CN105789571A - Porous carbon spheres-coated silicon/silicon dioxide nano-composite material and preparation method and application thereof - Google Patents

Porous carbon spheres-coated silicon/silicon dioxide nano-composite material and preparation method and application thereof Download PDF

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CN105789571A
CN105789571A CN201610051835.9A CN201610051835A CN105789571A CN 105789571 A CN105789571 A CN 105789571A CN 201610051835 A CN201610051835 A CN 201610051835A CN 105789571 A CN105789571 A CN 105789571A
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silicon
composite material
porous carbon
silicon dioxide
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CN105789571B (en
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侯仰龙
赛瑞丝雷曼
黄晓晓
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Peking University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386Silicon or alloys based on silicon
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention provides a porous carbon spheres-coated silicon/silicon dioxide nano-composite material and a preparation method and an application thereof. The porous carbon spheres-coated silicon/silicon dioxide nano-composite material comprises a silicon/silicon dioxide nano-composite material and porous carbon spheres, wherein the porous carbon spheres coat the silicon/silicon dioxide nano-composite material and comprise micropores and mesopores. The porous carbon spheres-coated silicon/silicon dioxide nano-composite material can form physical and chemical adsorption on polysulfide when used as an anode material for a lithium-sulfur battery, is high in sulfur loading capacity and demonstrates excellent electric capacity and cycling stability; and active materials are not easy to lose.

Description

Silicon/silicon dioxide nano composite material that porous carbon bag is wrapped up in and its preparation method and application
Technical field
The present invention relates to a kind of nano composite material, silicon/silicon dioxide nano composite material that particularly a kind of porous carbon bag is wrapped up in and its preparation method and application.
Background technology
Lithium-sulfur cell is a kind of using element sulphur as negative electrode, using lithium metal as the lithium battery of anode.During lithium-sulfur cell electric discharge, anode reaction is that lithium loses electronics and becomes lithium ion, and cathode reaction is that sulfur generates sulfide with lithium ion and electron reaction, and the electric potential difference of negative electrode and anode reaction is the discharge voltage that lithium-sulfur cell provides.The theoretical energy density of lithium-sulfur cell is more than five times of lithium ion battery theoretical energy density, and numerical value is approximately 2600Wh/kg.Additionally, the theoretical capacity of lithium-sulfur cell may be up to 1672mAh/g, and have the advantage of high environmental protection property and low cost.
Although lithium-sulfur cell has above-mentioned advantage, but still there are the following problems: 1, the electron conduction of elemental sulfur and ionic conductivity are poor, sulfur materials electrical conductivity at room temperature extremely low (10-30And the end product Li reacted S/cm),2S2And Li2S is also electronic body, is unfavorable for the high rate capability of battery;2, the middle discharging product (polysulfide intermediate or polysulfide anion) of lithium-sulfur cell can be dissolved in organic electrolyte, not only can reduce ionic conductivity, also results in the waste of active substance loss and electric energy;3, sulfur and lithium sulfide have the change in volume up to 80% in charge and discharge process, and it can cause the change of negative electrode pattern and structure, and cause the disengaging of sulfur and conducting matrix grain, thus causing the decay of capacity;4, lithium-sulfur cell is at present still in the laboratory research stage, and the sulfur carrying capacity in unit are is relatively low.
Solution to the problems described above generally can be started with from electrolyte and two aspects of cathode material.It is for instance possible to use the electrolyte of ethers is as the electrolyte of battery, and in electrolyte, add some additives, thus effectively alleviating the problems of dissolution of polysulfide intermediate;Further, it is also possible to sulfur and material with carbon element to be carried out compound, or sulfur and Organic substance are carried out compound, thus solving the problems such as the non-conductive of sulfur and volumetric expansion.
Though said method can improve the cycle performance of lithium-sulfur cell to a certain extent, but increase rate is limited, main cause may is that above-mentioned material lack can the sorption potential of strong adsorption polysulfide intermediate, therefore yet suffer from the loss of active substance.
