CN107732164A - The mesoporous unformed SiO of crystal type Si of sodium-ion battery2The preparation method and application of ordered mesoporous carbon composite material - Google Patents

The mesoporous unformed SiO of crystal type Si of sodium-ion battery2The preparation method and application of ordered mesoporous carbon composite material Download PDF

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CN107732164A
CN107732164A CN201710703399.3A CN201710703399A CN107732164A CN 107732164 A CN107732164 A CN 107732164A CN 201710703399 A CN201710703399 A CN 201710703399A CN 107732164 A CN107732164 A CN 107732164A
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mesoporous
ordered
crystal type
sio
carbon composite
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CN107732164B (en
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曾令兴
刘任嫔
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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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 present invention discloses a kind of sodium-ion battery with the mesoporous unformed SiO of crystal type Si2The preparation method and application of ordered mesoporous carbon composite material, the material have ordered mesopore structure, and crystal type Si and unformed SiO2It is evenly dispersed in phosphorus-ordered mesoporous carbon carrier.Technical scheme is as follows：First using ordered mesoporous silica dioxide as self-template, the ordered mesopore structure mesoporous SiO 2 carbon complex of co-continuous is made in In-situ reaction carbon source, then removes part SiO by etching2The synthesising mesoporous SiO of method2Ordered mesoporous carbon complex；Magnesiothermic reduction method is finally utilized, controls magnesium powder and the ratio of compound, reduces and the mesoporous unformed SiO of crystal type Si is made2Ordered mesoporous carbon composite material.As a result show, the anode material of lithium-ion battery has excellent storage sodium performance.The preparation technology is simple, workable, and raw material sources are extensive, and cost is cheap, can be mass-produced, and meets environmental requirement.

Description

The mesoporous unformed SiO of crystal type Si- of sodium-ion battery2- ordered mesopore carbon composite wood The preparation method and application of material
Technical field
The invention belongs to sodium-ion battery Material Field, more particularly to a kind of mesoporous crystal type Si- of high-performance are unformed SiO2The preparation method and application of-ordered mesoporous carbon composite material.
Background technology
In secondary energy sources storage system, lithium ion battery is along with portable electronic products, communication apparatus, electric automobile etc. Appear widely in our daily life and in energy market in occupation of main status.But in view of metal lithium resource Finiteness, the needs of mankind will be to future can not far be met by only solely relying on lithium ion battery.And metallic sodium and lithium have it is similar Physics and chemical property, and sodium source reserves more horn of plenty, therefore sodium-ion battery can be as the optimal replacement of lithium ion battery Selection, find with specific capacity it is high, can the electrode material of stable/embedding sodium have great importance.
On a series of Research foundation of lithium ion battery materials, three kinds of carbon material, alloy and oxide are still at present Compare popular anode material of lithium-ion battery.Wherein there is the alloy material of silicon class the theoretical storage sodium more than 500 mAh/g to hold Amount, but in charge and discharge process, the volumetric expansion of Si particles is larger and easy crushing, causes capacity attenuation, poor circulation.Carry The method of high Si classes negative material performance mainly by Si particle nanosizings, prepares SiOx composites, with carbon coating or incites somebody to action Carbon material is as carrier.In numerous carbon materials, ordered mesopore carbon is homogeneous because having aperture, and pore volume is big, and electric conductivity is excellent etc. Advantage and by the favor of researchers, buffer system can be used as, dispersed effect is played to active material particle, so as to The volumetric expansion during deintercalation sodium is buffered, improves the electric conductivity and cyclical stability of material.
The present invention be combined by self-template etching method and magnesium reduction process carry out preparing mesoporous crystal type Si- it is unformed SiO2- ordered mesoporous carbon composite material, the results showed that, the anode material of lithium-ion battery has excellent storage sodium performance.
