CN107146888B - Polymer-modified three-dimensional ordered mesoporous silicon negative electrode material and preparation method thereof - Google Patents
Polymer-modified three-dimensional ordered mesoporous silicon negative electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a polymer-modified three-dimensional ordered mesoporous silicon negative electrode material and a preparation method thereof, belonging to the technical field of lithium ion battery negative electrode materials. The material is prepared by mixing a three-dimensional ordered mesoporous silica precursor with magnesium powder, calcining in an inert atmosphere, removing impurities by using an acidic solution, sequentially adding a surfactant, a polymer monomer and an initiator, reacting for a period of time at a low temperature under an inert gas, and then performing suction filtration, washing and drying. The cathode material prepared by the preparation method takes the conductive polymer as a modifier, and the surface of the three-dimensional ordered mesoporous silicon is coated with a layer of the conductive polymer to provide a buffer layer for the volume expansion of the silicon, so that the conductivity and the cycling stability of the material are improved. The cathode material prepared by the invention has the advantages of high discharge specific capacity, good cycling stability and excellent rate capability, and can solve the problems of volume expansion and capacity fading in the cycling process of the conventional silicon-based cathode material.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery cathode materials, and particularly relates to a polymer-modified three-dimensional ordered mesoporous silicon cathode material and a preparation method thereof
Background
With the development of global economy, the problems of environmental deterioration, resource shortage and the like become more serious, and the development of new energy with high efficiency and environmental protection becomes the research focus of the current society. Lithium ion batteries are favored because of their high specific energy, good cycle performance, low self-discharge rate, no memory effect, and environmental friendliness.
In recent years, with the strong support of new energy automobiles in China, the market volume of clean and pollution-free electric automobiles is increased by well injection. However, currently commercialized lithium ion battery graphite (372 mAhg)-1) The cathode material can only reach 300-340 mAhg in practical application-1The capacity of the lithium ion battery is difficult to be improved, and the urgent need of new market users for high-performance lithium ion batteries cannot be met. Therefore, more and more people are working on developing high energy density battery materials. The silicon negative electrode material has higher theoretical specific capacity (3752 mAhg)-1) Environmentally friendly and inexpensive subject to researchersIt is expected to become the prime mover of the next-generation battery system. However, the development of silicon negative electrode materials has many problems, for example, the volume expansion effect of elemental silicon reaches as high as 300% in the charging and discharging processes, which causes the problems of easy collapse and easy pulverization of the internal structure, and seriously restricts the development and application of silicon as the negative electrode material of lithium ion batteries. To solve the above problems, it is a key to research to suppress the volume expansion effect in the electrode reaction and improve the poor conductivity of elemental silicon.
At present, the method for improving the silicon-based composite negative electrode material mainly adopts the nanometer silicon and the carbon material to carry out the compounding so as to achieve the purposes of high energy density, high rate performance and good cycle stability. The coated and embedded carbon-silicon composite materials are prepared by different methods, so that the stability of the electrode material is greatly improved. The structural design takes nano Si as an active material to provide high capacity, C as a dispersion phase to buffer the huge volume change of Si in the charge-discharge process, thereby ensuring that the structure of the material is not damaged, and improving the problems of poor electrical contact, rapid capacity attenuation and poor cycle performance of a Si negative electrode material and a current collector in the charge-discharge process. Among them, researchers have proposed an inverted microemulsion method to synthesize spherical silica garnet microbeads as a negative electrode material. Firstly, TEOS is adopted to coat SiO on silicon nano particles2Layer, Si @ SiO2The water solution of the nano particles is mixed with an emulsifier containing 0.3 percent of mass fraction to form emulsified oil in water. Then heat treatment is carried out in the air to remove organic matters and concentrate the particle swarm structure. The particle population is then coated with a formaldehyde Resin (RF) layer, which converts the formaldehyde resin layer into a carbon layer. The thickness of the carbon layer can be adjusted by changing the addition amount of formaldehyde resin molecules. Finally, SiO2The layer may be removed with hydrofluoric acid to form voids to accommodate large volume changes of the silicon material during charging and discharging. The specific energy of the nano silicon can reach 3050 mAh/g. The volumetric specific energy calculated by the volume of the electrode is up to 1270mAh/cm3Is a graphite negative electrode 600mAh/cm3More than twice as much. At C/2, the capacity retention rate is over 97% from 2 to 1000 cycles. After 1000 times of circulation, the specific capacity exceeds 1160mAh/g and exceeds 3 times of the theoretical specific capacity of the graphite. But it isThe complicated experimental steps and the harsh experimental conditions limit the wide-range practical application of the method. Patent CN102916167A discloses that a mesoporous silicon compound (Si/CoSi) is prepared by uniformly mixing silicon powder and cobalt silicide by ball milling, and coating with a carbon layer2and/C), the first discharge capacity of the prepared battery is 1457.6mAh/g, and the capacity retention rate after 100 circles is 56.8%. Although the cycle performance of the material is improved to a certain extent, the material shows a lower reversible capacity, and the complexity of the experimental preparation process is not favorable for the practical application.
