CN107732164B - Mesoporous crystalline Si-amorphous SiO for sodium ion battery2Preparation method and application of ordered mesoporous carbon composite material - Google Patents

Mesoporous crystalline Si-amorphous SiO for sodium ion battery2Preparation method and application of ordered mesoporous carbon composite material Download PDF

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CN107732164B
CN107732164B CN201710703399.3A CN201710703399A CN107732164B CN 107732164 B CN107732164 B CN 107732164B CN 201710703399 A CN201710703399 A CN 201710703399A CN 107732164 B CN107732164 B CN 107732164B
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ordered mesoporous
mesoporous
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amorphous sio
carbon composite
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CN107732164A (en
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曾令兴
刘任嫔
陈艺兰
钱庆荣
陈庆华
黄宝铨
肖荔人
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Fujian Normal University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a mesoporous crystalline Si-amorphous SiO for a sodium ion battery2Preparation method and application of ordered mesoporous carbon composite material, wherein the material has ordered mesoporous structure, and crystalline Si and amorphous SiO2Uniformly dispersed in the ordered mesoporous carbon support. The technical scheme is as follows: firstly, ordered mesoporous silicon dioxide is taken as a self-template, a carbon source is compounded in situ to prepare a bicontinuous ordered mesoporous structure silicon dioxide-mesoporous carbon compound, and then partial SiO is removed by etching2The method for synthesizing mesoporous SiO2-an ordered mesoporous carbon composite; finally, the ratio of magnesium powder to the compound is controlled by a magnesiothermic reduction method, and the mesoporous crystalline Si-amorphous SiO is prepared by reduction2-ordered mesoporous carbon composites. The result shows that the sodium ion battery negative electrode material has excellent sodium storage performance. The preparation method has the advantages of simple process, strong operability, wide raw material source, low cost, large-scale production and environmental protection.

Description

Mesoporous crystalline Si-amorphous SiO for sodium ion battery2Preparation method and application of ordered mesoporous carbon composite material
Technical Field
The invention belongs to the field of sodium ion battery materials, and particularly relates to a high-performance mesoporous crystalline Si-amorphous SiO2-order ofA preparation method and application of the mesoporous carbon composite material.
Background
In a secondary energy storage system, a lithium ion battery is widely seen in our daily life along with portable electronic products, communication equipment, electric vehicles, and the like, and occupies a major position in an energy market. However, considering the limited resource of metallic lithium, relying solely on lithium ion batteries is far from meeting the future demands of human beings. And the metal sodium and the lithium have similar physical and chemical properties, and the sodium source reserves are more abundant, so that the sodium ion battery can be used as the best alternative of a lithium ion battery, and the important significance is realized in searching for an electrode material which has high specific capacity and can stably remove/insert sodium.
On the basis of the research of a series of lithium ion battery materials, at present, three carbon materials, alloys and oxides are still the more popular negative electrode materials of sodium ion batteries. The silicon alloy material has a theoretical sodium storage capacity of more than 500 mAh/g, however, in the charging and discharging processes, the volume expansion of Si particles is large and the Si particles are easy to crush, so that the capacity attenuation and the cycle performance are poor. The method for improving the performance of the Si-based negative electrode material mainly comprises the steps of carrying out nanocrystallization on Si particles to prepare the SiOx composite material, and coating the SiOx composite material with carbon or using a carbon material as a carrier. Among many carbon materials, ordered mesoporous carbon is favored by researchers due to the advantages of uniform pore diameter, large pore volume, excellent conductivity and the like, and can be used as a buffer system to uniformly disperse active substance particles, so that the volume expansion in the process of sodium intercalation and deintercalation is buffered, and the conductivity and the cycle stability of the material are improved.
The invention prepares mesoporous crystalline Si-amorphous SiO by combining a self-template etching method and a magnesiothermic reduction method2The result shows that the sodium ion battery cathode material has excellent sodium storage performance.