The content of the invention
It is an object of the invention to provide a kind of mesoporous unformed SiO of crystal type Si- of high-performance2- ordered mesopore carbon is compound Material and its preparation method and application, technique is simple, workable, and raw material sources are extensive, and cost is cheap, can give birth on a large scale Production, meets environmental requirement.
To achieve the above object, the present invention adopts the following technical scheme that：
It is unformed that the method that the present invention is combined using self-template etching method and magnesium reduction process prepares mesoporous crystal type Si- SiO2- ordered mesoporous carbon composite material.It is comprised the following steps that：
1）Carbon source is weighed to be added in the solution containing the concentrated sulfuric acid and deionized water, it is rear to add ordered mesoporous silica dioxide white powder End, quick stirring；It is then transferred in 50-80 oC baking ovens, is risen to after insulation after 200-250 oC are incubated again and collect brown solid Sample；
2）By step 1）Gained brown solid is ground to powder, the 300-400 °C of calcining 3-5 hour in Ar atmosphere tube type stoves, receives Collect gray solid sample, as SiO2- ordered mesoporous carbon composite material；
3）By step 2）Gained gray solid sample 0.1-1 mol/L sodium hydroxide solution, 40-60 °C of hot bath stirring 3-30 minutes, centrifuge washing drying, collect black solid sample；
4）Then by step 3）Gained black sample is with Mg powder using mass ratio as 1:（2-5）Mixed grinding is carried out, is placed in tube furnace Middle 10%H2500-700 oC calcine 3-5 hours under/90%Ar atmosphere, will collect sample and are washed with 0.1-1 mol/L HCl solutions, After centrifugation drying, that is, obtain the mesoporous unformed SiO of crystal type Si-2- ordered mesoporous carbon composite material.
Above-mentioned steps 1）In, described carbon source is sucrose, fructose, glucose or Glucoamino acid；Step 1）In, it is described Be transferred in 50-80 oC baking ovens, insulation 2 hours after rise to 200-250 oC be incubated 10 hours, collect brown solid sample.
Above-mentioned steps 1）In, the mass ratio of the carbon source and ordered mesoporous silica dioxide white powder is 100：（20- 150）.
The mesoporous unformed SiO of crystal type Si- of high-performance sodium-ion battery made from the above-mentioned preparation method of the present invention2- Ordered mesoporous carbon composite material.
The mesoporous unformed SiO of crystal type Si-2Si in-ordered mesoporous carbon composite material is high-crystallinity silicon, high-crystallinity Silicon diffraction maximum position and JCPDS, 089-2749 standard diagram match；The nanocrystalline lattice fringe of described high-crystallinity silicon High-visible, corresponding interplanar distance is 0.311 nm, d in this X ray diffracting spectrum with silicon111Spacing matches；Mesoporous knot The unformed SiO of crystal formation Si-2SiO in-ordered mesoporous carbon composite material2For amorphous silica material, in mesoporous crystal type The unformed SiO of Si-2The diffraction maximum of silica is not observed in the X ray diffracting spectrum of-ordered mesoporous carbon composite material.
The mesoporous unformed SiO of crystal type Si- of high-performance sodium-ion battery made from described preparation method2- be situated between in order The application of hole carbon composite, it is characterised in that：The described mesoporous unformed SiO of crystal type Si-2- ordered mesopore carbon composite wood Material be applied to sodium-ion battery negative pole in, voltage be 0.01-3.0 V, current density be 50 mA/g when charge and discharge cycles 100 Secondary, specific capacity is up to 423 mAh/g；Charge and discharge cycles 100 times when current density is 200 mA/g, specific capacity is up to 339 mAh/ g；In 1 A/g of high current density after charge and discharge cycles 500 times, specific capacity is stable in 190 mAh/g.
A kind of sodium-ion battery, including working electrode, reference electrode and to electrode, it is characterised in that：It is in mass ratio：Power Profit requires the mesoporous unformed SiO of crystal type Si- made from any described preparation methods of 1-32- ordered mesoporous carbon composite material: The super P carbon of conductive agent:Binding agent PVDF=70:20:Equably it is coated in after 10 mixed grindings on copper foil and is used as working electrode, gold It is to electrode and reference electrode, 1 mol/L NaClO to belong to sodium piece4/ PC+EC is that electrolyte is assembled into 2025 type coin shapes electricity Pond.