Disclosure of Invention
Aiming at the problems of serious capacity decline caused by easy expansion and pulverization of the volume of the conventional silicon-based negative electrode material, poor cycle performance and the like, the invention provides a polymer-modified three-dimensional ordered mesoporous silicon negative electrode material and a preparation method thereof. The purpose of the invention is realized by the following technical scheme:
the invention aims to provide a polymer modified three-dimensional ordered mesoporous silicon cathode material, which is prepared by mixing a three-dimensional ordered mesoporous silicon dioxide precursor with magnesium powder, calcining the mixture in an inert atmosphere, removing impurities by using an acidic solution, sequentially adding a surfactant, a polymer monomer and an initiator, reacting the mixture for a period of time at a low temperature under an inert gas, and performing suction filtration, washing and drying.
According to a specific embodiment of the polymer-modified three-dimensional ordered mesoporous silicon anode material, the three-dimensional ordered mesoporous silicon dioxide precursor is prepared by hydrolyzing and hydrothermally reacting raw materials including P123 and tetraethoxysilane, and washing, drying and sintering an obtained product.
According to a specific embodiment of the polymer-modified three-dimensional ordered mesoporous silicon negative electrode material, the material has a lotus root-shaped rod-like structure in appearance, uniform particle size distribution and a porous structure, wherein the length of a lotus root node is 1-8 μm, and the width of the lotus root node is 0.5-1 μm.
The invention also aims to provide a preparation method of the polymer modified three-dimensional ordered mesoporous silicon anode material, which comprises the following steps:
1) dissolving P123 in an acidic solution, adding tetraethoxysilane for hydrolysis, and transferring the mixed solution to a reaction kettle for hydrothermal reaction;
2) carrying out suction filtration on a sample obtained by the hydrothermal reaction, washing the sample to be neutral, and then drying the sample;
3) heating the sample obtained in the step 2), heating to the end temperature at a certain heating rate, and cooling to room temperature after sintering to obtain a white three-dimensional ordered mesoporous silica precursor;
4) mixing the three-dimensional ordered mesoporous silicon dioxide precursor obtained in the step 3) with magnesium powder, calcining in an inert atmosphere to obtain a brown mixed sample, and putting the brown mixed sample into an acid solution to remove impurities to obtain brown three-dimensional ordered mesoporous silicon;
5) dispersing the three-dimensional ordered mesoporous silicon obtained in the step 4) in deionized water, adding a surfactant, performing ultrasonic dispersion, and stirring at low temperature.
6) Adding a polymer monomer into the solution obtained in the step 5), and dropwise adding an initiator into the solution;
7) and placing the whole reaction device at low temperature under inert gas for reaction for a period of time, and then carrying out suction filtration, washing and drying to obtain the polymer modified three-dimensional ordered mesoporous silicon cathode material.
According to a specific embodiment of the preparation method of the polymer-modified three-dimensional ordered mesoporous silicon negative electrode material, in the step 1), the mass ratio of the P123 to the tetraethoxysilane is 0.3-0.5, and the acidic solution is a hydrochloric acid solution or a sulfuric acid solution; the hydrolysis temperature is 30-40 ℃, and the hydrolysis time is 22-26 h; the temperature of the hydrothermal reaction is 100-110 ℃, and the time is 12-24 h; in the step 2), washing with absolute ethyl alcohol and deionized water; the drying temperature is 75-85 ℃, and the drying time is 10-14 h.
According to a specific embodiment of the preparation method of the polymer-modified three-dimensional ordered mesoporous silicon negative electrode material, in the step 3), the temperature rise rate is 3-10 ℃/min, and the end point temperature is 500-600 ℃; the sintering time is 4-8 h.
According to a specific embodiment of the preparation method of the polymer-modified three-dimensional ordered mesoporous silicon negative electrode material, in the step 4), the mass ratio of the three-dimensional ordered mesoporous silicon dioxide precursor to the magnesium powder is 0.7-1; the calcination temperature is 650-750 ℃, and the calcination time is 5-12 h; the inert atmosphere is a mixed gas of argon and hydrogen; wherein the volume ratio of argon is 80-99%, and the volume ratio of hydrogen is 1-20%; preferably, the acid solution is subjected to impurity removal in a hydrochloric acid or sulfuric acid solution, and then the acid solution is placed in a 1-5% hydrofluoric acid solution for impurity removal, wherein the impurity removal time is 2-6 h.
According to a specific embodiment of the preparation method of the polymer-modified three-dimensional ordered mesoporous silicon negative electrode material, in the step 5), the surfactant accounts for 3-7% of the mass of the three-dimensional ordered mesoporous silicon; the surfactant is one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and hexadecyl methyl ammonium bromide; the ultrasonic separation time is 25-30 min, the low-temperature stirring time is 25-30 min, and the low-temperature stirring temperature is 0-5 ℃.
According to a specific embodiment of the preparation method of the polymer-modified three-dimensional ordered mesoporous silicon negative electrode material, in step 6), the polymer monomer is one of an aniline monomer, a pyrrole monomer, dopamine or a thiophene monomer; the initiator is one of ammonium persulfate, ferric chloride or hydrogen peroxide; the mass ratio of the three-dimensional ordered mesoporous silicon to the polymer monomer is 1-3.5; the mass ratio of the polymer monomer to the initiator is 0.4-0.7.