Disclosure of Invention
The invention aims to provide high-performance mesoporous crystalline Si-amorphous SiO2The ordered mesoporous carbon composite material and the preparation method and the application thereof have the advantages of simple process, strong operability, wide raw material source and low costLow cost, large-scale production and environmental requirement compliance.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention adopts a method combining a self-template etching method and a magnesiothermic reduction method to prepare mesoporous crystalline Si-amorphous SiO2-ordered mesoporous carbon composites. The method comprises the following specific steps:
1) weighing a carbon source, adding the carbon source into a solution containing concentrated sulfuric acid and deionized water, adding ordered mesoporous silica white powder, and quickly stirring; then transferring the sample to a 50-80 ℃ drying oven, keeping the temperature, raising the temperature to 200 ℃ and 250 ℃, and then keeping the temperature to collect a brown solid sample;
2) grinding the brown solid obtained in the step 1) to powder, calcining the powder for 3 to 5 hours in an Ar atmosphere tube furnace at the temperature of 300 ℃ to 400 ℃, and collecting a gray solid sample, namely the SiO solid sample2-an ordered mesoporous carbon composite;
3) stirring the gray solid sample obtained in the step 2) by using 0.1-1 mol/L sodium hydroxide solution in a hot water bath at the temperature of 40-60 ℃ for 3-30 minutes, centrifugally washing and drying, and collecting a black solid sample;
4) then mixing and grinding the black sample obtained in the step 3) and Mg powder according to the mass ratio of 1 (2-5), and placing the mixture in a tube furnace with 10% of H2Calcining at 500 ℃ and 700 ℃ for 3-5 hours in the atmosphere of 90% Ar, washing the collected sample with 0.1-1 mol/L HCl solution, and centrifugally drying to obtain the mesoporous crystalline Si-amorphous SiO2-ordered mesoporous carbon composites.
In the step 1), the carbon source is sucrose, fructose, glucose or glucose amino acid; in the step 1), the sample is transferred into an oven at 50-80 ℃, the temperature is maintained for 2 hours, then the sample is heated to 200 ℃ and 250 ℃ and maintained for 10 hours, and a brown solid sample is collected.
In the step 1), the mass ratio of the carbon source to the white powder of the ordered mesoporous silica is 100: (20-150).
The mesoporous crystalline Si-amorphous SiO for the high-performance sodium-ion battery prepared by the preparation method2-ordered mesoporous carbon composites.
Mesoporous crystalline Si-amorphous SiO2Si in the ordered mesoporous carbon composite material is high-crystallinity silicon, and the diffraction peak position of the high-crystallinity silicon is matched with a JCPDS, 089-2749 standard map; the nano crystal lattice fringes of the high-crystallinity silicon are clearly visible, and the corresponding interplanar spacing is 0.311 nm, which is equal to d in an X-ray diffraction pattern of the silicon111The space is matched; mesoporous crystalline Si-amorphous SiO2SiO in ordered mesoporous carbon composites2Is amorphous silicon dioxide material, in mesoporous crystalline Si-amorphous SiO2No diffraction peak of silica is observed in the X-ray diffraction pattern of the ordered mesoporous carbon composite.
The mesoporous crystalline Si-amorphous SiO for the high-performance sodium-ion battery prepared by the preparation method2-use of an ordered mesoporous carbon composite, characterized in that: the mesoporous crystalline Si-amorphous SiO2The ordered mesoporous carbon composite material is applied to a negative electrode of a sodium ion battery, and is subjected to charge-discharge circulation for 100 times when the voltage is 0.01-3.0V and the current density is 50 mA/g, and the specific capacity is up to 423 mAh/g; the charge and discharge cycle is 100 times when the current density is 200 mA/g, and the specific capacity is up to 339 mAh/g; after 500 times of charge-discharge circulation under the condition of large current density of 1A/g, the specific capacity is stabilized at 190 mAh/g.
A sodium ion battery, comprising a working electrode, a reference electrode and a counter electrode, characterized in that: the weight ratio is as follows: mesoporous crystalline Si-amorphous SiO prepared by the preparation method according to any one of claims 1 to 32An ordered mesoporous carbon composite material, a conductive agent, super P carbon, a binder, PVDF (polyvinylidene fluoride), 70:20:10, are mixed and ground, and then are uniformly coated on a copper foil to serve as a working electrode, a metal sodium sheet serves as a counter electrode and a reference electrode, and 1 mol/L of NaClO4the/PC + EC is an electrolyte to assemble a 2025 type button cell.
