
The structure of the lithium ion battery provided according to the present invention may be well known to those skilled in the art, and generally, the separator is located between the positive electrode tab and the negative electrode tab. The positive plate contains the positive electrode material, and the negative plate contains the silicon-based negative electrode material. In the present invention, the specific composition of the lithium element-containing positive electrode material is not particularly limited, and may be a lithium element-containing positive electrode material conventionally used in the art.
According to the lithium ion battery provided by the invention, the separator can be selected from various separators used in the lithium ion battery known to those skilled in the art, such as a polypropylene microporous membrane, a polyethylene felt, a glass fiber felt or an ultrafine glass fiber paper.
According to the lithium ion battery provided by the invention, the electrolyte can be various conventional electrolytes, such as a nonaqueous electrolyte. The nonaqueous electrolytic solution is a solution of an electrolytic lithium salt in a nonaqueous solvent, and a conventional nonaqueous electrolytic solution known to those skilled in the art can be used. For example, the electrolyte may be selected from lithium hexafluorophosphate (LiPF)6) Lithium perchlorate (LiClO)4) Lithium tetrafluoroborate (LiBF)4) Lithium hexafluoroarsenate (LiAsF)6) And lithium hexafluorosilicate (LiSiF)6) At least one of (1). The non-aqueous solvent may be selected from a mixed solution of a chain acid ester and a cyclic acid ester, wherein the chain acid ester may be dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), propyl methyl carbonate (MPC), and carbonic acidDipropyl ester (DPC). The cyclic acid ester may be at least one of Ethylene Carbonate (EC), Propylene Carbonate (PC), and Vinylene Carbonate (VC).
In the invention, a Scanning Electron Microscope (SEM) is adopted to characterize the morphology of the silicon-based negative electrode material, specifically, the SEM is a TECNALG2F20(200kv) model of FEI company in America, and the test conditions are as follows: the sample was pressed directly onto the sample stage containing the conductive tape and then observed by insertion into an electron microscope. The observation was performed using 8000 magnifications.
In the present invention, the observation was carried out by a Transmission Electron Microscope (TEM) of JEM-2100, manufactured by Nippon electronics Co. And (3) testing conditions are as follows: the sample was placed on a copper support grid and observed by insertion into an electron microscope.
In the invention, an ESCALB 250Xi model X-ray photoelectron spectrum tester of ThermoFisher Scientific company in USA is adopted to characterize the battery cathode material, and the test conditions comprise: room temperature 25 deg.C, vacuum degree less than 5 × 10-10mba, working voltage 15KV, Al K alpha is used as a ray source.
In the invention, the electrochemical performance of the assembled lithium ion battery is tested by adopting a Wuhan blue battery testing system (CT 2001B). The test conditions included: the voltage range is 0.005V-3V, and the current range is 0.05A-2A. Each sample was assembled with 10 coin cells and the cell performance was tested at the same voltage and current and averaged.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, the room temperature is 25 ℃.
In the following examples and comparative examples, aniline, thiophene, pyrrole, phytic acid, citric acid, ammonium persulfate were purchased from Shanghai Aladdin Biotech Co., Ltd. The artificial graphite is purchased from Luoyang Yuexing New energy science and technology company and is marked as TB-216.
In the following examples and comparative examples, the median particle size of the silica nanopowder used was 100 nm.
Example 1
(1) Weighing 4.65g of aniline and 6.6g of phytic acid, uniformly mixing, adding 11.25g of nano silicon powder, uniformly dispersing, and then naming as a mixture A.
(2) 2.85g of ammonium persulfate was dissolved in 10mL of deionized water and designated as solution B.
(3) And mixing the mixture A and the solution B, uniformly stirring, putting the mixed solution into an ultrasonic instrument (ultrasonic frequency is 40KHz), and carrying out ultrasonic treatment at 25 ℃ for 2min to gradually change the solution into dark green viscous slurry, wherein the volume of the viscous slurry is increased. And transferring the slurry into a vacuum oven, and drying.
(4) And (4) repeatedly washing the solid obtained in the step (3) with deionized water for 3 times, and drying in vacuum at 80 ℃ for 4 hours to obtain the gel type silicon-based negative electrode S-1.