According to a specific embodiment of the preparation method of the polymer-modified three-dimensional ordered mesoporous silicon anode material, in the step 7), the inert gas is one or two of nitrogen and argon; the reaction time is 12-24 h; the washing is alternately washed by absolute ethyl alcohol and deionized water; the drying temperature is 55-65 ℃, and the drying time is 4-8 h.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, tetraethoxysilane is used as a silicon source, P123 is added as a structure directing agent, a surfactant and a pore-making agent to prepare a three-dimensional ordered mesoporous silicon dioxide precursor, magnesium powder is used as a reducing agent, and the surfactant, a polymer monomer and an initiator are sequentially added after acid impurity removal to prepare the polymer modified three-dimensional ordered mesoporous silicon cathode material. The preparation method of the cathode material has the advantages of simplicity, easiness in implementation, wide applicability, easiness in repetition and the like.
2. The cathode material prepared by the preparation method takes the conductive polymer as a modifier, and the surface of the three-dimensional ordered mesoporous silicon is coated with a layer of the conductive polymer to provide a buffer layer for the volume expansion of the silicon, so that the conductivity and the cycling stability of the material are improved.
3. Compared with the existing silicon-based cathode material, the polymer-modified three-dimensional ordered mesoporous silicon cathode material fully utilizes the developed and abundant pore structure of the three-dimensional ordered mesoporous silicon, provides a high-speed channel for the insertion and the extraction of lithium ions in the rapid charge and discharge process, and greatly improves the conductivity and the structural stability of the material by the coating of the conductive polymer.
4. The polymer-modified three-dimensional ordered mesoporous silicon negative electrode material has the advantages of high discharge specific capacity, good cycling stability and excellent rate capability, and can well solve the problems of volume expansion and capacity decline in the cycling process of the conventional silicon-based negative electrode material.
5. The polymer-modified three-dimensional ordered mesoporous silicon negative electrode material can meet the use requirements of high-rate and rapid charge and discharge of a power lithium ion battery, and has good application prospects in the fields of lithium ion energy storage and power batteries.
Drawings
Fig. 1 is an infrared spectrum of the polypyrrole-modified three-dimensional ordered mesoporous silicon negative electrode material in example 1.
Fig. 2 is an SEM image of the polypyrrole-modified three-dimensional ordered mesoporous silicon negative electrode material in example 1.
Fig. 3 is a cycle life diagram of the polypyrrole-modified three-dimensional ordered mesoporous silicon negative electrode material in example 1.
Fig. 4 is a rate performance graph of the polypyrrole-modified three-dimensional ordered mesoporous silicon negative electrode material in example 1.
FIG. 5 shows a polypyrrole-modified three-dimensional ordered mesoporous silicon negative electrode material N in example 12Adsorption and desorption isotherm graphs.
Fig. 6 is an XRD pattern of the polypyrrole-modified three-dimensional ordered mesoporous silicon negative electrode material of example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The polymer modified three-dimensional ordered mesoporous silicon negative electrode material and the preparation method thereof are explained below by combining a specific reaction principle.
The preparation process of the polymer modified three-dimensional ordered mesoporous silicon negative electrode material comprises the following steps:
1) dissolving P123 in an acidic solution, adding tetraethoxysilane for hydrolysis, and transferring the mixed solution to a reaction kettle for hydrothermal reaction;
specifically, a certain amount of P123 template agent is ultrasonically dissolved in an acid solution, and then a certain amount of tetraethoxysilane is added to hydrolyze at the temperature of 30-40 ℃ for 22-26 hours; and then transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene material lining, sealing, and carrying out hydrolysis reaction for 12-24 hours at the temperature of 100-110 ℃.
The P123 in the invention is a triblock copolymer of polyethylene oxide-polypropylene oxide-polyethylene oxide.
Further, the mass ratio of the P123 to the tetraethoxysilane is 0.3-0.5. P123 is used as a structure directing agent, a surfactant and a pore-forming agent, and the proportion of the P123 to tetraethoxysilane can directly influence the lotus root-shaped rod-like morphology, the length and the particle size of the precursor material; the formula for hydrolyzing tetraethoxysilane as a silicon source to generate the three-dimensional ordered mesoporous silica precursor is as follows:
Si(OCH2CH3)4+2H2O＝SiO2+4C2H5OH。
further, the acid solution is one or two of hydrochloric acid or sulfuric acid solution. Still more preferably, the concentration of the hydrochloric acid or sulfuric acid solution is 2 mol/L. Under the acidic condition, P123 is dissolved to form sol-gel, and the added tetraethoxysilane can be hydrolyzed and self-assembled to form a three-dimensional ordered mesoporous silica precursor with a regular pore channel structure under the action of an interface guiding force between inorganic acid and P123.
2) Carrying out suction filtration on a sample obtained by the hydrothermal reaction, washing the sample to be neutral, and then drying the sample;
specifically, a sample obtained through the hydrothermal reaction in the step 1) is subjected to suction filtration, then is washed to be neutral by using absolute ethyl alcohol and water, and then is dried by blowing air at the temperature of 75-85 ℃ for 10-14 hours.