The above-mentioned mesoporous unformed SiO of crystal type Si- of high-performance2The application of-ordered mesoporous carbon composite material is by high-performance The mesoporous unformed SiO of crystal type Si-2- ordered mesoporous carbon composite material is applied in sodium-ion battery negative pole.Sodium-ion battery group Dress：It is the mesoporous unformed SiO of crystal type Si- in mass ratio2- ordered mesoporous carbon composite material：The super P carbon of conductive agent：Binding agent PVDF=70: 20 :Work electrode is equably coated on copper foil after 10 mixed grindings, and metallic sodium piece is to electrode and reference Electrode, 1 mol/L NaClO4/ PC+EC is that electrolyte is assembled into button cell；All assemblings are in inert atmosphere gloves Carried out in case.
The mesoporous unformed SiO of crystal type Si- prepared using the present invention2- ordered mesoporous carbon composite material：Conductive agent is super P carbon：Binding agent PVDF is according to mass percent 70: 20 :Work electricity is equably coated on copper foil after 10 mixed grindings Pole, metallic sodium piece are to electrode and reference electrode, 1 mol/L NaClO4/ PC+EC is that electrolyte is assembled into button cell； All assemblings are carried out in inert-atmosphere glove box.
The remarkable advantage of the present invention is：
1）Ordered mesoporous silica dioxide used in the present invention functions as self-template and silicon source, is first formed in orderly duct Ordered mesopore carbon, the unformed SiO of the mesoporous high dispersive of then etching generation2The structure being embedded in mesoporous carbon duct, last magnesium Thermal reduction produces the mesoporous unformed SiO of crystal type Si-2It is carried in ordered mesopore carbon.On the one hand, ordered mesoporous silica dioxide is made For ordered mesopore structure silica-ordered mesoporous carbon complex of templated synthesis co-continuous.On the other hand, mesoporous silicon oxide It is partially etched to obtain mesoporous SiO as silicon source2- ordered mesoporous carbon complex.
2）Ordered mesopore carbon used in the present invention functions as carrier, to described crystallization Si and unformed SiO2Rise To important confinement effect and the electric conductivity of increase material.On the one hand, ordered mesopore carbon and unformed SiO2Buffer body It is to provide certain free space with contraction for the volumetric expansion of Si particles during de-/embedding sodium.On the other hand, it is order mesoporous The pore passage structure of carbon is advantageous to the diffusion of electrolyte, is favorably improved electron conductivity.
3）Magnesium reduction process used in the present invention is dexterously by controlling SiO2The ratio of-ordered mesopore carbon and magnesium powder, will Partial SiO2It is reduced to crystal type Si simple substance so that crystal type Si and unformed SiO2It is present in simultaneously in compound；Described Si is high-crystallinity silicon, high-crystallinity silicon diffraction maximum position and standard diagram（JCPDS, 089-2749）Match；Described height The nanocrystalline lattice fringe of crystallinity silicon is high-visible, and corresponding interplanar distance is 0.311 nm, this X-ray diffractogram with silicon D in spectrum111Spacing matches；Described SiO2For amorphous silica material, in the mesoporous unformed SiO of crystal type Si-2- have The diffraction maximum of silica is not observed in the X ray diffracting spectrum of sequence mesoporous carbon composite material, and in charge and discharge process, Unformed SiO2It may also function as the effect of buffering crystal type Si particle volume changes.