Summary of the invention
The present invention provides silicon/silicon dioxide nano composite material that a kind of porous carbon bag wraps up in and its preparation method and application, this nano composite material can utilize the porous carbon ball with large specific surface area that polysulfide intermediate is carried out physical absorption, the electrostatic interaction attraction polysulfide intermediate of silicon/silicon dioxide nanoparticle and polysulfide intermediate can also be utilized simultaneously, the load capacity of sulfur is big, and active substance not easily loses.
The present invention provides the silicon/silicon dioxide nano composite material (hereinafter referred to as nano composite material) that a kind of porous carbon bag is wrapped up in, including silicon/silicon dioxide nanoparticle (Si/SiO2) and wrap up described silicon/silicon dioxide nanoparticle porous carbon ball, described porous carbon ball has micropore and mesopore.
In the present invention, described silicon/silicon dioxide nanoparticle has cross-linked network;That is, described silicon/silicon dioxide nanoparticle can be obtained by cross-linking reaction;It is possible to further adopt containing carbon and Si/SiO2Precursor (such as octaphenyl eight silsesquioxane etc.) and cross-linking agent (such as CCl4Deng) carry out cross-linking reaction.Additionally, described porous carbon ball can obtain by the organic material of carbon containing is carried out carbonization, for instance the silicon/silicon dioxide nanoparticle of carbon containing is carried out carbonization and obtains;It is possible to further by char-forming material being performed etching formation micropore and mesopore;Wherein, the aperture < 2nm of described micropore;The aperture of described mesopore is 2-50nm.Micropore and mesopore can promote cross-linked network have higher sulphur analysis and suppress the dissolving of polysulfide anion.
Further, the silicon/silicon dioxide nano composite material that the porous carbon bag of the present invention is wrapped up in can be passed through containing carbon and Si/SiO2The cross-linking reaction product of precursor and cross-linking agent carry out carbonization treatment and etching processing obtains.Further, precursor can at catalyst (such as AlCl with the cross-linking reaction of cross-linking agent3Deng) exist under carry out.
Above-mentioned cross-linking reaction can make silicon/silicon dioxide nanoparticle form cross-linked network, and this cross-linked network has rigidity, is not result in follow-up carbonization treatment process silicon/silicon dioxide and reunites, thus silicon and silicon dioxide are evenly distributed in porous carbon ball.Further, after the carbonization process, silicon/silicon dioxide and porous carbon ball form mutual winding;Additionally, etching processing can optimize the content of silicon/silicon dioxide in this material and form micropore and mesopore, thus providing more storage sulfur space (with reference to Fig. 1).
In the present invention, in the silicon/silicon dioxide nano composite material that described porous carbon bag is wrapped up in, the mass content of silicon/silicon dioxide nanoparticle is 1-30%;That is, in the silicon/silicon dioxide nano composite material that described porous carbon bag is wrapped up in, the gross mass content of silicon and silicon dioxide is 1-30%.
Further, the silicon/silicon dioxide nano composite material that described porous carbon bag is wrapped up in can be particle diameter is the spherical nano composite material of 350-500nm, for instance 400-450nm.
In the present invention, the specific surface area of the silicon/silicon dioxide nano composite material that described porous carbon bag is wrapped up in is 600-800m2/g;Total pore volume is 0.4-0.8cm3/g。
The silicon/silicon dioxide nano composite material that above-mentioned porous carbon bag is wrapped up in has good pore-size distribution, high specific surface area and the active site being completely exposed, and it carrys out physical absorption polysulfide not only by porous carbon ball, it is also possible to by the Si/SiO of positively charged2And the electrostatic interaction absorption polysulfide between polysulfide, this material is as the carrier of sulfur, it is possible to solve the problems of dissolution of polysulfide preferably;Additionally, Si/SiO2Cross-linked network can promote the stability of redox active in cyclic process, and good pore-size distribution, high surface area and the active site that is completely exposed can overcome the restriction of low-sulfur load, moreover it is possible to promote Li+Absorption and releasing, thus producing high rate capability, this material demonstrates excellent capacitance and cyclical stability, and capability retention is good, capacity attenuation slow (with reference to Fig. 2).