The high-performance mesoporous crystalline Si-amorphous SiO2The application of the-ordered mesoporous carbon composite material is to mix high-performance mesoporous crystalline Si-amorphous SiO2The ordered mesoporous carbon composite material is applied to a sodium ion battery cathode. Assembling the sodium-ion battery: mesoporous crystalline Si-amorphous SiO in mass ratio2-ordered mesoporous carbon composite: conductive agent super P carbon: binder PVDF 70:20:10 blendUniformly coating the ground solution on copper foil to be used as a working electrode, taking a metal sodium sheet as a counter electrode and a reference electrode, and taking 1 mol/L NaClO4The button cell is assembled by adopting/PC + EC as electrolyte; all assembly was carried out in an inert atmosphere glove box.
The mesoporous crystalline Si-amorphous SiO prepared by the invention2-ordered mesoporous carbon composite: conductive agent super P carbon: PVDF binder is mixed and ground according to the mass percentage of 70:20:10, and then is uniformly coated on a copper foil to be used as a working electrode, a metal sodium sheet is used as a counter electrode and a reference electrode, and 1 mol/L of NaClO is used4The button cell is assembled by adopting/PC + EC as electrolyte; all assembly was carried out in an inert atmosphere glove box.
The invention has the following remarkable advantages:
1) the ordered mesoporous silicon dioxide used in the invention is used as a self-template and a silicon source, ordered mesoporous carbon is formed in an ordered pore passage, and then the ordered mesoporous carbon is etched to generate mesoporous highly-dispersed amorphous SiO2A structure embedded in the mesoporous carbon pore canal, and finally carrying out magnesium thermal reduction to generate mesoporous crystalline Si-amorphous SiO2Loaded in ordered mesoporous carbon. On the one hand, the ordered mesoporous silica is used as a template to synthesize the bicontinuous ordered mesoporous structure silica-ordered mesoporous carbon composite. On the other hand, the mesoporous silicon dioxide is partially etched to obtain mesoporous SiO as a silicon source2-ordered mesoporous carbon composites.
2) The ordered mesoporous carbon used in the invention is used as a carrier for the crystalline Si and the amorphous SiO2Plays an important role in limiting the range and increasing the conductivity of the material. In one aspect, ordered mesoporous carbon and amorphous SiO2The buffer system provides a certain free space for the volume expansion and contraction of Si particles in the process of sodium removal/sodium insertion. On the other hand, the pore structure of the ordered mesoporous carbon is beneficial to the permeation and diffusion of the electrolyte and is beneficial to improving the electronic conductivity.
3) The magnesiothermic reduction method used in the invention skillfully controls SiO2-ratio of ordered mesoporous carbon to magnesium powder, partial SiO2Reducing into crystalline Si simple substance to obtain crystalline Si and amorphous SiO2Co-exist at the same timeIn a complex; the Si is high-crystallinity silicon, and the diffraction peak position of the high-crystallinity silicon is matched with a standard map (JCPDS, 089-; the nano crystal lattice fringes of the high-crystallinity silicon are clearly visible, and the corresponding interplanar spacing is 0.311 nm, which is equal to d in an X-ray diffraction pattern of the silicon111The space is matched; the SiO2Is an amorphous silicon dioxide material, in mesoporous crystalline Si-amorphous SiO2No diffraction peak of silica is observed in the X-ray diffraction pattern of the ordered mesoporous carbon composite material, and amorphous SiO is observed during charging and discharging2And also can play a role in buffering the volume change of the crystal Si particles.
4) The mesoporous crystalline Si-amorphous SiO of the invention2The ordered mesoporous carbon composite material is a brand new sodium ion battery cathode, and the mesoporous crystalline Si-amorphous SiO obtained in the embodiment 1 of the invention2When the ordered mesoporous carbon composite material is used as a negative electrode material of a sodium ion battery, the ordered mesoporous carbon composite material has very high specific capacity and cycling stability. For example, when the voltage is 0.01-3.0V and the current density is 50 mA/g, the specific capacity is up to 423 mAh/g after 100 times of charge-discharge circulation; when the current density is 200 mA/g, the specific capacity is stabilized at 339mAh/g after 100 times of charge-discharge circulation; and simultaneously, the high-current charge-discharge performance is excellent, and the specific capacity is stabilized at 190 mAh/g after 500 times of charge-discharge cycles even at the high-current density of 1A/g.
