CN108417810B - Preparation method of polyaniline/graphene/silicon composite material with three-dimensional network structure - Google Patents
Preparation method of polyaniline/graphene/silicon composite material with three-dimensional network structure Download PDFInfo
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Abstract
The invention discloses a preparation method of a polyaniline/graphene/silicon composite material with a three-dimensional network structure, which comprises the following steps: adding p-phenylenediamine into water, stirring and dissolving in a water bath, adding a silicon source, stirring and dispersing, adding graphene oxide, uniformly dispersing, and carrying out hydrothermal reaction to obtain hydrogel M1; adding hydrogel M1 into hydrochloric acid for precooling, and adding NaNO2Solution and HBF4Respectively precooling the solution, and dropwise adding precooled NaNO into hydrochloric acid containing hydrogel M1 in an ice water bath2Solution and precooled HBF4Carrying out solution and then carrying out diazotization reaction to obtain hydrogel M2; dissolving aniline monomer in sulfuric acid solution, adding hydrogel M2, soaking, and precooling to obtain a first mixed solution; dissolving ammonium persulfate in a sulfuric acid solution, and precooling to obtain a second mixed solution; and dropwise adding the second mixed solution into the first mixed solution in an ice-water bath, and adjusting the temperature to perform polymerization reaction to obtain the polyaniline/graphene/silicon composite material with the three-dimensional network structure.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a preparation method of a polyaniline/graphene/silicon composite material with a three-dimensional network structure.
Background
With the development of electric vehicles and portable electric appliances, the demand of high-energy density lithium ion batteries is increasing day by day. The theoretical specific capacity of the traditional graphite negative electrode material is only 372mAh/g, and the market demand is difficult to meet. The first gram capacity of the silicon material is 4200mAh/g, the lithium embedding platform is higher, the earth crust is rich in storage, the silicon material is environment-friendly and the like, and gradually attracts the wide attention of researchers.
However, the volume expansion of silicon is as high as 300%, which not only causes the silicon to separate from the surrounding conductive carbon network and form "dead silicon" during cycling, but also causes the silicon to delaminate from the current collector. Secondly, the larger volume expansion can also cause the continuous recombination damage of the SEI film on the surface, so that the SEI film becomes thicker and thicker, and the Li of the anode is continuously consumed+The coulomb efficiency decreases. Finally, the large volume expansion leads to dusting of the silicon material late in the cycle, and these problems ultimately lead to a dramatic deterioration in cycle performance.
Currently, researchers have mainly solved the above problems by compounding silicon with a carbon material, compounding with a metal material, or using silica. In the aspect of metal silicon alloy, the volume expansion of the material is buffered mainly by compounding with metals such as Al, Ti, Mg and the like, and the cycle performance of the silicon can be greatly improved. In the aspect of silicon-carbon materials, the defects of silicon materials are mainly improved by means of solid/liquid phase mixing, liquid phase coating, spray drying granulation, high-temperature sintering and the like of the silicon materials and the carbon materials, so that the electric conductivity of the materials can be improved, the volume expansion of the materials is buffered, and the circulation stability of the materials is improved to a certain extent. In addition, some studies have been made on silica materials which have a reduced gram capacity but improved cycle performance relative to the silicon material. The biggest problem is that the first effect is low and is only 65-70%, and in the actual use process, the pre-lithiation is needed, but the pre-lithiation process is not mature, and the pre-lithiation is used after being mixed with graphite at present.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a preparation method of a polyaniline/graphene/silicon composite material with a three-dimensional network structure, which overcomes the defects in the prior art, can effectively buffer the volume expansion of silicon, improve the electronic and ionic conductivity of the material and improve the interface performance of the material, and the obtained composite material is in a three-dimensional network structure, not only provides a path for the transmission of lithium ions, but also can buffer the volume deformation of the silicon material in the charging and discharging process. In addition, the polyaniline can improve the interface performance of the material, is in a chain structure in the composite material, and provides an electron channel and an ion channel between silicon particles in the charging and discharging processes. Finally, the graphene and the polyaniline can also improve the electronic conductivity of the silicon material, reduce the polarization of the material and improve the cycling stability of the silicon-based material to a certain extent.