3) Heating the sample obtained in the step 2), heating to the end temperature at a certain heating rate, and cooling to room temperature after sintering to obtain a white three-dimensional ordered mesoporous silica precursor;
specifically, the dried sample obtained in the step 2) is placed in a muffle furnace, the temperature is raised to 500-600 ℃ at the heating rate of 3-10 ℃/min, and the mixture is sintered for 4-8 hours and then cooled to room temperature to obtain a white three-dimensional ordered mesoporous silica precursor. Redundant P123 and tetraethoxysilane in the sample can be removed completely within the set sintering temperature range; the three-dimensional ordered mesoporous silicon dioxide in the set sintering time range has larger specific surface area, pore volume and mesoporous pore size distribution.
4) Mixing the three-dimensional ordered mesoporous silicon dioxide obtained in the step 3) with magnesium powder, calcining in an inert atmosphere to obtain a brown mixed sample, and putting the brown mixed sample into an acid solution to remove impurities to obtain brown three-dimensional ordered mesoporous silicon;
specifically, the three-dimensional ordered mesoporous silica obtained in the step 3) is uniformly mixed with magnesium powder, and is calcined for 5-12 hours at the temperature of 650-750 ℃ in the atmosphere protected by inert gas to obtain a brown mixed sample; and (3) putting the brown mixed sample into an acid solution to remove impurities for a period of time, and removing magnesium powder, magnesium oxide and silicon dioxide which are not completely reacted to obtain a brown sample three-dimensional ordered mesoporous silicon.
Further, the mass ratio of the three-dimensional ordered mesoporous silica to the magnesium powder is 0.7-1. Too little or too much magnesium powder results in the formation of side reactions and the formation of impurities such as magnesium silicate and magnesium silicide.
Further, the inert gas is preferably a mixed gas of argon and hydrogen; preferably, the volume of the argon gas is 80-99%, and the volume of the hydrogen gas is 1-20%. The inert atmosphere can prevent the magnesium powder from being oxidized to lose the effect of the reducing agent and ensure that the generated three-dimensional ordered mesoporous silicon is not oxidized.
Preferably, the acid solution impurity removal is carried out in a hydrochloric acid or sulfuric acid solution, and then the acid solution is placed in a 1-5% hydrofluoric acid solution to remove impurities. Further, the concentration of the hydrochloric acid or sulfuric acid solution is 2 mol/L. The selected hydrochloric acid or sulfuric acid solution can remove magnesium silicate, magnesium silicide and magnesium powder which does not participate in the reaction during the magnesium thermal reaction; the hydrofluoric acid solution can remove the three-dimensional ordered mesoporous silica which does not participate in the reaction. Further, the impurity removal time is 2-6 h. The time for removing the impurities in the hydrochloric acid or sulfuric acid or hydrofluoric acid may be set according to the specific effect of removing the impurities, and is conventional for those skilled in the art, and is not specifically illustrated and limited herein.
5) Dispersing the three-dimensional ordered mesoporous silicon obtained in the step 4) in deionized water, adding a surfactant, performing ultrasonic dispersion, and stirring at low temperature.
Specifically, dispersing the three-dimensional ordered mesoporous silicon obtained in the step 4) in deionized water, adding a surfactant, ultrasonically dispersing for 25-30 min, stirring at a low temperature for 25-30 min, and controlling the low temperature at 0-5 ℃.
Further, the surfactant is preferably 3-7% of the mass of the three-dimensional ordered mesoporous silicon. The surfactant can perform a surface modification function, and increase the active sites for successful attachment and polymerization of the polymer monomer.
Further, the surfactant is preferably one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and hexadecyl methyl ammonium bromide. According to the invention, the surfactant modification of the anion group is preferably selected, the negative electricity group is formed on the surface of the three-dimensional ordered mesoporous silicon, the polymer monomer is firstly ionized into the positive electricity group before polymerization, and the surface of the polymer monomer is better coated with the conductive polymer under the action of mutual attraction force.
6) Adding a polymer monomer into the solution obtained in the step 5), and dropwise adding an initiator into the solution;
specifically, adding a polymer monomer into the solution obtained in the step 5), stirring uniformly at low temperature, dissolving a certain amount of initiator into deionized water, transferring to a constant-pressure dropping funnel, and dropwise adding into the solution.
Further, the polymer monomer is one of aniline monomer, pyrrole monomer, dopamine or thiophene monomer; the initiator is one of ammonium persulfate, ferric chloride or hydrogen peroxide.
Further, the mass ratio of the three-dimensional ordered mesoporous silicon to the polymer monomer is 1-3.5; the mass ratio of the polymer monomer to the initiator is 0.4-0.7. Too little initiator will affect the degree of polymerization of the polymer monomer; too much results in a non-uniform coating at too fast a polymerization rate.
7) And placing the whole reaction device at low temperature under inert gas for reaction for a period of time, and then carrying out suction filtration, washing and drying to obtain the polymer modified three-dimensional ordered mesoporous silicon cathode material.
Specifically, the whole reaction device added with the initiator is placed at a low temperature and under inert gas to react for 12-24 hours, then is subjected to suction filtration, then is alternately washed by absolute ethyl alcohol and deionized water, and finally is dried at the temperature of 55-65 ℃ for 4-8 hours to obtain the polymer modified three-dimensional ordered mesoporous silicon cathode material.
Further, the low-temperature is 0-5 ℃.
Further, the inert gas is one or two of nitrogen or argon.