4）The mesoporous unformed SiO of crystal type Si- of the present invention2- ordered mesoporous carbon composite material be a kind of brand-new sodium from Sub- GND, the mesoporous unformed SiO of crystal type Si- that the embodiment of the present invention 1 obtains2The conduct of-ordered mesoporous carbon composite material During anode material of lithium-ion battery, there is very high specific capacity and stable circulation performance.It is 0.01-3.0 V, electric current such as in voltage 100 specific capacities of charge and discharge cycles are up to 423 mAh/g when density is 50 mA/g；The charge and discharge when current density is 200 mA/g It is stable in 339mAh/g that electricity circulates 100 specific capacities；Excellent high rate during charging-discharging is shown simultaneously, even in high current 500 specific capacities of charge and discharge cycles are stable in 190 mAh/g during 1 A/g of density.
5）The mesoporous unformed SiO of crystal type Si-2- ordered mesoporous carbon composite material is that a kind of good sodium-ion battery is born Pole material, the present invention provide one kind and prepare the mesoporous unformed SiO of crystal type Si- first2The side of-ordered mesoporous carbon composite material Method, the preparation technology is simple, and equipment is easy to get, and workable, raw material sources are extensive, and cost is cheap, can largely produce, meet ring Border requires.
Brief description of the drawings
Fig. 1 is the mesoporous unformed SiO of crystal type Si- of the gained of embodiment 12The XRD of-ordered mesoporous carbon composite material.
Fig. 2 is the mesoporous unformed SiO of crystal type Si- of the gained of embodiment 12The SEM/ of-ordered mesoporous carbon composite material TEM/EDS schemes.
Fig. 3 is the mesoporous unformed SiO of crystal type Si- of the gained of embodiment 12The TEM- of-ordered mesoporous carbon composite material Mapping schemes.
Fig. 4 is the mesoporous unformed SiO of crystal type Si- of the gained of embodiment 12- ordered mesoporous carbon composite material as sodium from Cycle performance figure during sub- cell negative electrode material under 50 mA/g and 200 mA/g current densities.
Fig. 5 is the mesoporous unformed SiO of crystal type Si- of the gained of embodiment 12- ordered mesoporous carbon composite material as sodium from Cycle performance figure forthright again during sub- cell negative electrode material under 1 A/g current densities.
Fig. 6 is the mesoporous unformed SiO of crystal type Si- of the gained of embodiment 12- ordered mesoporous carbon composite material is as sodium Charging and discharging curve figure during ion battery cathode material under 200 mA/g current densities.
Embodiment
Embodiment 1
1）100 grams of sucrose are weighed to be added to containing the concentrated sulfuric acid and 100 mL deionized waters that 10 mL mass fractions are 70 wt% In mixed solution, 120 grams of ordered mesoporous silica dioxides are added afterwards（Nanjing pioneer's nanometer company, production code member XFF01）White powder End, quick stirring.It is then transferred in 80 oC baking ovens, insulation rises to 200 oC and is incubated 10 hours after 2 hours, collect brown and consolidate Body sample；
2）By step 1）Gained brown solid is ground to powder, is calcined 3 hours for 350 °C in Ar atmosphere tube type stoves, collects grey Solid sample, as SiO2- ordered mesoporous carbon composite material；
3）By step 2）Gained gray solid sample is added in the sodium hydroxide solution that 1 L concentration is 1 mol/L, 50 oC heat Stirring in water bath 10 minutes, centrifuge washing drying, collects black solid sample；
4）Then by step 3）Gained black sample is with Mg powder using mass ratio as 1:2 carry out mixed grinding, are placed in 10 in tube furnace vol%H2700 oC are calcined 5 hours under/90 vol%Ar atmosphere, will be collected sample and are washed with 0.5 mol/L HCl solutions, are centrifuged After drying, that is, obtain the mesoporous unformed SiO of crystal type Si-2- ordered mesoporous carbon composite material.