The invention provides a preparation method of a polyaniline/graphene/silicon composite material with a three-dimensional network structure, which comprises the following steps:
s1, adding p-phenylenediamine into deionized water, stirring and dissolving in a water bath, adding a silicon source, stirring and dispersing, adding graphene oxide, dispersing uniformly, and carrying out hydrothermal reaction to obtain hydrogel M1;
s2, adding hydrogel M1 into hydrochloric acid for precooling, and then adding NaNO2Solution and HBF4Respectively precooling the solution, and dropwise adding precooled NaNO into hydrochloric acid containing hydrogel M1 in an ice water bath2Solution and precooled HBF4Carrying out a diazotization reaction on the solution, and washing the solution by deionized water to obtain hydrogel M2;
s3, dissolving aniline monomer in sulfuric acid solution, adding hydrogel M2, soaking, and precooling to obtain a first mixed solution; dissolving ammonium persulfate in a sulfuric acid solution, and precooling to obtain a second mixed solution; and dropwise adding the second mixed solution into the first mixed solution in an ice water bath, adjusting the temperature to perform polymerization reaction, washing with a sulfuric acid solution, and drying to obtain the polyaniline/graphene/silicon composite material with the three-dimensional network structure.
Preferably, in S1, the silicon source is at least one of nano-silicon particles, silicon nanowires, silicon nano-films, and silicon monoxide.
Preferably, in S1, the mass ratio of p-phenylenediamine to graphene oxide is 8-12: 1.
preferably, in S1, the mass ratio of the silicon source to the graphene oxide is 7-57: 3.
preferably, in S1, the water bath temperature is 50-90 ℃.
Preferably, in S1, the hydrothermal reaction temperature is 120-200 ℃ and the hydrothermal reaction time is 0.5-10 h.
Preferably, in S2, the pre-cooling temperature is 0 ℃.
Preferably, the concentration of the hydrochloric acid in S2 is 0.8-1.2 mol/L.
Preferably, in S2, NaNO2NaNO in solution2And HBF4HBF in solution4The mass ratio of (1): 1 to 4.
Preferably, in S2, the diazotization reaction temperature is-10-20 ℃, and the diazotization reaction time is 0.5-4 h.
Preferably, in S3, the soaking time is 2-10 h.
Preferably, in S3, the pre-cooling temperature is 0 ℃.
Preferably, in S3, the molar ratio of aniline monomer to ammonium persulfate is 1:1 to 4.
Preferably, in S3, the concentration of the sulfuric acid solution is 0.4-0.6 mol/L.
Preferably, in S3, the polymerization temperature is-10 to 20 ℃ and the polymerization time is 2 to 12 hours.
Preferably, in S3, the drying temperature is 60-100 ℃.
Compared with the prior art, the invention has the advantages that:
(1) the polyaniline/graphene/silicon composite material is of a three-dimensional network structure, can buffer the volume expansion of a silicon-based material in the charging and discharging processes, and provides a channel for the rapid transmission of lithium ions;
(2) the polyaniline adopted by the invention can improve the interface performance of the material and improve the interface stability, and because the polyaniline is in a chain structure, even if part of silicon particles are broken in the charging and discharging process, the polyaniline can still provide an electron channel and an ion channel for the silicon particles, thereby greatly improving the cycle performance of the material;
(3) according to the invention, the electronic conductivity of the silicon-based material can be improved by adopting the graphene and the polyaniline, the polarization of the material is reduced, and the multiplying power performance of the material is improved;
(4) the method is simple, easy to control and realize industrial operation, and the obtained polyaniline/graphene/silicon composite material has good cycling stability and rate capability.
Drawings
Fig. 1 is an SEM image of the polyaniline/graphene/silicon composite material obtained in example 1 of the present invention.
Fig. 2 is a TEM image of the polyaniline/graphene/silicon composite material obtained in example 1 of the present invention at a low magnification.
Fig. 3 is a TEM image of the polyaniline/graphene/silicon composite material obtained in example 1 of the present invention at a high magnification.
Fig. 4 is a first charge-discharge curve of the polyaniline/graphene/silicon composite material obtained in example 1 of the present invention and a comparative example.