5) Mesoporous crystalline Si-amorphous SiO2The invention provides a method for preparing mesoporous crystalline Si-amorphous SiO for the first time2The method for preparing the ordered mesoporous carbon composite material has the advantages of simple preparation process, easily obtained equipment, strong operability, wide raw material source, low cost, mass production and environmental friendliness.
Drawings
FIG. 1 shows mesoporous crystalline Si-amorphous SiO obtained in example 12-XRD pattern of ordered mesoporous carbon composite.
FIG. 2 shows mesoporous crystalline Si-amorphous SiO obtained in example 12SEM/TEM/EDS picture of ordered mesoporous carbon composite.
FIG. 3 shows mesoporous crystalline Si-amorphous SiO obtained in example 12TEM-Mapping of ordered mesoporous carbon composites.
FIG. 4 shows mesoporous crystalline Si-amorphous SiO obtained in example 12-cycle performance plot at 50 mA/g and 200 mA/g current density for ordered mesoporous carbon composite as sodium ion battery anode material.
FIG. 5 shows mesoporous crystalline Si-amorphous SiO obtained in example 12-a rate-dependent cycle performance diagram at a current density of 1A/g when the ordered mesoporous carbon composite material is used as a sodium ion battery negative electrode material.
FIG. 6 shows mesoporous crystalline Si-amorphous SiO obtained in example 12-a charge-discharge curve diagram at a current density of 200 mA/g when the ordered mesoporous carbon composite material is used as a cathode material of a sodium ion battery.
Detailed Description
Example 1
1) 100 g of sucrose is weighed and added into a mixed solution containing 10 mL of concentrated sulfuric acid with the mass fraction of 70 wt% and 100mL of deionized water, then 120 g of white powder of ordered mesoporous silica (Nanjing Pioneng nanometer company, product number XFF 01) is added, and the mixture is rapidly stirred. Then transferring the sample to an oven with the temperature of 80 ℃, keeping the temperature for 2 hours, raising the temperature to 200 ℃, keeping the temperature for 10 hours, and collecting a brown solid sample;
2) grinding the brown solid obtained in the step 1) into powder, calcining the powder for 3 hours at 350 ℃ in an Ar atmosphere tubular furnace, and collecting a gray solid sample, namely SiO2-an ordered mesoporous carbon composite;
3) adding the gray solid sample obtained in the step 2) into 1L of sodium hydroxide solution with the concentration of 1 mol/L, stirring for 10 minutes in a hot water bath at 50 ℃, centrifugally washing and drying, and collecting a black solid sample;
4) then mixing and grinding the black sample obtained in the step 3) and Mg powder according to the mass ratio of 1:2, and placing the mixture in a tube furnace with 10 vol% of H2Calcining at 700 ℃ for 5 hours in Ar atmosphere of 90 vol%, washing a collected sample with 0.5 mol/L HCl solution, and centrifugally drying to obtain the mesoporous crystalline Si-amorphous SiO2-ordered mesoporous carbon composites.
XRD experiment shows that the mesoporous crystalline Si-amorphous SiO in figure 1 is obtained2XRD pattern of ordered mesoporous carbon composite, as can be seen from FIG. 1, the synthesized high crystallinity silicon has diffraction peak position matching with standard pattern of Si (JCPDS, 089-2749). The corresponding indices of the respective crystal planes are shown in FIG. 1. The mesoporous crystalline Si-amorphous SiO in figure 2 is obtained by the experiments of a scanning electron microscope and a transmission electron microscope2SEM/TEM/EDS picture of ordered mesoporous carbon composite. As can be seen from FIG. 2 (a), the complex is in the form of a short rod; as can be further seen from the graphs (b) and (c) in FIG. 2, the composite shows a mesoporous channel structure, the lattice fringes of the crystalline Si are clearly visible, and the interplanar spacing corresponding to the lattice fringes of the nanocrystal is 0.311 nm, which is similar to d in the X-ray diffraction pattern of Si111The spacing is identical. In addition, the energy spectrum test result also confirms that the compound contains C, O, Si three elements, and the element ratio of O to Si is 1: 1.1, which shows that the composite obtained in example 1 is mesoporous crystalline Si-amorphous SiO2-ordered mesoporous carbon composites. The mesoporous crystalline Si-amorphous SiO of FIG. 3 is obtained by high-power transmission electron microscope experiment2Mapping of ordered mesoporous carbon composites. As can be seen from FIG. 3, C, O, Si elements in the composite are uniformly distributed in the carrier.