The mesoporous unformed SiO of crystal type Si- for obtaining Fig. 1 are tested through XRD2The XRD of-ordered mesoporous carbon composite material, From in Fig. 1, synthesis obtains the silicon of high-crystallinity, its diffraction maximum position and Si standard diagram (JCPDS, 089-2749) Match.Corresponding each indices of crystallographic plane are as shown in Figure 1.Scanned Electronic Speculum, transmission electron microscope experiment obtain Fig. 2 mesoporous crystal type The unformed SiO of Si-2The SEM/TEM/EDS figures of-ordered mesoporous carbon composite material.By in Fig. 2（a）Figure understands that the compound is Corynebacterium；By in Fig. 2（b）With（c）Figure can further learn that the compound shows mesoporous pore passage structure, and crystal type Si lattice fringe is high-visible, meanwhile, the nm of interplanar distance 0.311 corresponding to nanocrystalline lattice fringe, this and Si X is penetrated D in ray diffraction diagram spectrum111Spacing matches.In addition, power spectrum test result, which also confirms that, contains tri- kinds of elements of C, O, Si in compound, And O and Si element ratio is 1：1.1, illustrate that the compound that embodiment 1 obtains is the mesoporous unformed SiO of crystal type Si-2- in order Mesoporous carbon composite material.The mesoporous unformed SiO of crystal type Si- for obtaining Fig. 3 are tested through high power transmission electron microscope2- ordered mesopore carbon The Mapping figures of composite.Tri- kinds of elements of C, O, Si are evenly distributed in carrier respectively in the compound as shown in Figure 3.
Using the mesoporous unformed SiO of crystal type Si- manufactured in the present embodiment2- ordered mesoporous carbon composite material：Conductive agent surpasses Level P carbon：Binding agent PVDF is according to mass percent 70: 20 :Equably it is coated on copper foil and works after 10 mixed grindings Electrode, metallic sodium piece are to electrode and reference electrode, 1 mol/L NaClO4/ PC+EC is that electrolyte is assembled into button electricity Pond；All assemblings are carried out in inert-atmosphere glove box.Under 50 mA/g, 200 mA/g, 1 A/g current densities, test Cycle performance.As shown in Fig. 4 and Fig. 5, the mesoporous unformed SiO of crystal type Si-2- ordered mesoporous carbon composite material is as sodium ion During cell negative electrode material, voltage be 0.01-3.0 V, current density be 50 mA/g when 100 specific capacity height of charge and discharge cycles Up to 423 mAh/g；100 specific capacities of charge and discharge cycles are stable in 339 mAh/g when current density is 200 mA/g；Table simultaneously Reveal excellent high rate during charging-discharging, 500 specific capacities stabilizations of charge and discharge cycles exist when 1 A/g of high current density 190 mAh/g.Separately by the electrode material it can be seen from Fig. 6 charging and discharging curve after discharging first, charging and discharging curve overlaps Property is preferable, illustrates that the material has excellent cyclical stability.Therefore, the mesoporous unformed SiO of crystal type Si-2- ordered mesopore carbon Composite has the charge-discharge characteristic of high specific capacity, high-rate performance and long circulation life, is environmentally friendly high property Energy anode material of lithium-ion battery, has a good application prospect.
Embodiment 2
1）Weigh 100 grams of Glucoamino acid be added to containing 10 mL mass fractions be 70 wt% the concentrated sulfuric acid and 100 mL go In the mixed solution of ionized water, 80 grams of ordered mesoporous silica dioxides are added afterwards（Nanjing pioneer's nanometer company, production code member XFF01） White powder, quick stirring.It is then transferred in 80 oC baking ovens, insulation rises to 250 oC and is incubated 10 hours after 2 hours, collect Brown solid sample；
2）By step 1）Gained brown solid is ground to powder, is calcined 5 hours for 300 °C in Ar atmosphere tube type stoves, collects grey Solid sample, as SiO2- ordered mesoporous carbon composite material；
3）By step 2）Gained gray solid sample is added in the sodium hydroxide solution that 1 L concentration is 1 mol/L, 50 oC heat Stirring in water bath 10 minutes, centrifuge washing drying, collects black solid sample；
4）Then by step 3）Gained black sample is with Mg powder using mass ratio as 1:3 carry out mixed grinding, are placed in 10 in tube furnace vol %H2700 oC are calcined 3 hours under/90 vol %Ar atmosphere, will be collected sample and are washed with 0.5 mol/L HCl solutions, from After heart drying, that is, obtain the mesoporous unformed SiO of crystal type Si-2- ordered mesoporous carbon composite material.