The preparation method that the present invention also provides for the silicon/silicon dioxide nano composite material that any of the above-described described porous carbon bag is wrapped up in, comprises the steps:
1) in the presence of a catalyst, octaphenyl eight silsesquioxane (octaphenyl-POSS) and cross-linking agent are carried out cross-linking reaction;
2) product of described cross-linking reaction is carried out carbonization treatment;
3) product of described carbonization treatment is performed etching process, obtain the silicon/silicon dioxide nano composite material that described porous carbon bag is wrapped up in.
In the solution of the present invention, step 1) particularly as follows: after octaphenyl eight silsesquioxane is mixed with organic solvent, add catalyst and cross-linking agent carry out cross-linking reaction.
Wherein, described catalyst can be AlCl3;Described cross-linking agent can be CCl4;Described organic solvent can be dichloroethanes.And it is possible to the temperature controlling described cross-linking reaction is 50-70 DEG C, for instance 60 DEG C, the time is 5-24h, for instance 10h.Additionally, the mol ratio of octaphenyl eight silsesquioxane and catalyst can be (1-3): (1-10), for instance 1.5:2, namely octaphenyl eight silsesquioxane of 1-3mmol uses the catalyst of 1-10mmol;The molal quantity of octaphenyl eight silsesquioxane and the volume ratio of cross-linking agent can be (1-3): (10-100), for instance 1.5:40, and namely octaphenyl eight silsesquioxane of 1-3mmol uses the cross-linking agent of 10-100mL.
In the solution of the present invention, step 2) particularly as follows: add reaction terminating agent to the product of described cross-linking reaction, filter subsequently, clean, dry, then the intensification of dried cross-linking reaction product is carried out carbonization treatment.
Wherein, reaction terminating agent can be the mixed solution of the alcoholic solution of 95wt% and water, and in mixed solution, the alcoholic solution of 95wt% can be 4:1 with the volume ratio of water;Cleaning can adopt the mixed solution of alcoholic solution and dilute hydrochloric acid solution and pure water to carry out, and wherein the concentration of alcoholic solution can be 95wt%, and the concentration of dilute hydrochloric acid solution can be 5wt%;Drying and can carry out at 80 DEG C, drying time can be 12h.
It is possible to further the temperature controlling described carbonization treatment is 600-1000 DEG C, for instance 900 DEG C;Time is 1-4h, for instance 3h;Heating rate is 1-15 DEG C/min, for instance 2 DEG C/min;That is, cross-linking reaction product it is warming up to 600-1000 DEG C with the heating rate of 1-15 DEG C/min and is incubated 1-4h.
In the solution of the present invention, step 3) particularly as follows: the product of described carbonization treatment is placed in etching solution and performs etching process, wash subsequently, filter, dry, obtain the silicon/silicon dioxide nano composite material that described porous carbon bag is wrapped up in.
Wherein, etching solution can be NaOH solution, and the concentration of NaOH solution can be 10-30wt%, for instance 20wt%;It is possible to further the time controlling described etching processing is 6-24h.Etching processing can optimize Si/SiO2Content and improve the porosity of porous carbon ball, thus providing more storage sulfur space, improve the load capacity of sulfur.
The present invention also provides for the application as battery cathode material of silicon/silicon dioxide nano composite material that any of the above-described described porous carbon bag wraps up in.Further, described battery cathode material is specially lithium-sulfur cell cathode material.
The present invention also provides for a kind of lithium-sulfur cell cathode material, including the silicon/silicon dioxide nano composite material that sulfur and any of the above-described described porous carbon bag wrapping up described sulfur are wrapped up in.
Further, in described lithium-sulfur cell cathode material, the mass content of sulfur is 50-70%.