The mesoporous crystalline Si-amorphous SiO prepared by the present example2-ordered mesoporous carbon composite: conductive agent super P carbon: PVDF binder is mixed and ground according to the mass percentage of 70:20:10, and then is uniformly coated on a copper foil to be used as a working electrode, a metal sodium sheet is used as a counter electrode and a reference electrode, and 1 mol/L of NaClO is used4The button cell is assembled by adopting/PC + EC as electrolyte; all assembly was carried out in an inert atmosphere glove box. The cycling performance was tested at a current density of 50 mA/g, 200 mA/g, 1A/g. As shown in FIGS. 4 and 5, the mesoporous crystalline Si-amorphous SiO2When the ordered mesoporous carbon composite material is used as a negative electrode material of a sodium ion battery, the specific capacity of 423 mAh/g is reached after 100 times of charge-discharge circulation when the voltage is 0.01-3.0V and the current density is 50 mA/g; when the current density is 200 mA/g, the specific capacity is stabilized at 339mAh/g after 100 times of charge-discharge circulation; simultaneously exhibits excellent large current charge and dischargeThe performance, even at a large current density of 1A/g, the specific capacity is stabilized at 190 mAh/g after 500 times of charge-discharge circulation. As can be seen from the charge and discharge curves in fig. 6, the coincidence of the charge and discharge curves of the electrode material is good after the first discharge, which indicates that the material has excellent cycle stability. Thus, mesoporous crystalline Si-amorphous SiO2The ordered mesoporous carbon composite material has the characteristics of high specific capacity, high current performance and long cycle life, is an environment-friendly high-performance sodium ion battery cathode material, and has good application prospect.
Example 2
1) 100 g of glucose amino acid is weighed and added into a mixed solution containing 10 mL of concentrated sulfuric acid with the mass fraction of 70 wt% and 100mL of deionized water, and then 80 g of white powder of ordered mesoporous silica (Nanjing Pioneng Nanko, product number XFF 01) is added and rapidly stirred. Then transferring the mixture into an oven with the temperature of 80 ℃, keeping the temperature for 2 hours, raising the temperature to 250 ℃, keeping the temperature for 10 hours, and collecting a brown solid sample;
2) grinding the brown solid obtained in the step 1) into powder, calcining the powder for 5 hours at 300 ℃ in an Ar atmosphere tubular furnace, and collecting a gray solid sample, namely SiO2-an ordered mesoporous carbon composite;
3) adding the gray solid sample obtained in the step 2) into 1L of sodium hydroxide solution with the concentration of 1 mol/L, stirring for 10 minutes in a hot water bath at 50 ℃, centrifugally washing and drying, and collecting a black solid sample;
4) then mixing and grinding the black sample obtained in the step 3) and Mg powder according to the mass ratio of 1:3, and placing the mixture in a tube furnace with 10 vol% of H2Calcining at 700 ℃ for 3 hours in Ar atmosphere of 90 vol%, washing a collected sample with 0.5 mol/L HCl solution, and centrifugally drying to obtain the mesoporous crystalline Si-amorphous SiO2-ordered mesoporous carbon composites.
The mesoporous crystalline Si-amorphous SiO prepared by the present example2-ordered mesoporous carbon composite: conductive agent super P carbon: PVDF binder is mixed and ground according to the mass percentage of 70:20:10, and then is uniformly coated on a copper foil to be used as a working electrode, a metal sodium sheet is used as a counter electrode and a reference electrode, and 1 mol/L of NaClO is used4The button cell is assembled by adopting/PC + EC as electrolyte; all assembly was carried out in an inert atmosphere glove box.