Using the mesoporous unformed SiO of crystal type Si- manufactured in the present embodiment2- ordered mesoporous carbon composite material：Conductive agent surpasses Level P carbon：Binding agent PVDF is according to mass percent 70: 20 :Equably it is coated on copper foil and works after 10 mixed grindings Electrode, metallic sodium piece are to electrode and reference electrode, 1 mol/L NaClO4/ PC+EC is that electrolyte is assembled into button electricity Pond；All assemblings are carried out in inert-atmosphere glove box.
Embodiment 3
1）100 grams of glucose are weighed to be added to containing the concentrated sulfuric acid and 100 mL deionized waters that 10 mL mass fractions are 70 wt% Mixed solution in, afterwards add 120 grams of ordered mesoporous silica dioxides（Nanjing pioneer's nanometer company, production code member XFF01）White Powder, quick stirring.It is then transferred in 80 oC baking ovens, insulation rises to 200 oC and is incubated 10 hours after 2 hours, collect brown Solid sample；
2）By step 1）Gained brown solid is ground to powder, is calcined 5 hours for 400 °C in Ar atmosphere tube type stoves, collects grey Solid sample, as SiO2- ordered mesoporous carbon composite material；
3）By step 2）Gained gray solid sample is added in the sodium hydroxide solution that 1 L concentration is 0.1 mol/L, 40 oC Hot bath is stirred 30 minutes, centrifuge washing drying, collects black solid sample；
4）Then by step 3）Gained black sample is with Mg powder using mass ratio as 1:5 carry out mixed grinding, are placed in 10% in tube furnace vol H2500 oC are calcined 3 hours under/90 vol %Ar atmosphere, will be collected sample and are washed with 1 mol/L HCl solutions, centrifugation is dried After dry, that is, obtain the mesoporous unformed SiO of crystal type Si-2- ordered mesoporous carbon composite material.
Using the mesoporous unformed SiO of crystal type Si- manufactured in the present embodiment2- ordered mesoporous carbon composite material：Conductive agent surpasses Level P carbon：Binding agent PVDF is according to mass percent 70: 20 :Equably it is coated on copper foil and works after 10 mixed grindings Electrode, metallic sodium piece are to electrode and reference electrode, 1 mol/L NaClO4/ PC+EC is that electrolyte is assembled into button electricity Pond；All assemblings are carried out in inert-atmosphere glove box.
Embodiment 4
1）100 grams of fructose are weighed to be added to containing the concentrated sulfuric acid and 100 mL deionized waters that 10 mL mass fractions are 70 wt% In mixed solution, 100 grams of ordered mesoporous silica dioxides are added afterwards（Nanjing pioneer's nanometer company, production code member XFF01）White powder End, quick stirring.It is then transferred in 50 oC baking ovens, insulation rises to 250 oC and is incubated 10 hours after 2 hours, collect brown and consolidate Body sample；
2）By step 1）Gained brown solid is ground to powder, is calcined 3 hours for 400 °C in Ar atmosphere tube type stoves, collects grey Solid sample, as SiO2- ordered mesoporous carbon composite material；
3）By step 2）Gained gray solid sample is added in the sodium hydroxide solution that 1 L concentration is 1 mol/L, 60 oC heat Stirring in water bath 3 minutes, centrifuge washing drying, collects black solid sample；
4）Then by step 3）Gained black sample is with Mg powder using mass ratio as 1:2 carry out mixed grinding, are placed in 10 in tube furnace vol %H2700 oC are calcined 5 hours under/90 vol %Ar atmosphere, will be collected sample and are washed with 0.2 mol/L HCl solutions, from After heart drying, that is, obtain the mesoporous unformed SiO of crystal type Si-2- ordered mesoporous carbon composite material.