Fig. 1 is an SEM image of the gel-type silicon-based negative electrode, in fig. 1, a is a powdered silicon source coated with polyaniline, and B is a polymer skeleton formed by polyaniline crosslinking. As can be seen from FIG. 1, the polyaniline-coated powdered silicon source in the silicon-based negative electrode is uniformly dispersed in the polyaniline skeleton, and the porous structure is favorable for Li+Diffusion migration, in turn, provides a buffer space, inhibiting volume expansion.
FIG. 2 is a TEM image of the polyaniline-coated silicon, wherein C is a silicon source and D is polyaniline. As can be seen from fig. 2, the surface of the silicon source is uniformly coated with polyaniline, and there is no phase separation between the two phases, indicating that polyaniline is generated by in-situ polymerization on the surface of the silicon source.
Fig. 3 is a real image of the gel-type silicon-based negative electrode S-1. As can be seen from fig. 3, the material did not flow and deform when placed upside down, indicating that the material was a gel.
The lithium-containing silicon-based negative electrode material S-1 obtained in example 1 and a metal lithium sheet are respectively used as a positive electrode and a negative electrode, and 1mol/L LiPF is used6The solution (in which ethylene carbonate and diethyl carbonate are mixed in a volume ratio of 3: 7 as a solvent) is used as an electrolyte, a polypropylene microporous membrane is used as a diaphragm, and the solution is assembled into a CR2016 coin cell, which represents the cycling stability of the gel-type silicon-based negative electrode S-1 described in example 1.
FIG. 4 shows the cycle stability test curve (discharge capacity) of a coin cell based on the gel-type silicon-based negative electrode S-1 described in example 1Flow 0.2C). As shown in FIG. 4, the reversible capacity of the gel-type silicon-based negative electrode S-1 described in example 1 was 1620mA · h · g-1Under the constant current discharge rate of 0.2C, after 400 cycles, the capacity retention rate is 82%.
Example 2
(1) Weighing 4.2g of thiophene and 6.6g of phytic acid, uniformly mixing, adding 10.8g of nano silicon powder, and uniformly dispersing to obtain a mixture A.
(2) 2.85g of ammonium persulfate was dissolved in 10mL of deionized water and designated as solution B.
(3) And mixing the mixture A and the solution B, uniformly stirring, putting the mixed solution into an ultrasonic instrument (ultrasonic frequency is 40KHz), and carrying out ultrasonic treatment at 35 ℃ for 10min to gradually change the solution into viscous slurry, wherein the volume of the viscous slurry is increased. And transferring the slurry into a vacuum oven, and drying.
(4) And (4) repeatedly washing the solid obtained in the step (3) with deionized water for 3 times, and drying in vacuum at 60 ℃ for 4 hours to obtain the gel type silicon-based negative electrode S-2.
A battery was assembled and tested for electrical properties according to the method of example 1, except that the silicon-based negative electrode material S-1 was replaced with the material S-2 prepared in example 2. The test result shows that the capacity retention rate of the material S-2 in the example 2 is about 83% after 400 cycles under the constant current discharge rate of 0.2C.
Example 3
(1) Weighing 3.35g of pyrrole and 6.6g of phytic acid, uniformly mixing, adding 9.95g of nano silicon powder, and uniformly dispersing to obtain a mixture A.
(2) 2.85g of ammonium persulfate was dissolved in 10ml of deionized water and designated as solution B.
(3) Mixing the mixture A and the solution B, stirring uniformly, placing the mixed solution in an ultrasonic instrument (ultrasonic frequency is 20KHz), performing ultrasonic treatment at 25 ℃ for 30min, and gradually changing the solution into viscous slurry with increased volume. And transferring the slurry into a vacuum oven, and drying.
(4) And (4) repeatedly washing the solid obtained in the step (3) with deionized water for 3 times, and drying in vacuum at 80 ℃ for 4 hours to obtain the gel type silicon-based negative electrode S-3.
A battery was assembled and tested for electrical properties according to the method of example 1, except that the silicon-based negative electrode material S-1 was replaced with the material S-3 prepared in example 3. The test result shows that the capacity retention rate of the material S-3 in example 3 is about 84% after 400 cycles under the constant current discharge rate of 0.2C.
Example 4
(1) 5.4g of p-phenylenediamine and 6.6g of phytic acid are weighed, uniformly mixed, added with 12g of nano silicon powder, uniformly dispersed and named as a mixture A.
(2) 2.85g of ammonium persulfate was dissolved in 10mL of deionized water and designated as solution B.