The preparation method that the present invention also provides for above-mentioned lithium-sulfur cell cathode material, the silicon/silicon dioxide nano composite material that sulfur is wrapped up in any of the above-described described porous carbon bag is mixed, subsequently the mixture being mixed to form is sequentially carried out grinding and heating, prepares described cathode materials for lithium battery.
Further, the mass ratio of the silicon/silicon dioxide nano composite material that porous carbon bag is wrapped up in and sulfur can be 1:(3-5), for instance 1:4.Above-mentioned grinding is used for making sulfur mix homogeneously with nano composite material;Above-mentioned heating is for promoting that sulfur enters in the silicon/silicon dioxide nano composite material that porous carbon bag is wrapped up in, and the temperature of heating can be 100-300 DEG C, for instance 157 DEG C, and heat time heating time can be 8-16h, for instance 12h.
Further, the step removing unnecessary sulfur can also be included after the heating;The step of the unnecessary sulfur of this removal is specifically as follows: be heated (such as under argon atmosphere) under atmosphere of inert gases, for instance can heat 30min at 200 DEG C, to remove unnecessary sulfur.
Accompanying drawing explanation
Fig. 1 is the building-up process schematic diagram of the lithium-sulfur cell cathode material of the present invention;
Fig. 2 is the action principle schematic diagram of the lithium-sulfur cell cathode material of the present invention;
Fig. 3 is the TEM figure of the carbonized product of embodiment 1;
Fig. 4 is the TEM figure of the nano composite material of embodiment 1;
Fig. 5 is the XRD analysis figure of the nano composite material of embodiment 1;
Fig. 6 is the TG analysis chart of the nano composite material of embodiment 1;
Fig. 7 is the N2 adsorption-desorption isotherm of the nano composite material of embodiment 1;
Fig. 8 is the TEM figure of the lithium-sulfur cell cathode material of embodiment 4;
Fig. 9 is the XPS analysis figure of the lithium-sulfur cell cathode material of embodiment 4;
Figure 10 is the performance of the lithium-sulfur cell made with the lithium-sulfur cell cathode material of embodiment 4;
Figure 11 is the performance of the lithium-sulfur cell made with the lithium-sulfur cell cathode material of embodiment 5;
Figure 12 is the performance of the lithium-sulfur cell made with the lithium-sulfur cell cathode material of embodiment 6.
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention clearly, below in conjunction with embodiments of the invention, the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that, described embodiment is a part of embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art obtain under not making creative work premise, broadly fall into the scope of protection of the invention.
Embodiment 1
Octaphenyl-the POSS of 1.5mmol is dissolved in 1, the 2-dichloroethanes that 70mL temperature is about 60 DEG C, about magnetic agitation 1h at 60 DEG C, adds the AlCl of 2mmol3The CCl of catalyst and 40mL4Cross-linking agent carries out cross-linking reaction, and after reacting 10 hours, the alcoholic solution of 95wt% adding 100mL terminates reaction with the mixed solution (in mixed solution, alcoholic solution is 4:1 with the volume ratio of water) of water, filters subsequently, obtains cross-linking reaction product.
Cross-linking reaction product is carried out by the mixed solution (in mixed solution, alcoholic solution is 3:1 with the volume ratio of dilute hydrochloric acid solution) and the water that adopt the dilute hydrochloric acid solution of the alcoholic solution of 95wt% and 5wt%, then dries 12h at 80 DEG C again;Subsequently, dried cross-linking reaction product it is warming up to 900 DEG C with the heating rate of 2 DEG C/min under nitrogen atmosphere and is incubated 3h, obtaining carbonized product.
Above-mentioned carbonized product is placed in the sodium hydroxide solution of 20wt% and etches 12h, take out subsequently, through washing, filtration, dry, obtain the silicon/silicon dioxide nano composite material that porous carbon bag is wrapped up in.