Using the mesoporous unformed SiO of crystal type Si- manufactured in the present embodiment2- ordered mesoporous carbon composite material：Conductive agent surpasses Level P carbon：Binding agent PVDF is according to mass percent 70: 20 :Equably it is coated on copper foil and works after 10 mixed grindings Electrode, metallic sodium piece are to electrode and reference electrode, 1 mol/L NaClO4/ PC+EC is that electrolyte is assembled into button electricity Pond；All assemblings are carried out in inert-atmosphere glove box.
The foregoing is only presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with Modification, it should all belong to the covering scope of the present invention.

Claims (7)

  1. A kind of 1. mesoporous unformed SiO of crystal type Si- of sodium-ion battery2The preparation method of-ordered mesoporous carbon composite material, bag Include following steps：
    1）Carbon source is weighed to be added in the solution containing the concentrated sulfuric acid and deionized water, it is rear to add ordered mesoporous silica dioxide white powder End, quick stirring；It is then transferred in 50-80 oC baking ovens, is risen to after insulation after 200-250 oC are incubated again and collect brown solid Sample；
    2）By step 1）Gained brown solid is ground to powder, the 300-400 °C of calcining 3-5 hour in Ar atmosphere tube type stoves, receives Collect gray solid sample, as SiO2- ordered mesoporous carbon composite material；
    3）By step 2）Gained gray solid sample 0.1-1 mol/L sodium hydroxide solution, 40-60 °C of hot bath stirring 3-30 minutes, centrifuge washing drying, collect black solid sample；
    4）Then by step 3）Gained black sample is with Mg powder using mass ratio as 1:（2-5）Mixed grinding is carried out, is placed in tube furnace Middle 10%H2500-700 oC calcine 3-5 hours under/90%Ar atmosphere, will collect sample and are washed with 0.1-1 mol/L HCl solutions, After centrifugation drying, that is, obtain the mesoporous unformed SiO of crystal type Si-2- ordered mesoporous carbon composite material.
  2. 2. the mesoporous unformed SiO of crystal type Si- of sodium-ion battery according to claim 12- ordered mesopore carbon composite wood The preparation method of material, it is characterised in that
    Step 1）In, described carbon source is sucrose, fructose, glucose or Glucoamino acid；
    Step 1）In, described is transferred in 50-80 oC baking ovens, and insulation rises to 200-250 oC and is incubated 10 hours after 2 hours, Collect brown solid sample.
  3. 3. the mesoporous unformed SiO of crystal type Si- of sodium-ion battery according to claim 1 or 22- ordered mesopore carbon is compound The preparation method of material, it is characterised in that step 1）In, the carbon source and the mass ratio of ordered mesoporous silica dioxide white powder For 100：（20-150）.
  4. 4. the mesoporous unformed SiO of crystal type Si- of sodium-ion battery made from any described preparation methods of claim 1-32- Ordered mesoporous carbon composite material.
  5. 5. the mesoporous unformed SiO of crystal type Si- according to claim 42- ordered mesoporous carbon composite material, its feature exist In：The mesoporous unformed SiO of crystal type Si-2Si in-ordered mesoporous carbon composite material is high-crystallinity silicon, and high-crystallinity silicon spreads out Peak position and JCPDS are penetrated, 089-2749 standard diagrams match；The nanocrystalline lattice fringe of described high-crystallinity silicon is clear It can be seen that corresponding interplanar distance is 0.311 nm, d in this X ray diffracting spectrum with silicon111Spacing matches；Mesoporous crystal type The unformed SiO of Si-2SiO in-ordered mesoporous carbon composite material2For amorphous silica material, in mesoporous crystal type Si- Unformed SiO2The diffraction maximum of silica is not observed in the X ray diffracting spectrum of-ordered mesoporous carbon composite material.