According to the invention, tetraethoxysilane is used as a silicon source, P123 is added as a surfactant and a pore-forming agent to prepare the three-dimensional ordered mesoporous silicon dioxide, and then magnesium powder is used as a reducing agent to prepare the three-dimensional ordered mesoporous silicon. The preparation method of the invention takes the conductive polymer as a modifier, coats a layer of conductive polymer on the surface of the three-dimensional ordered mesoporous silicon, and provides a buffer layer for the volume expansion of the silicon, thereby improving the conductivity and the cycle stability of the material.
The method for preparing the polymer modified three-dimensional ordered mesoporous silicon composite cathode material not only fully utilizes the developed and rich pore structure of the three-dimensional ordered mesoporous silicon, but also obtains a product with high crystallinity and uniform particle size distribution, and has simple and environment-friendly production process and low cost by taking the conductive polymer as a modifier.
The polymer-modified three-dimensional ordered mesoporous silicon negative electrode material prepared by the invention has excellent cycle performance and good rate performance, can meet the use requirements of lithium ion energy storage and power batteries, and has good application prospect.
The technical solution and effects of the present invention will be further described with reference to the following specific embodiments.
Example 1
The specific preparation process of the polymer-modified three-dimensional ordered mesoporous silicon negative electrode material of the embodiment is as follows:
1. weighing 3g of triblock copolymer (P123), fully dissolving the triblock copolymer in a 2M HCl solution, keeping the temperature at 35 ℃ for 1h, adding 8g of tetraethoxysilane, and carrying out oil bath at the constant temperature of 35 ℃ for 24 h; then transferring the mixed solution to a stainless steel reaction kettle with a polytetrafluoroethylene material lining for hydrothermal reaction, and sealing; controlling the hydrothermal reaction temperature to be 105 ℃ and the reaction time to be 16 h;
2. carrying out suction filtration on a sample obtained by the hydrothermal reaction, alternately washing the sample to be neutral by using absolute ethyl alcohol and deionized water, and carrying out forced air drying at the temperature of 80 ℃ for 12 hours;
3. placing the sample in a muffle furnace, heating to a set temperature of 550 ℃ at a heating rate of 5 ℃/min, sintering for 6 hours, and cooling to room temperature along with the furnace to obtain a white three-dimensional ordered mesoporous silica precursor;
4. and then mixing the obtained three-dimensional ordered mesoporous silica precursor with magnesium powder according to the mass ratio of 1: 1, and calcining for 6 hours at 650 ℃ in an atmosphere of inert gases argon (95%) and hydrogen (5%) to obtain a brown mixed sample; and (3) firstly putting the brown mixed sample into 2M hydrochloric acid to remove magnesium oxide and unreacted magnesium powder, and then putting the brown mixed sample into 5% hydrofluoric acid solution to remove impurities for 2h to remove silicon dioxide, thus preparing the three-dimensional ordered mesoporous silicon (OMP) sample.
5. Ultrasonically dispersing the obtained three-dimensional ordered mesoporous silicon (OMP) sample in 250ml of deionized water, adding a surfactant sodium dodecyl benzene sulfonate which accounts for 5% of the mass of the sample, ultrasonically dispersing for 30min, stirring for 30min at low temperature, and controlling the temperature to be 0-5 ℃.
6. Adding 0.03ml of pyrrole monomer into the low-temperature solution, and stirring and dispersing uniformly at low temperature; then, 0.17g of ammonium persulfate was dissolved in distilled water, transferred to a constant pressure dropping funnel, and the above solution was dropped dropwise.
7. Stirring and reacting for 24h at low temperature in the presence of nitrogen, filtering the sample, washing with absolute ethyl alcohol and deionized water for 3 times alternately, and drying at 60 ℃ for 6h to obtain the polypyrrole-modified three-dimensional ordered mesoporous silicon negative electrode material (OMP @ PPy).
Fig. 1 is an infrared spectrum analysis diagram of the three-dimensional ordered mesoporous silicon negative electrode material prepared in this embodiment, and as can be seen from fig. 1, PPy peaks in the polypyrrole-modified three-dimensional ordered mesoporous silicon material correspond to characteristic peaks of an infrared spectrum of pure PPy one-to-one. Fig. 2 is an SEM image of the polypyrrole-modified three-dimensional ordered mesoporous silicon negative electrode material, and it can be seen from the SEM image that the negative electrode material prepared in this example has a lotus-root-shaped rod-like morphology, and the morphology remains continuous after reduction with magnesium powder and polypyrrole coating. FIG. 5 is a nitrogen adsorption and desorption isothermal curve of polypyrrole-coated three-dimensional ordered mesoporous silicon, and the test result shows that the specific surface area of the polypyrrole-coated three-dimensional ordered mesoporous silicon is up to 177.4m2The pore size distribution is mainly 4nm, a high-speed channel is provided for the insertion and the extraction of lithium ions by rich pore channel structures, and the structural stability of high-current-density rapid charge and discharge of the polypyrrole-coated and connected nanoparticles is improved.