Example 3
1) 100 g of glucose is weighed and added into a mixed solution containing 10 mL of concentrated sulfuric acid with the mass fraction of 70 wt% and 100mL of deionized water, then 120 g of white powder of ordered mesoporous silica (Nanjing Pioneng nanometer company, product number XFF 01) is added, and the mixture is rapidly stirred. Then transferring the sample to an oven with the temperature of 80 ℃, keeping the temperature for 2 hours, raising the temperature to 200 ℃, keeping the temperature for 10 hours, and collecting a brown solid sample;
2) grinding the brown solid obtained in the step 1) into powder, calcining the powder for 5 hours at 400 ℃ in an Ar atmosphere tubular furnace, and collecting a gray solid sample, namely SiO2-an ordered mesoporous carbon composite;
3) adding the gray solid sample obtained in the step 2) into 1L of sodium hydroxide solution with the concentration of 0.1 mol/L, stirring for 30 minutes in a hot water bath at 40 ℃, centrifugally washing and drying, and collecting a black solid sample;
4) then mixing and grinding the black sample obtained in the step 3) and Mg powder according to the mass ratio of 1:5, and placing the mixture in a tube furnace with 10% vol H2Calcining at 500 ℃ for 3 hours in Ar atmosphere of 90 vol%, washing a collected sample by using 1 mol/L HCl solution, and centrifugally drying to obtain the mesoporous crystalline Si-amorphous SiO2-ordered mesoporous carbon composites.
The mesoporous crystalline Si-amorphous SiO prepared by the present example2-ordered mesoporous carbon composite: conductive agent super P carbon: PVDF binder is mixed and ground according to the mass percentage of 70:20:10, and then is uniformly coated on a copper foil to be used as a working electrode, a metal sodium sheet is used as a counter electrode and a reference electrode, and 1 mol/L of NaClO is used4The button cell is assembled by adopting/PC + EC as electrolyte; all assembly was carried out in an inert atmosphere glove box.
Example 4
1) 100 g of fructose is weighed and added into a mixed solution containing 10 mL of concentrated sulfuric acid with the mass fraction of 70 wt% and 100mL of deionized water, then 100 g of white powder of ordered mesoporous silica (Nanjing Pioneng nanometer company, product number XFF 01) is added, and the mixture is rapidly stirred. Then transferring the mixture into a 50 ℃ oven, keeping the temperature for 2 hours, raising the temperature to 250 ℃ and keeping the temperature for 10 hours, and collecting a brown solid sample;
2) grinding the brown solid obtained in the step 1) into powder, calcining the powder for 3 hours at 400 ℃ in an Ar atmosphere tubular furnace, and collecting a gray solid sample, namely SiO2-an ordered mesoporous carbon composite;
3) adding the gray solid sample obtained in the step 2) into 1L of sodium hydroxide solution with the concentration of 1 mol/L, stirring for 3 minutes in a hot water bath at 60 ℃, centrifugally washing and drying, and collecting a black solid sample;
4) then mixing and grinding the black sample obtained in the step 3) and Mg powder according to the mass ratio of 1:2, and placing the mixture in a tube furnace with 10 vol% of H2Calcining at 700 ℃ for 5 hours in Ar atmosphere of 90 vol%, washing a collected sample with 0.2 mol/L HCl solution, and centrifugally drying to obtain the mesoporous crystalline Si-amorphous SiO2-ordered mesoporous carbon composites.
The mesoporous crystalline Si-amorphous SiO prepared by the present example2-ordered mesoporous carbon composite: conductive agent super P carbon: PVDF binder is mixed and ground according to the mass percentage of 70:20:10, and then is uniformly coated on a copper foil to be used as a working electrode, a metal sodium sheet is used as a counter electrode and a reference electrode, and 1 mol/L of NaClO is used4The button cell is assembled by adopting/PC + EC as electrolyte; all assembly was carried out in an inert atmosphere glove box.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.