(3) And mixing the mixture A and the solution B, uniformly stirring, putting the mixed solution into an ultrasonic instrument (ultrasonic frequency is 30KHz), and performing ultrasonic treatment at 40 ℃ for 30min to gradually change the solution into viscous slurry, wherein the volume of the viscous slurry is increased. And transferring the slurry into a vacuum oven, and drying.
(4) And (4) repeatedly washing the solid obtained in the step (3) with deionized water for 3 times, and drying in vacuum at 70 ℃ for 4 hours to obtain the gel type silicon-based negative electrode S-4.
A battery was assembled and tested for electrical properties according to the method of example 1, except that the silicon-based negative electrode material S-1 was replaced with the material S-4 prepared in example 4. The test result shows that the capacity retention rate of the material S-4 in example 4 is about 82% after 400 cycles under the constant current discharge rate of 0.2C.
Example 5
(1) Weighing 1.86g of aniline and 1.92g of citric acid, uniformly mixing, adding 3.78g of nano silicon powder, and uniformly dispersing to obtain a mixture A.
(2) 1.14g of ammonium persulfate was dissolved in 10mL of deionized water and designated as solution B.
(3) And mixing the mixture A and the solution B, uniformly stirring, putting the mixed solution into an ultrasonic instrument (ultrasonic frequency is 40KHz), and carrying out ultrasonic treatment at 40 ℃ for 2min to gradually change the solution into viscous slurry, wherein the volume of the viscous slurry is increased. And transferring the slurry into a vacuum oven, and drying.
(4) And (4) repeatedly washing the solid obtained in the step (3) with deionized water for 3 times, and drying in vacuum at 80 ℃ for 4 hours to obtain the gel type silicon-based negative electrode S-5.
A battery was assembled and tested for electrical properties according to the method of example 1, except that the silicon-based negative electrode material S-1 was replaced with the material S-5 prepared in example 5. The test result shows that the capacity retention rate of the material S-5 in example 5 is about 82% after 400 cycles under the constant current discharge rate of 0.2C.
Example 6
(1) Weighing 2.79g of aniline and 1.18g of succinic acid, uniformly mixing, adding 3.97g of nano silicon powder, and uniformly dispersing to obtain a mixture A.
(2) 1.71g of ammonium persulfate was dissolved in 10mL of deionized water and designated as solution B.
(3) And mixing the mixture A and the solution B, uniformly stirring, putting the mixed solution into an ultrasonic instrument (ultrasonic frequency is 40KHz), and carrying out ultrasonic treatment at 30 ℃ for 60min to gradually change the solution into viscous slurry, wherein the volume of the viscous slurry is increased. And transferring the slurry into a vacuum oven, and drying.
(4) And (4) repeatedly washing the solid obtained in the step (3) with deionized water for 3 times, and drying in vacuum at 70 ℃ for 4 hours to obtain the gel type silicon-based negative electrode S-6.
A battery was assembled and tested for electrical properties according to the method of example 1, except that the silicon-based negative electrode material S-1 was replaced with the material S-6 prepared in example 6. The test result shows that the capacity retention rate of the material S-6 in example 6 is about 80% after 400 cycles under the constant current discharge rate of 0.2C.
Example 7
(1) Weighing 3.72g of aniline and 6.6g of phytic acid, uniformly mixing, adding 16.38g of nano silicon powder and 26.7g of artificial graphite, and uniformly dispersing to obtain a mixture A.
(2) 2.28g of ammonium persulfate was dissolved in 10mL of deionized water and designated as solution B.
(3) And mixing the mixture A and the solution B, uniformly stirring, putting the mixed solution into an ultrasonic instrument (ultrasonic frequency is 40KHz), and carrying out ultrasonic treatment at 25 ℃ for 5min to gradually change the solution into viscous slurry, wherein the volume of the viscous slurry is increased. And transferring the slurry into a vacuum oven, and drying.
(4) And (4) repeatedly washing the solid obtained in the step (3) with deionized water for 3 times, and drying in vacuum at 60 ℃ for 6 hours to obtain the gel type silicon-based negative electrode S-7.
A battery was assembled and tested for electrical properties according to the method of example 1, except that the silicon-based negative electrode material S-1 was replaced with the material S-7 prepared in example 7. The test result shows that the capacity retention rate of the material S-7 in example 7 is about 84% after 400 cycles under the constant current discharge rate of 0.2C.
Example 8
(1) Weighing 4.65g of aniline and 6.6g of phytic acid, uniformly mixing, adding 14.53g of nano silicon powder and 25.78g of artificial graphite, and uniformly dispersing to obtain a mixture A.