Assembling the polypyrrole-modified three-dimensional ordered mesoporous silicon negative electrode material synthesized in this embodiment into a button battery, using N-methylpyrrolidone (NMP) as a solvent, and mixing the polypyrrole-modified three-dimensional mesoporous silicon composite material synthesized in this embodiment with polyvinylidene fluoride (PVDF) and acetylene black in a ratio of 7: 1: 2, coating the mixture on copper foil to prepare a negative pole piece, and assembling the lithium ion battery by taking the lithium piece as a positive pole. Measuring the first discharge specific capacity of 1320.9mAh/g under the conditions of 0.1A/g and 0.01-1.5V at room temperature; the capacity is 1214mAh/g after 100 cycles under the conditions of 0.5A/g and 0.01-1.5V, which is shown in figure 3. Under the current density conditions of 0.5A/g, 1A/g, 2A/g, 4A/g, 8A/g and 10A/g, the capacity is still 1199mAh/g, and electrochemical tests show that the polypyrrole-modified three-dimensional ordered mesoporous silicon negative electrode material obtained in the embodiment has higher capacity and better rate capability, and the rate capability of the polypyrrole-modified three-dimensional ordered mesoporous silicon negative electrode material is shown in FIG. 4.
Example 2
The specific preparation process of the polymer-modified three-dimensional ordered mesoporous silicon negative electrode material of the embodiment is as follows:
1. weighing 4g of triblock copolymer (P123), fully dissolving the triblock copolymer in 18ml of distilled water of a 2M sulfuric acid solution, keeping the temperature at 35 ℃ for 1h, adding 8.4g of tetraethoxysilane, and carrying out oil bath at the constant temperature of 35 ℃ for 24 h; then transferring the mixed solution to a stainless steel reaction kettle with a polytetrafluoroethylene material lining for hydrothermal reaction, and sealing; the hydrothermal reaction temperature is controlled at 100 ℃ for 24 h.
2. The obtained sample is filtered by suction, washed to be neutral by absolute ethyl alcohol and water, and dried by air blowing for 12 hours at the temperature of 80 ℃.
3. And placing the obtained sample in a muffle furnace, heating to the set temperature of 550 ℃ at the heating rate of 3 ℃/min, sintering for 6 hours, and cooling to room temperature along with the furnace to obtain the white three-dimensional ordered mesoporous silica precursor.
4. Mixing the obtained three-dimensional ordered mesoporous silicon dioxide and magnesium powder in a proportion of 1: 0.88, calcining for 9 hours at 700 ℃ in the atmosphere of inert gases of argon (90%) and hydrogen (10%) to obtain a brown mixed sample, removing magnesium oxide and unreacted magnesium powder by using 2M sulfuric acid, removing impurities by using 1% HF for 6 hours to remove silicon dioxide, and preparing the three-dimensional ordered mesoporous silicon sample.
5. Ultrasonically dispersing the obtained sample three-dimensional ordered mesoporous silicon in 250ml of deionized water, adding a surfactant CTAB which is 5% of the mass of the sample, ultrasonically dispersing for 30min, stirring for 30min at low temperature, and controlling the temperature to be 0-5 ℃.
6. Adding 0.04ml aniline monomer into the low-temperature solution, and stirring and dispersing uniformly at low temperature; then, 0.34g of ferric chloride was dissolved in distilled water, and transferred to a constant pressure dropping funnel, and the above solution was added dropwise.
7. Stirring the mixture for 24 hours at low temperature in the presence of argon, filtering the sample, washing the sample with absolute ethyl alcohol and deionized water for 3 times alternately, and finally drying the washed sample at the temperature of 60 ℃ for 6 hours to obtain the green polyaniline-modified three-dimensional ordered mesoporous silicon cathode material.
Assembling the polyaniline-modified three-dimensional ordered mesoporous silicon negative electrode material synthesized in the embodiment into a button battery, using N-methylpyrrolidone (NMP) as a solvent, and mixing the polyaniline-modified three-dimensional ordered mesoporous silicon composite material synthesized in the embodiment with acetylene black and polyvinylidene fluoride (PVDF) according to a ratio of 7: 2: 1, coating the mixture on copper foil to prepare a negative pole piece, and then assembling the lithium ion battery by taking a lithium piece as a positive pole. Measuring the first discharge specific capacity of 1298.4mAh/g under the conditions of 0.1A/g and 0.01-1.5V at room temperature; the capacity is 1075mAh/g after 100 cycles under the conditions of 0.5A/g and 0.01-1.5V. Under the current density conditions of 0.5A/g, 1A/g, 2A/g, 4A/g, 8A/g and 10A/g, the current density returns to 0.5A/g, and the capacity still remains 1127 mAh/g; electrochemical tests show that the polyaniline-modified three-dimensional ordered mesoporous silicon anode material obtained in the embodiment has higher capacity and excellent rate capability, and the polyaniline-modified three-dimensional ordered mesoporous silicon anode material is also benefited from the rod-shaped appearance and the stable structure.
Example 3
1. 3g of triblock copolymer (P123) is fully dissolved in 2M sulfuric acid solution and 18ml of distilled water, 6.2g of ethyl orthosilicate is added after the temperature of 35 ℃ is kept constant for 1h, and then the mixture is subjected to oil bath at the constant temperature of 35 ℃ for 24 h; then transferring the mixed solution to a stainless steel reaction kettle with a polytetrafluoroethylene material lining for hydrothermal reaction, and sealing; controlling the hydrothermal reaction temperature to be 110 ℃ and the reaction time to be 12 h.