The nano composite material of above-mentioned preparation is analyzed.Wherein, X-ray diffraction analysis (XRD) adopts X'Pert3Powder x-ray diffraction (production of PANalytical company) carries out, and its assembling CuK α radiation, accelerating potential and electric current respectively 40kV and 40mA, the opereating specification of 2 θ in XRD figure picture is 10-70 °;The morphological characteristic of material uses FEITecnaiT20 and F30 transmission electron microscope (TEM) to carry out;Elemental composition analysis adopts x-ray photoelectron spectroscopy (XPS), uses monochromatic AlK α to radiate (KratosAxisUltra, 1486.6eV);BET analyzes the analyser adopting model to be ASAP2010 and carries out;Thermogravimetric analysis (TGA) and means of differential scanning calorimetry (DSC) measure the analyser (U.S.) adopting model to be SDTQ600 to carry out, and wherein in the firing rate 10 DEG C/min of air, heating interval is 25 to 800 DEG C.
Fig. 3 is the TEM figure of the carbonized product of above-mentioned preparation;Fig. 4 is the TEM figure of the nano composite material of above-mentioned preparation.In conjunction with, shown in Fig. 3 and Fig. 4, forming substantial amounts of micropore and mesopore after carbonized product is etched, the nano composite material of preparation is particle diameter is the spheroidal material of about 420nm, and its specific surface area and total pore volume are in Table 1.Owing to the bond distance of sulfur is in the scope of 0.188-2.072nm, a large amount of micropores and mesopore that therefore above-mentioned nano composite material has can provide higher sulphur analysis and suppress the dissolving of polysulfide anion.
As it is shown in figure 5, XRD analysis result shows: Si and SiO in this nano composite material2The position of diffraction maximum and intensity all mesh well in Si (JCPDS89-9056) and SiO2The standard card of (No. JCPDS89-3436), it was shown that there is the silicon/silicon dioxide of pure phase in this nano composite material.
As shown in Figure 6, TGA analyzes result and shows, in the nano composite material of above-mentioned preparation, carbon (76.2wt%) is run off rapidly by oxidation at 551 DEG C, Si/SiO in nano composite material2Content be 15.5wt%.
As it is shown in fig. 7, N2 adsorption-desorption isotherm shows that the nano composite material of above-mentioned preparation has high surface and IV type sluggishness, it was shown that containing substantial amounts of micropore and mesopore in porous carbon ball.
Embodiment 2
Adopt after preparing carbonized product with the identical method of embodiment 1, carbonized product be placed in the sodium hydroxide solution of 20wt% etching 6h, take out subsequently, through washing, filter, dry, obtain the silicon/silicon dioxide nano composite material that porous carbon bag is wrapped up in.
Adopt embodiment 1 method that the nano composite material of above-mentioned preparation is analyzed.Result shows: this nano composite material is particle diameter is the spheroidal material of about 420nm, wherein has substantial amounts of micropore and a mesopore, and there is the silicon/silicon dioxide of pure phase, and its specific surface area and total pore volume are in Table 1.Additionally, Si/SiO in this nano composite material2Content be 24.7wt%.
Embodiment 3
Adopt after preparing carbonized product with the identical method of embodiment 1, carbonized product be placed in the sodium hydroxide solution of 20wt% etching 24h, take out subsequently, through washing, filter, dry, obtain the silicon/silicon dioxide nano composite material that porous carbon bag is wrapped up in.
Adopt embodiment 1 method that the nano composite material of above-mentioned preparation is analyzed.Result shows: this nano composite material is particle diameter is the spheroidal material of about 420nm, wherein has substantial amounts of micropore and a mesopore, and there is the silicon/silicon dioxide of pure phase, and its specific surface area and total pore volume are in Table 1.Additionally, Si/SiO in this nano composite material2Content be 4.6wt%.
Embodiment 4
The silicon/silicon dioxide nano composite material that the porous carbon bag of embodiment 1 is wrapped up in is mixed according to mass ratio 1:4 with business sulfur, the mixture grind into powder that will be formed after mixing, then at 157 DEG C, heat 12h, under argon atmosphere, heat 30min to remove unnecessary sulfur in 200 DEG C again, obtain the lithium-sulfur cell cathode material that sulfur content is 69.6wt%.