(2) 0.43g of hydrogen peroxide was dissolved in 10mL of deionized water and designated as solution B.
(3) And mixing the mixture A and the solution B, uniformly stirring, putting the mixed solution into an ultrasonic instrument (ultrasonic frequency is 40KHz), and carrying out ultrasonic treatment at 25 ℃ for 5min to gradually change the solution into viscous slurry, wherein the volume of the viscous slurry is increased. And transferring the slurry into a vacuum oven, and drying.
(4) And (4) repeatedly washing the solid obtained in the step (3) with deionized water for 3 times, and drying in vacuum at 80 ℃ for 4 hours to obtain the gel type silicon-based negative electrode S-8.
A battery was assembled and tested for electrical properties according to the method of example 1, except that the silicon-based negative electrode material S-1 was replaced with the material prepared in example 8. The test result shows that the capacity retention rate of the material S-8 in example 8 is about 82% after 400 cycles under the constant current discharge rate of 0.2C.
Example 9
(1) 8.58g of aniline and 6.6g of phytic acid are weighed and mixed uniformly, 7.67g of nano silicon powder and 17.24g of artificial graphite are added, and the mixture is named as a mixture A after being dispersed uniformly.
(2) 5.58g of benzoyl peroxide was dissolved in 10ml of deionized water and named solution B.
(3) And mixing the mixture A and the solution B, uniformly stirring, putting the mixed solution into an ultrasonic instrument (ultrasonic frequency is 40KHz), and carrying out ultrasonic treatment at 25 ℃ for 2min to gradually change the solution into viscous slurry, wherein the volume of the viscous slurry is increased. And transferring the slurry into a vacuum oven, and drying.
(4) And (4) repeatedly washing the solid obtained in the step (3) with deionized water for 3 times, and drying in vacuum at 80 ℃ for 4 hours to obtain the gel type silicon-based negative electrode S-9.
A battery was assembled and tested for electrical properties according to the method of example 1, except that the silicon-based negative electrode material S-1 was replaced with the material S-9 prepared in example 9. The test result shows that the capacity retention rate of the material S-9 in example 9 is about 86% after 400 cycles under the constant current discharge rate of 0.2C.
Example 10
(1) Weighing 2.79g of aniline and 6.6g of phytic acid, uniformly mixing, adding 0.8g of nano silicon powder, and uniformly dispersing to obtain a mixture A.
(2) 1.71g of ammonium persulfate was dissolved in 10mL of deionized water and designated as solution B.
(3) And mixing the mixture A and the solution B, uniformly stirring, putting the mixed solution into an ultrasonic instrument (ultrasonic frequency is 40KHz), and carrying out ultrasonic treatment at 25 ℃ for 10min to gradually change the solution into viscous slurry, wherein the volume of the viscous slurry is increased. And transferring the slurry into a vacuum oven, and drying.
(4) And (4) repeatedly washing the solid obtained in the step (3) with deionized water for 3 times, and drying in vacuum at 70 ℃ for 4 hours to obtain the gel type silicon-based negative electrode S-10.
A battery was assembled and tested for electrical properties according to the method of example 1, except that the silicon-based negative electrode material S-1 was replaced with the material S-10 prepared in example 10. The test result shows that the capacity retention rate of the material S-10 in example 10 is about 84% after 400 cycles under the constant current discharge rate of 0.2C.
Example 11
(1) 2.79g of aniline and 6.6g of phytic acid are weighed, mixed uniformly, 0.8g of silica SiO is added, and the mixture is named as a mixture A after being dispersed uniformly.
(2) 1.71g of ammonium persulfate was dissolved in 10mL of deionized water and designated as solution B.
(3) And mixing the mixture A and the solution B, uniformly stirring, putting the mixed solution into an ultrasonic instrument (ultrasonic frequency is 40KHz), and carrying out ultrasonic treatment at 25 ℃ for 10min to gradually change the solution into viscous slurry, wherein the volume of the viscous slurry is increased. And transferring the slurry into a vacuum oven, and drying.
(4) And (4) repeatedly washing the solid obtained in the step (3) with deionized water for 3 times, and drying in vacuum at 70 ℃ for 4 hours to obtain the gel type silicon-based negative electrode S-11.
A battery was assembled and tested for electrical properties according to the method of example 1, except that the silicon-based negative electrode material S-1 was replaced with the material S-11 prepared in example 11. The test result shows that the capacity retention rate of the material S-11 in example 11 is about 86% after 400 cycles under the constant current discharge rate of 0.2C.