2. The obtained sample is filtered by suction, washed to be neutral by absolute ethyl alcohol and water, and dried by air blowing for 12 hours at the temperature of 80 ℃.
3. And placing the obtained sample in a muffle furnace, heating to the set temperature of 550 ℃ at the heating rate of 10 ℃/min, sintering for 6 hours, and cooling to room temperature along with the furnace to obtain the white three-dimensional ordered mesoporous silica.
4. Mixing white three-dimensional ordered mesoporous silicon dioxide and magnesium powder in a proportion of 1: 0.88, calcining for 6 hours at 750 ℃ in the atmosphere of inert gases argon (85%) and hydrogen (15%) to obtain a brown mixed sample, removing magnesium oxide and unreacted magnesium powder by using 2M sulfuric acid, removing silicon dioxide by using 5% HF for 0.5 hour to remove impurities, and preparing the three-dimensional ordered mesoporous silicon sample.
5. Ultrasonically dispersing the obtained three-dimensional ordered mesoporous silicon sample in 250ml of deionized water, adding a surfactant SDS (sodium dodecyl sulfate) which accounts for 5% of the mass of the sample, ultrasonically dispersing for 30min, stirring for 30min at low temperature, and controlling the temperature to be 0-5 ℃.
6. Dispersing 0.05ml of thiophene monomer in the low-temperature solution, and stirring and uniformly dispersing at low temperature; then 0.7g of hydrogen peroxide is transferred into a constant pressure dropping funnel, and the solution is dropwise added.
7. Stirring the mixture for 24 hours at low temperature in the presence of argon, filtering the sample, washing the sample with absolute ethyl alcohol and deionized water for 3 times alternately, and finally drying the washed sample at the temperature of 60 ℃ for 6 hours to obtain the polythiophene-modified three-dimensional ordered mesoporous silicon cathode material.
Assembling the polythiophene-modified three-dimensional ordered mesoporous silicon negative electrode material synthesized in the embodiment into a button battery, using N-methylpyrrolidone (NMP) as a solvent, and mixing the polythiophene-modified three-dimensional ordered mesoporous silicon negative electrode material synthesized in the embodiment with acetylene black and polyvinylidene fluoride (PVDF) according to a ratio of 7: 2: 1, coating the mixture on copper foil to prepare a negative pole piece, and then assembling the lithium ion battery by taking a lithium piece as a positive pole. Measuring the first discharge specific capacity of 1307.6mAh/g under the conditions of 0.1A/g and 0.01-1.5V at room temperature; the capacity is 1124.6mAh/g after 100 cycles under the conditions of 0.5A/g and 0.01-1.5V. Has good circulation stability.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (3)
1. A preparation method of a polymer-modified three-dimensional ordered mesoporous silicon negative electrode material is characterized by comprising the following steps:
1) weighing triblock copolymer P1233 g, fully dissolving in 2M HCl solution, keeping the temperature at 35 ℃ for 1h, adding 8g of tetraethoxysilane, and carrying out oil bath at the constant temperature of 35 ℃ for 24 h; then transferring the mixed solution to a stainless steel reaction kettle with a polytetrafluoroethylene material lining for hydrothermal reaction, and sealing; controlling the hydrothermal reaction temperature to be 105 ℃ and the reaction time to be 16 h;
2) filtering a sample obtained by the hydrothermal reaction, alternately washing the sample to be neutral by using absolute ethyl alcohol and deionized water, and drying the sample by blowing air at the temperature of 80 ℃ for 12 hours;
3) placing the sample in a muffle furnace, heating to a set temperature of 550 ℃ at a heating rate of 5 ℃/min, sintering for 6 hours, and cooling to room temperature along with the furnace to obtain a white three-dimensional ordered mesoporous silica precursor;
4) and then mixing the obtained three-dimensional ordered mesoporous silica precursor with magnesium powder according to the mass ratio of 1: 1, and calcining for 6 hours at 650 ℃ in the atmosphere of inert gases of argon gas 95% and hydrogen gas 5% to obtain a brown mixed sample; firstly putting the brown mixed sample into 2M hydrochloric acid to remove magnesium oxide and unreacted magnesium powder, and then putting the brown mixed sample into 5% hydrofluoric acid solution to remove impurities for 2h to remove silicon dioxide, thereby preparing the three-dimensional ordered mesoporous silicon;
5) ultrasonically dispersing the obtained three-dimensional ordered mesoporous silicon in 250ml of deionized water, adding a surfactant sodium dodecyl benzene sulfonate which accounts for 5% of the mass of the sample, ultrasonically dispersing for 30min, stirring for 30min at low temperature, and controlling the temperature to be 0-5 ℃;
6) adding 0.03ml of pyrrole monomer into the low-temperature solution, and stirring and dispersing uniformly at low temperature; dissolving 0.17g of ammonium persulfate in distilled water, transferring the solution to a constant-pressure dropping funnel, and dropping the solution dropwise;
7) stirring and reacting for 24 hours at low temperature in the presence of nitrogen, filtering the sample, washing with absolute ethyl alcohol and deionized water for 3 times alternately, and drying at 60 ℃ for 6 hours to obtain the polypyrrole-modified three-dimensional ordered mesoporous silicon negative electrode material;
the polypyrrole-modified three-dimensional ordered mesoporous silicon negative electrode material is of a lotus root-shaped rod-like structure, and the specific surface area is 177.4m2In terms of/g, the pore size distribution is predominantly at 4 nm.