Claims (7)

1. Mesoporous crystalline Si-amorphous SiO for sodium ion battery2-a method for preparing an ordered mesoporous carbon composite comprising the steps of:
1) weighing a carbon source, adding the carbon source into a solution containing concentrated sulfuric acid and deionized water, adding ordered mesoporous silica white powder, and quickly stirring; then transferring the sample to a 50-80 ℃ drying oven, keeping the temperature, raising the temperature to 200 ℃ and 250 ℃, and then keeping the temperature to collect a brown solid sample;
2) will be step 1)Grinding the obtained brown solid to powder, calcining the powder for 3 to 5 hours at the temperature of 300 ℃ and 400 ℃ in an Ar atmosphere tube furnace, and collecting a gray solid sample, namely the SiO solid sample2-an ordered mesoporous carbon composite;
3) stirring the gray solid sample obtained in the step 2) by using 0.1-1 mol/L sodium hydroxide solution in a hot water bath at the temperature of 40-60 ℃ for 3-30 minutes, centrifugally washing and drying, and collecting a black solid sample;
4) then mixing and grinding the black solid sample obtained in the step 3) and Mg powder according to the mass ratio of 1 (2-5), and placing the mixture in a tube furnace with 10% of H2Calcining at 500 ℃ and 700 ℃ for 3-5 hours in the atmosphere of 90% Ar, washing the collected sample with 0.1-1 mol/L HCl solution, and centrifugally drying to obtain the mesoporous crystalline Si-amorphous SiO2-ordered mesoporous carbon composites.
2. The mesoporous crystalline Si-amorphous SiO for sodium-ion battery according to claim 12A method for preparing an ordered mesoporous carbon composite material, characterized in that
In the step 1), the carbon source is sucrose, fructose, glucose or glucose amino acid;
in the step 1), transferring the sample to an oven at 50-80 ℃, keeping the temperature for 2 hours, raising the temperature to 200 ℃ and 250 ℃ and keeping the temperature for 10 hours, and collecting a brown solid sample.
3. The mesoporous crystalline Si-amorphous SiO for sodium-ion battery according to claim 1 or 22The preparation method of the ordered mesoporous carbon composite material is characterized in that in the step 1), the mass ratio of the carbon source to the ordered mesoporous silica white powder is 100: (20-150).
4. Mesoporous crystalline Si-amorphous SiO for sodium-ion battery prepared by the preparation method of any one of claims 1 to 32-ordered mesoporous carbon composites.
5. The mesoporous crystalline Si-amorphous SiO of claim 42-an ordered mesoporous carbon composite characterized in that: mesoporous crystalline Si-amorphousType SiO2Si in the ordered mesoporous carbon composite material is high-crystallinity silicon, and the diffraction peak position of the high-crystallinity silicon is matched with a JCPDS, 089-2749 standard map; the nano crystal lattice fringes of the high-crystallinity silicon are clearly visible, and the corresponding interplanar spacing is 0.311 nm, which is equal to d in an X-ray diffraction pattern of the silicon111The space is matched; mesoporous crystalline Si-amorphous SiO2SiO in ordered mesoporous carbon composites2Is amorphous silicon dioxide material, in mesoporous crystalline Si-amorphous SiO2No diffraction peak of silica is observed in the X-ray diffraction pattern of the ordered mesoporous carbon composite.
6. Mesoporous crystalline Si-amorphous SiO for sodium-ion battery prepared by the preparation method of any one of claims 1 to 32-use of an ordered mesoporous carbon composite, characterized in that: the mesoporous crystalline Si-amorphous SiO2The ordered mesoporous carbon composite material is applied to a negative electrode of a sodium ion battery, and is subjected to charge-discharge circulation for 100 times when the voltage is 0.01-3.0V and the current density is 50 mA/g, and the specific capacity is up to 423 mAh/g; the charge and discharge cycle is 100 times when the current density is 200 mA/g, and the specific capacity is up to 339 mAh/g; after 500 times of charge-discharge circulation under the condition of large current density of 1A/g, the specific capacity is stabilized at 190 mAh/g.
7. A sodium ion battery, comprising a working electrode, a reference electrode and a counter electrode, characterized in that: the weight ratio is as follows: mesoporous crystalline Si-amorphous SiO prepared by the preparation method according to any one of claims 1 to 32An ordered mesoporous carbon composite material, a conductive agent, super P carbon, a binder, PVDF (polyvinylidene fluoride), 70:20:10, are mixed and ground, and then are uniformly coated on a copper foil to serve as a working electrode, a metal sodium sheet serves as a counter electrode and a reference electrode, and 1 mol/L of NaClO4the/PC + EC is an electrolyte to assemble a 2025 type button cell.
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