Example 12
(1) Weighing 2.79g of aniline and 6.6g of phytic acid, uniformly mixing, adding 0.8g of powder Si-Al alloy, and uniformly dispersing to obtain a mixture A.
(2) 1.71g of ammonium persulfate was dissolved in 10mL of deionized water and designated as solution B.
(3) And mixing the mixture A and the solution B, uniformly stirring, putting the mixed solution into an ultrasonic instrument (ultrasonic frequency is 40KHz), and carrying out ultrasonic treatment at 25 ℃ for 10min to gradually change the solution into viscous slurry, wherein the volume of the viscous slurry is increased. And transferring the slurry into a vacuum oven, and drying.
(4) And (4) repeatedly washing the solid obtained in the step (3) with deionized water for 3 times, and drying in vacuum at 70 ℃ for 4 hours to obtain the gel type silicon-based negative electrode S-12.
A battery was assembled and tested for electrical properties according to the method of example 1, except that the silicon-based negative electrode material S-1 was replaced with the material S-12 prepared in example 12. The test result shows that the capacity retention rate of the material S-12 in example 12 is about 83% after 400 cycles under the constant current discharge rate of 0.2C.
Example 13
(1) Weighing 2.79g of aniline and 6.6g of phytic acid, adding the aniline and the phytic acid into 20mL of ethanol solution, uniformly mixing, adding 0.8g of nano silicon powder, and uniformly dispersing to obtain a mixture A.
(2) 1.71g of ammonium persulfate was dissolved in 10mL of deionized water and designated as solution B.
(3) And mixing the mixture A and the solution B, uniformly stirring, putting the mixed solution into an ultrasonic instrument (ultrasonic frequency is 40KHz), and carrying out ultrasonic treatment at 25 ℃ for 10min to gradually change the solution into viscous slurry, wherein the volume of the viscous slurry is increased. And transferring the slurry into a vacuum oven, and drying.
(4) And (4) repeatedly washing the solid obtained in the step (3) with deionized water for 3 times, and drying in vacuum at 70 ℃ for 4 hours to obtain the gel type silicon-based negative electrode S-13.
A battery was assembled and tested for electrical properties according to the method of example 1, except that the silicon-based negative electrode material S-1 was replaced with the material S-13 prepared in example 13. The test result shows that the capacity retention rate of the material S-13 in example 13 is about 82% after 400 cycles under the constant current discharge rate of 0.2C.
Comparative example 1
(1) Weighing 4.65g of aniline, uniformly mixing, adding 11.25g of nano silicon powder, and uniformly dispersing to obtain a mixture A.
(2) 2.85g of ammonium persulfate was dissolved in 10mL of deionized water and designated as solution B.
(3) And mixing the mixture A and the solution B, uniformly stirring, putting the mixed solution into an ultrasonic instrument (ultrasonic frequency is 40KHz), carrying out ultrasonic treatment at 25 ℃ for 2min, and standing, wherein only black precipitate (named as D-1) appears in the solution at the moment, and no gel appears. SEM characterization results prove that the black precipitate is a mixture of polyaniline solid and nano silicon powder.
Comparative example 2
(1) Weighing 4.65g of aniline and 6.6g of phytic acid, uniformly mixing, adding 11.25g of nano silicon powder, uniformly dispersing, and then naming as a mixture A.
(2) 2.85g of ammonium persulfate was dissolved in 10mL of deionized water and designated as solution B.
(3) And mixing the mixture A and the solution B, uniformly stirring, standing for 10min, gradually thickening the solution into thick slurry, keeping the volume unchanged, keeping the system color brown, drying, and then naming the mixture as D-2, and performing SEM characterization. SEM characterization results prove that the polymer and the silicon powder in the mixture are separated seriously and no three-dimensional network structure is formed.
Comparative example 3
(1) Weighing 4.65g of aniline and 6.6g of phytic acid, uniformly mixing, adding 11.25g of nano silicon powder, uniformly dispersing, and then naming as a mixture A.
(2) 2.85g of ammonium persulfate was dissolved in 10mL of deionized water and designated as solution B.
(3) Mixing the mixture A and the solution B, performing ultrasonic treatment (ultrasonic frequency 40KHz) for 2min during stirring, and standing, wherein dark green precipitate (named as D-3) appears in the solution. SEM characterization results prove that D-3 is a particle with the nano-silicon powder wrapped by polyaniline.