Fig. 8 is the TEM figure of the lithium-sulfur cell cathode material of above-mentioned preparation.As shown in Figure 8, the lithium-sulfur cell cathode material formed after noting sulfur in nano composite material remains in that as spherical, and surface is without sulfur particle or aggregation, and sulfur is limited in nano composite material equably, and its specific surface area and total pore volume are in Table 1.
In addition, as shown in Figure 9, X-ray photoelectron spectroscopic analysis shows the characteristic peak of Si (at about 102 volts and the 200 volts elements corresponding to Si2p and Si2s), C (284 electron-volts), O (at 560 electron-volts) and sulfur, it was demonstrated that there is above-mentioned chemical element in this lithium-sulfur cell cathode material.
Embodiment 5
The silicon/silicon dioxide nano composite material that the porous carbon bag of embodiment 2 is wrapped up in is mixed according to mass ratio 1:4 with business sulfur, the mixture grind into powder that will be formed after mixing, then at 157 DEG C, heat 12h, under argon atmosphere, heat 30min to remove unnecessary sulfur in 200 DEG C again, obtain the lithium-sulfur cell cathode material that sulfur content is 58.3wt%.
Analysis result shows: this lithium-sulfur cell cathode material is spherical, wherein contains Si, C, O and S element, and this material surface is without sulfur particle or aggregation, and sulfur is limited in nano composite material equably, and its specific surface area and total pore volume are in Table 1.
Embodiment 6
The silicon/silicon dioxide nano composite material that the porous carbon bag of embodiment 3 is wrapped up in is mixed according to mass ratio 1:4 with business sulfur, the mixture grind into powder that will be formed after mixing, then at 157 DEG C, heat 12h, under argon atmosphere, heat 30min to remove unnecessary sulfur in 200 DEG C again, obtain the lithium-sulfur cell cathode material that sulfur content is 73.2wt%.
Analysis result shows: this lithium-sulfur cell cathode material is spherical, wherein contains Si, C, O and S element, and this material surface is without sulfur particle or aggregation, and sulfur is limited in nano composite material equably, and its specific surface area and total pore volume are in Table 1.
Reference examples 1
Using the carbonized product (namely processing without subsequent etching) of embodiment 1 preparation as compareing nano composite material, it is mixed according to mass ratio 1:4 with business sulfur, the mixture grind into powder that will be formed after mixing, then at 157 DEG C, heat 12h, under argon atmosphere, heat 30min to remove unnecessary sulfur in 200 DEG C again, obtain comparison lithium-sulfur cell cathode material.
Si/SiO in each material of table 12Content and specific surface area and total pore volume
Test example 1
The chemical property of lithium-sulfur cell cathode material prepared by testing example 4-6 on the analyser that model is LANDCT2001A, wherein potential windows is at 1.7-2.8VvsLi+Between/Li, test under different current values.Test battery includes two electrodes, and wherein lithium paper tinsel is as reference electrode with to electrode, and by lithium-sulfur cell cathode material, (load capacity is 3.1-3.5mg/cm to working electrode2), conductive agent (acetylene black) and polymer adhesive (politef, PTFE) prepare.The all components of working electrode is sufficiently mixed in isopropanol and is pasted onto on aluminium foil, slurry at 80 DEG C vacuum drying 14 hours to remove moisture or solvent composition, the thickness of electrode is 150 microns, uses 2300 films of Celgard company to make dividing plate and negative electrode and anode is separated.Electrolyte is double; two (fluoroform) sulfimide lithiums (LiTFSI) of 1M, and it is dissolved in containing 0.1MLiNO3DOX/1, in 2-dimethoxy-ethane (DOL/DME) (1:1, v/v) mixed solution.Being placed in by battery in the glove box of full argon (advanced instrument company GPR1900), wherein moisture and oxygen content are maintained at below 1ppm.Cyclic voltammetry (CV) curve of material all carries out at the test speed of 0.1mV, and voltage tester ranges for 1.7-2.8V.Electrochemical impedance spectroscopy (EIS) uses CHI760C (Shanghai occasion China) to test between 100KHz to 10MHz.