  6. 6. the mesoporous unformed SiO of crystal type Si- of sodium-ion battery made from any described preparation methods of claim 1-32- The application of ordered mesoporous carbon composite material, it is characterised in that：The described mesoporous unformed SiO of crystal type Si-2- ordered mesopore carbon Composite be applied to sodium-ion battery negative pole in, voltage be 0.01-3.0 V, current density be 50 mA/g when discharge and recharge follow Ring 100 times, specific capacity is up to 423 mAh/g；Charge and discharge cycles 100 times when current density is 200 mA/g, specific capacity is up to 339 mAh/g；In 1 A/g of high current density after charge and discharge cycles 500 times, specific capacity is stable in 190 mAh/g.
  7. 7. a kind of sodium-ion battery, including working electrode, reference electrode and to electrode, it is characterised in that：It is in mass ratio：Right It is required that the mesoporous unformed SiO of crystal type Si- made from any described preparation methods of 1-32- ordered mesoporous carbon composite material:Lead The electric super P carbon of agent:Binding agent PVDF=70:20:Equably it is coated in after 10 mixed grindings on copper foil and is used as working electrode, metal Sodium piece is to electrode and reference electrode, 1 mol/L NaClO4/ PC+EC is that electrolyte is assembled into 2025 type coin shapes electricity Pond.
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CN111883754A (en) * 2020-07-21 2020-11-03 合肥国轩高科动力能源有限公司 Iron nitride-ordered mesoporous carbon composite material and preparation method and application thereof
CN111969243A (en) * 2020-08-28 2020-11-20 杭州肄康新材料有限公司 Sodium ion solid-state battery and preparation process thereof
CN112479177A (en) * 2020-11-26 2021-03-12 天能帅福得能源股份有限公司 Preparation method of ordered mesoporous silicon-carbon composite material
CN113745491A (en) * 2021-08-10 2021-12-03 扬州大学 SnO with double-wall hollow sphere structure2@ C material and preparation method thereof

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US20090258213A1 (en) * 2008-02-07 2009-10-15 The Regents Of The University Of California Carbon materials with interconnected pores
CN102969489A (en) * 2012-12-05 2013-03-13 奇瑞汽车股份有限公司 Silicon-carbon composite material, preparation method of silicon-carbon composite material, and lithium ion battery containing silicon-carbon composite material
CN105070891A (en) * 2015-09-06 2015-11-18 福建师范大学 Preparation of Ge/GeO2-mesoporous carbon composite electrode material for lithium ion battery and application of Ge/GeO2-mesoporous carbon composite electrode material

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US20090258213A1 (en) * 2008-02-07 2009-10-15 The Regents Of The University Of California Carbon materials with interconnected pores
CN102969489A (en) * 2012-12-05 2013-03-13 奇瑞汽车股份有限公司 Silicon-carbon composite material, preparation method of silicon-carbon composite material, and lithium ion battery containing silicon-carbon composite material
CN105070891A (en) * 2015-09-06 2015-11-18 福建师范大学 Preparation of Ge/GeO2-mesoporous carbon composite electrode material for lithium ion battery and application of Ge/GeO2-mesoporous carbon composite electrode material

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111883754A (en) * 2020-07-21 2020-11-03 合肥国轩高科动力能源有限公司 Iron nitride-ordered mesoporous carbon composite material and preparation method and application thereof
CN111969243A (en) * 2020-08-28 2020-11-20 杭州肄康新材料有限公司 Sodium ion solid-state battery and preparation process thereof
CN112479177A (en) * 2020-11-26 2021-03-12 天能帅福得能源股份有限公司 Preparation method of ordered mesoporous silicon-carbon composite material
CN113745491A (en) * 2021-08-10 2021-12-03 扬州大学 SnO with double-wall hollow sphere structure2@ C material and preparation method thereof
CN113745491B (en) * 2021-08-10 2022-11-29 扬州大学 SnO with double-wall hollow ball structure 2 @ C material and preparation method thereof

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