The embodiment and the result show that the silicon-based negative electrode material provided by the invention can obviously improve the cycle stability of the silicon-based negative electrode material, and can improve the energy density of a lithium battery when being applied to the lithium ion battery.
Claims (14)
1. The gel type silicon-based negative electrode material is characterized by comprising conductive polymer gel and a powder silicon source, wherein the conductive polymer gel is of a three-dimensional network structure, and the surface of the powder silicon source is coated by the conductive polymer gel and is dispersed in a framework of the three-dimensional network structure of the conductive polymer gel.
2. The silicon-based anode material as claimed in claim 1, wherein the conductive polymer is an organic acid-doped conductive polymer; the organic acid is selected from one or more of phytic acid, citric acid, succinic acid and tartaric acid.
3. The silicon-based anode material as claimed in claim 2, wherein the organic acid is doped in an amount such that the molar ratio of the organic acid to the monomer used in the conductive polymer is 1: 2-10.
4. The silicon-based anode material as claimed in claim 1, wherein the powdered silicon source is bonded to the conductive polymer by an R (O) -O-Si bond.
5. The silicon-based anode material of claim 1, further comprising an additive selected from any one or more of natural graphite, artificial graphite, carbon nanotubes, and carbon black.
6. The silicon-based anode material according to claim 1 or 5, wherein the silicon source powder comprises 5% to 75% of the total mass of the silicon-based anode material, the conductive polymer gel comprises 5% to 95% of the conductive polymer, and the additive comprises 0% to 50%;
preferably, the silicon source content is 5% to 50%, the conductive polymer gel content is 5% to 65% and the additive content is 30% to 50% based on the total mass of the silicon-based negative electrode material.
7. The silicon-based negative electrode material as claimed in claim 1, wherein the median particle diameter of the powdered silicon source is 0.05-5.0 μm; and/or the conductive polymer is one or more of polyaniline, polyaniline derivatives, polythiophene derivatives, polypyrrole and polypyrrole derivatives.
8. A method for preparing a silicon-based anode material as claimed in any one of claims 1 to 7, comprising:
and carrying out in-situ polymerization on the conductive polymer in the powdered silicon source dispersion liquid under the ultrasonic condition.
9. The preparation method according to claim 8, wherein the preparation method of the silicon-based anode material specifically comprises the following steps:
(1) mixing a monomer for synthesizing a conductive polymer, an organic acid and a powdery silicon source to obtain a mixture A;
(2) preparing a catalyst into a solution B;
(3) and uniformly mixing the mixture A and the solution B, carrying out polymerization reaction under the ultrasonic condition to obtain viscous slurry, and drying to obtain the gel type silicon-based negative electrode material.
10. The method according to claim 9, wherein the monomer in step (1) is at least one of aniline, aniline derivatives, thiophene derivatives, pyrrole, and pyrrole derivatives;
and/or the powdery silicon source in the step (1) is at least one of simple substance silicon, silicon-oxygen compound and silicon alloy;
and/or, the catalyst in the step (2) is at least one of ammonium persulfate, hydrogen peroxide, ferric trichloride, benzoyl peroxide, ammonium ceric sulfate, sodium persulfate and ceric sulfate;
and/or the dosage of the catalyst is 0.1 to 0.5 time of the molar weight of the conductive polymer monomer;
and/or the organic acid is selected from one or more of phytic acid, citric acid, succinic acid and tartaric acid; the molar ratio of the organic acid to the polymer monomer is 1: 2-10.
11. The preparation method of claim 9, wherein the reaction solvent is added in step (1), and the reaction cosolvent is selected from any one or more of water, alcohols, amides, ketones and ethers.
12. The production method according to claim 8 or 9, wherein the polymerization reaction conditions in the step (3) are as follows: the reaction temperature is 20-40 ℃, the ultrasonic frequency is 20KHz-40KHz, and the ultrasonic time is 1min-60 min.
13. Use of a silicon-based negative electrode material according to any one of claims 1 to 7 or a silicon-based negative electrode material prepared by a method according to any one of claims 8 to 13 in a lithium ion battery.
14. A lithium ion battery, which comprises the silicon-based negative electrode material of any one of claims 1 to 7 or the silicon-based negative electrode material prepared by the method of any one of claims 8 to 13, a positive electrode material containing lithium, a separator and an electrolyte.
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