Fig. 5 is a graph of the cycle performance of the polyaniline/graphene/silicon composite material obtained in example 1 of the present invention and the comparative example at a current density of 0.1C.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
A preparation method of a polyaniline/graphene/silicon composite material with a three-dimensional network structure comprises the following steps:
s1, adding 0.288g of p-phenylenediamine into 100mL of deionized water, stirring and dissolving in a water bath at 60 ℃, adding 0.684g of nano silicon, stirring and dispersing, then adding 12mL of graphene oxide dispersion liquid with the mass fraction of 3mg/mL, uniformly dispersing, and then carrying out hydrothermal reaction at 180 ℃ for 2 hours to obtain hydrogel M1;
s2, adding hydrogel M1 into 100mL of hydrochloric acid with the concentration of 1mol/L for precooling to 0 ℃; 0.2g NaNO was added2Adding into 4mL deionized water, measuring 8mL HBF with mass fraction of 14 wt%4Pre-cooling the two solutions to 0 deg.C; adding pre-cooled NaNO dropwise into hydrochloric acid containing hydrogel M1 in ice water bath2Solution and precooled HBF4Carrying out diazotization reaction on the solution at the temperature of 0 ℃ for 2h, and washing with deionized water to obtain hydrogel M2;
s3, dissolving 10mL of aniline monomer with the molar concentration of 0.01mol/L into sulfuric acid solution with the concentration of 0.5mol/L, adding hydrogel M2, soaking for 7 hours, and precooling to 0 ℃ to obtain first mixed liquid; dissolving 0.03g of ammonium persulfate in 3mL of sulfuric acid solution with the molar concentration of 0.5mol/L, and precooling to 0 ℃ to obtain a second mixed solution; and dropwise adding the second mixed solution into the first mixed solution in an ice-water bath, then carrying out polymerization reaction at the temperature of 0 ℃ for 6 hours, washing with sulfuric acid solution for 3-5 times, and completely drying in an oven at the temperature of 80 ℃ to obtain the polyaniline/graphene/silicon composite material with the three-dimensional network structure.
Fig. 1 is an SEM image of the polyaniline/graphene/silicon composite material obtained in this example, and it can be found from fig. 1 that: the graphene is in a three-dimensional network structure, and the nano silicon is dispersed in three-dimensional network channels of the graphene. Fig. 2 is a TEM image of the polyaniline/graphene/silicon composite material obtained in example 1 of the present invention at a low magnification, fig. 3 is a TEM image of the polyaniline/graphene/silicon composite material obtained in example 1 of the present invention at a high magnification, and it can be found from fig. 2 and fig. 3 that: the size of the nano silicon particles is about 50-80 nm, and the nano silicon particles are uniformly distributed on the surface of the graphene.
The polyaniline/graphene/silicon composite material obtained in the embodiment and Super-P, LA133 are subjected to grinding, slurry mixing and coating according to a ratio of 8:1:1, a button CR2016 battery is assembled, and an electrochemical performance test is performed by using 1mol/L EC + DMC solution of LiPF6 as an electrolyte.
Example 2
A preparation method of a polyaniline/graphene/silicon composite material with a three-dimensional network structure comprises the following steps:
s1, adding 0.432g of p-phenylenediamine into 100mL of deionized water, stirring and dissolving in a water bath at 50 ℃, adding 0.684g of silicon nanowire, stirring and dispersing, then adding 12mL of graphene oxide dispersion liquid with the mass fraction of 3mg/mL, uniformly dispersing, and then carrying out hydrothermal reaction at the temperature of 120 ℃ for 0.5h to obtain hydrogel M1;
s2, adding hydrogel M1 into 100mL of hydrochloric acid with the concentration of 1mol/L for precooling to 0 ℃; 0.2g NaNO was added2Adding into 4mL deionized water, weighing 32mL HBF with mass fraction of 4 wt%4Pre-cooling the two solutions to 0 deg.C; adding pre-cooled NaNO dropwise into hydrochloric acid containing hydrogel M1 in ice water bath2Solution and precooled HBF4Carrying out diazotization reaction on the solution at the temperature of 0 ℃ for 4h, and washing with deionized water to obtain hydrogel M2;
s3, dissolving 10mL of aniline monomer with the molar concentration of 0.01mol/L into sulfuric acid solution with the concentration of 0.5mol/L, adding hydrogel M2, soaking for 7 hours, and precooling to 0 ℃ to obtain first mixed liquid; dissolving 0.03g of ammonium persulfate in 3mL of sulfuric acid solution with the molar concentration of 0.5mol/L, and precooling to 0 ℃ to obtain a second mixed solution; and dropwise adding the second mixed solution into the first mixed solution in an ice-water bath, then carrying out polymerization reaction at the temperature of 0 ℃ for 12 hours, washing with sulfuric acid solution for 3-5 times, and completely drying in a drying oven at the temperature of 100 ℃ to obtain the polyaniline/graphene/silicon composite material with the three-dimensional network structure.