2. A preparation method of a polymer-modified three-dimensional ordered mesoporous silicon negative electrode material is characterized by comprising the following steps:
1) weighing triblock copolymer P1234 g, fully dissolving in 18ml of distilled water of 2M sulfuric acid solution, keeping the temperature at 35 ℃ for 1h, adding 8.4g of ethyl orthosilicate, and carrying out oil bath at the constant temperature of 35 ℃ for 24 h; then transferring the mixed solution to a stainless steel reaction kettle with a polytetrafluoroethylene material lining for hydrothermal reaction, and sealing; controlling the hydrothermal reaction temperature at 100 ℃ for 24 hours;
2) carrying out suction filtration on the obtained sample, washing the sample to be neutral by using absolute ethyl alcohol and water, and carrying out forced air drying at the temperature of 80 ℃ for 12 hours;
3) placing the obtained sample in a muffle furnace, heating to a set temperature of 550 ℃ at a heating rate of 3 ℃/min, sintering for 6 hours, and cooling to room temperature along with the furnace to obtain a white three-dimensional ordered mesoporous silica precursor;
4) and mixing the obtained three-dimensional ordered mesoporous silicon dioxide and magnesium powder in a proportion of 1: 0.88, calcining for 9 hours at 700 ℃ in the atmosphere of 90% of inert gas argon and 10% of hydrogen to obtain a brown mixed sample, removing magnesium oxide and unreacted magnesium powder by using 2M sulfuric acid, removing impurities by using 1% HF for 6 hours to remove silicon dioxide, and preparing the three-dimensional ordered mesoporous silicon;
5) ultrasonically dispersing the obtained three-dimensional ordered mesoporous silicon in 250ml of deionized water, adding a surfactant CTAB which is 5% of the mass of the sample, ultrasonically dispersing for 30min, stirring for 30min at low temperature, and controlling the temperature to be 0-5 ℃;
6) adding 0.04ml of aniline monomer into the low-temperature solution, and stirring and dispersing uniformly at low temperature; dissolving 0.34g of ferric chloride in distilled water, transferring the solution into a constant-pressure dropping funnel, and dropwise adding the solution;
7) and stirring the mixture at a low temperature for 24 hours in the presence of argon, filtering the sample, washing the sample with absolute ethyl alcohol and deionized water for 3 times in an alternating manner, and finally drying the washed sample at the temperature of 60 ℃ for 6 hours to obtain the green polyaniline-modified three-dimensional ordered mesoporous silicon cathode material.
3. A preparation method of a polymer-modified three-dimensional ordered mesoporous silicon negative electrode material is characterized by comprising the following steps:
1) 3g of triblock copolymer P123 is fully dissolved in 2M sulfuric acid solution and 18ml of distilled water, 6.2g of ethyl orthosilicate is added after the temperature of 35 ℃ is kept constant for 1h, and then the mixture is subjected to oil bath at the constant temperature of 35 ℃ for 24 h; then transferring the mixed solution to a stainless steel reaction kettle with a polytetrafluoroethylene material lining for hydrothermal reaction, and sealing; controlling the hydrothermal reaction temperature to be 110 ℃ for hydrothermal reaction for 12 hours;
2) carrying out suction filtration on the obtained sample, washing the sample to be neutral by using absolute ethyl alcohol and water, and carrying out forced air drying at the temperature of 80 ℃ for 12 hours;
3) placing the obtained sample in a muffle furnace, heating to the set temperature of 550 ℃ at the heating rate of 10 ℃/min, sintering for 6 hours, and cooling to room temperature along with the furnace to obtain white three-dimensional ordered mesoporous silica;
4) mixing white three-dimensional ordered mesoporous silicon dioxide and magnesium powder in a proportion of 1: 0.88, calcining for 6 hours at 750 ℃ in the atmosphere of 85 percent of inert gas argon and 15 percent of hydrogen to obtain a brown mixed sample, removing magnesium oxide and unreacted magnesium powder by 2M sulfuric acid, removing silicon dioxide by 5 percent of HF for 0.5 hour to prepare a three-dimensional ordered mesoporous silicon sample;
5) ultrasonically dispersing the obtained three-dimensional ordered mesoporous silicon sample in 250ml of deionized water, adding a surfactant SDS (sodium dodecyl sulfate) which accounts for 5% of the mass of the sample, ultrasonically dispersing for 30min, stirring for 30min at low temperature, and controlling the temperature to be 0-5 ℃;
6) dispersing 0.05ml of thiophene monomer in the low-temperature solution, and stirring and dispersing uniformly at low temperature; then 0.7g of hydrogen peroxide is transferred into a constant pressure dropping funnel, and the solution is dropwise added;
7) and stirring the mixture at a low temperature for 24 hours in the presence of argon, filtering the sample, washing the sample with absolute ethyl alcohol and deionized water for 3 times in an alternating manner, and finally drying the washed sample at the temperature of 60 ℃ for 6 hours to obtain the polythiophene-modified three-dimensional ordered mesoporous silicon cathode material.
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