Example 3
A preparation method of a polyaniline/graphene/silicon composite material with a three-dimensional network structure comprises the following steps:
s1, adding 0.432g of p-phenylenediamine into 100mL of deionized water, stirring and dissolving in a water bath at 50 ℃, adding 0.684g of silicon oxide, stirring and dispersing, then adding 12mL of graphene oxide dispersion liquid with the mass fraction of 3mg/mL, uniformly dispersing, and then carrying out hydrothermal reaction at 120 ℃ for 0.5h to obtain hydrogel M1;
s2, adding hydrogel M1 into 100mL of hydrochloric acid with the concentration of 1mol/L for precooling to 0 ℃; 0.2g NaNO was added2Adding into 4mL deionized water, weighing 32mL HBF with mass fraction of 4 wt%4Pre-cooling the two solutions to 0 deg.C; adding pre-cooled NaNO dropwise into hydrochloric acid containing hydrogel M1 in ice water bath2Solution and precooled HBF4Carrying out diazotization reaction on the solution at the temperature of 0 ℃ for 0.5h, and washing with deionized water to obtain hydrogel M2;
s3, dissolving 10mL of aniline monomer with the molar concentration of 0.01mol/L into sulfuric acid solution with the concentration of 0.5mol/L, adding hydrogel M2, soaking for 6 hours, and precooling to 0 ℃ to obtain first mixed liquid; dissolving 0.023g of ammonium persulfate in 3mL of sulfuric acid solution with the molar concentration of 0.5mol/L, and precooling to 0 ℃ to obtain a second mixed solution; and dropwise adding the second mixed solution into the first mixed solution in an ice-water bath, then carrying out polymerization reaction at the temperature of 0 ℃ for 2 hours, washing with a sulfuric acid solution for 3-5 times, and completely drying in a 60 ℃ drying oven to obtain the polyaniline/graphene/silicon composite material with the three-dimensional network structure.
Example 4
A preparation method of a polyaniline/graphene/silicon composite material with a three-dimensional network structure comprises the following steps:
s1, adding 0.288g of p-phenylenediamine into 100mL of deionized water, stirring and dissolving in a water bath at 50 ℃, adding 0.684g of silicon oxide, stirring and dispersing, then adding 12mL of graphene oxide dispersion liquid with the mass fraction of 3mg/mL, uniformly dispersing, and then carrying out hydrothermal reaction at the temperature of 120 ℃ for 0.5h to obtain hydrogel M1;
s2, adding hydrogel M1 into 100mL of hydrochloric acid with the concentration of 1mol/L for precooling to 0 ℃; 0.2g NaNO was added2Adding into 4mL deionized water, weighing 32mL HBF with mass fraction of 4 wt%4Pre-cooling the two solutions to 0 deg.C; adding pre-cooled NaNO dropwise into hydrochloric acid containing hydrogel M1 in ice water bath2Solution and precooled HBF4Carrying out diazotization reaction on the solution at the temperature of 0 ℃ for 0.5h, and washing with deionized water to obtain hydrogel M2;
s3, dissolving 10mL of aniline monomer with the molar concentration of 0.01mol/L into sulfuric acid solution with the concentration of 0.5mol/L, adding hydrogel M2, soaking for 6 hours, and precooling to 0 ℃ to obtain first mixed liquid; dissolving 0.023g of ammonium persulfate in 3mL of sulfuric acid solution with the molar concentration of 0.5mol/L, and precooling to 0 ℃ to obtain a second mixed solution; and dropwise adding the second mixed solution into the first mixed solution in an ice-water bath, then carrying out polymerization reaction at the temperature of 0 ℃ for 2 hours, washing with a sulfuric acid solution for 3-5 times, and completely drying in a 60 ℃ drying oven to obtain the polyaniline/graphene/silicon composite material with the three-dimensional network structure.
Comparative example
Grinding, slurry mixing and coating are carried out on the nano silicon and the Super-P, LA133 according to the ratio of 8:1:1, a button CR2016 battery is assembled, and an EC + DMC solution of 1mol/L LiPF6 is selected as an electrolyte to carry out an electrochemical performance test.
Fig. 4 and 5 are graphs of the first charge and discharge curves and cycle performance of the materials prepared in example 1 and comparative example. Under the current density of 0.1C, the initial charging specific capacity of the polyaniline/graphene/silicon composite material is 2685mAh/g, the initial effect is 85%, the charging specific capacity of the material after 50 weeks is 2499mAh/g, and the capacity retention rate is 93%; the first charging specific capacity of the nano silicon material used in the comparative example is 2244mAh/g, the first coulombic efficiency is 61.7%, and the specific capacity after 30-week circulation is only 300mAh/g, so that the circulation stability of the polyaniline/graphene/silicon composite material with the three-dimensional network structure obtained by the method is greatly improved.
The improvement of the electrical property is that the polyaniline/graphene/silicon composite material is in a three-dimensional network structure, so that a path is provided for the transmission of lithium ions, and the volume deformation of the silicon material in the charging and discharging process can be buffered. In addition, the polyaniline can improve the interface performance of the material, is in a chain structure in the composite material, and provides an electron channel and an ion channel between silicon particles in the charging and discharging processes. Finally, the graphene and the polyaniline can also improve the electronic conductivity of the silicon material, reduce the polarization of the material and improve the cycling stability of the silicon-based material to a certain extent.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (7)
1. A preparation method of a polyaniline/graphene/silicon composite material with a three-dimensional network structure is characterized by comprising the following steps:
s1, adding p-phenylenediamine into deionized water, stirring and dissolving in a water bath, adding a silicon source, stirring and dispersing, and then adding graphene oxide, wherein the mass ratio of the p-phenylenediamine to the graphene oxide is 8-12: 1, the mass ratio of the silicon source to the graphene oxide is 7-57: 3; then carrying out hydrothermal reaction to obtain hydrogel M1;
s2, adding hydrogel M1 into hydrochloric acid for precooling, and then adding NaNO2Solution and HBF4Respectively precooling the solution, and dropwise adding precooled NaNO into hydrochloric acid containing hydrogel M1 in an ice water bath2Solution and precooled HBF4Carrying out solution and then carrying out diazotization reaction to obtain hydrogel M2;
s3, dissolving aniline monomer in sulfuric acid solution, adding hydrogel M2, soaking, and precooling to obtain a first mixed solution; dissolving ammonium persulfate in a sulfuric acid solution, and precooling to obtain a second mixed solution; dropwise adding the second mixed solution into the first mixed solution in an ice-water bath, and adjusting the temperature to perform polymerization reaction to obtain a polyaniline/graphene/silicon composite material with a three-dimensional network structure;
in S1, the silicon source is at least one of nano-silicon particles, silicon nanowires, silicon nano-films and silicon monoxide;
wherein in S1, the hydrothermal reaction temperature is 120-200 ℃ and the hydrothermal reaction time is 0.5-10 h.
2. The preparation method of the polyaniline/graphene/silicon composite material with the three-dimensional network structure according to claim 1, wherein in S1, the water bath temperature is 50-90 ℃.
3. The preparation method of the polyaniline/graphene/silicon composite material with the three-dimensional network structure according to claim 1 or 2, wherein in S2, the precooling temperature is 0 ℃; in S2, the concentration of hydrochloric acid is 0.8-1.2 mol/L.
4. The preparation method of the polyaniline/graphene/silicon composite material with the three-dimensional network structure according to claim 1 or 2, wherein in S2, the diazotization reaction temperature is-10-20 ℃, and the diazotization reaction time is 0.5-4 h.
5. The preparation method of the polyaniline/graphene/silicon composite material with the three-dimensional network structure according to claim 1 or 2, wherein in S3, the soaking time is 2-10 h; in S3, the precooling temperature is 0 ℃.
6. The preparation method of the polyaniline/graphene/silicon composite material with the three-dimensional network structure according to claim 1 or 2, wherein in S3, the concentration of a sulfuric acid solution is 0.4-0.6 mol/L.
7. The preparation method of the polyaniline/graphene/silicon composite material with the three-dimensional network structure according to claim 1 or 2, wherein in S3, the polymerization reaction temperature is-10-20 ℃, and the polymerization reaction time is 2-12 h.
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