The performance map of the lithium-sulfur cell that the lithium-sulfur cell cathode material of Figure 10 to Figure 12 respectively embodiment 4 to 6 makes.Figure 10 result shows: the lithium-sulfur cell cathode material of embodiment 4 has the high initial specific capacities of 1215mAh/g (for theoretical capacity 74%), and still there is for 100 times the capability retention (82.9%) of excellence, stable cycle performance in circulation.Figure 11 result shows: the powerful capacity of the lithium-sulfur cell cathode material of embodiment 5 is 1065mAh/g, and is 833mAh/g 100 circulations, has the capability retention of about 78.2%.Figure 12 result shows: the discharge capacity of the lithium-sulfur cell cathode material of embodiment 6 is very rapidly down to 707mAh/g from 993mAh/g, and capability retention is 71.1%.
The resistance data of each material of table 2
Last it is noted that various embodiments above is only in order to illustrate technical scheme, it is not intended to limit;Although the present invention being described in detail with reference to foregoing embodiments, it will be understood by those within the art that: the technical scheme described in foregoing embodiments still can be modified by it, or wherein some or all of technical characteristic is carried out equivalent replacement;And these amendments or replacement, do not make the essence of appropriate technical solution depart from the scope of various embodiments of the present invention technical scheme.

Claims (10)

1. the silicon/silicon dioxide nano composite material that a porous carbon bag is wrapped up in, it is characterised in that including silicon/silicon dioxide nanoparticle and wrap up the porous carbon ball of described silicon/silicon dioxide nanoparticle, described porous carbon ball has micropore and mesopore.
2. the silicon/silicon dioxide nano composite material that porous carbon bag according to claim 1 is wrapped up in, it is characterised in that in the silicon/silicon dioxide nano composite material that described porous carbon bag is wrapped up in, the mass content of silicon/silicon dioxide nanoparticle is 1-30%.
3. the silicon/silicon dioxide nano composite material that porous carbon bag according to claim 1 is wrapped up in, it is characterised in that the silicon/silicon dioxide nano composite material that described porous carbon bag is wrapped up in is particle diameter is the spherical nano composite material of 350-500nm.
4. the preparation method of the silicon/silicon dioxide nano composite material that the arbitrary described porous carbon bag of claims 1 to 3 is wrapped up in, it is characterised in that comprise the steps:
1) in the presence of a catalyst, octaphenyl eight silsesquioxane and cross-linking agent are carried out cross-linking reaction;
2) product of described cross-linking reaction is carried out carbonization treatment;
3) product of described carbonization treatment is performed etching process, obtain the silicon/silicon dioxide nano composite material that described porous carbon bag is wrapped up in.
5. preparation method according to claim 4, it is characterised in that described catalyst is AlCl3, described cross-linking agent is CCl4, and the temperature controlling described cross-linking reaction is 50-70 DEG C, the time is 5-24h.
6. preparation method according to claim 4, it is characterised in that the temperature controlling described carbonization treatment is 600-1000 DEG C, the time is 1-4h, and heating rate is 1-15 DEG C/min.
7. preparation method according to claim 4, it is characterised in that adopt NaOH solution to carry out described etching processing, and the time controlling described etching processing is 6-24h.
8. the silicon/silicon dioxide nano composite material that the arbitrary described porous carbon bag of claims 1 to 3 is wrapped up in is as the application of battery cathode material.
9. a lithium-sulfur cell cathode material, it is characterised in that include sulfur and wrap up the silicon/silicon dioxide nano composite material that the arbitrary described porous carbon bag of claims 1 to 3 of described sulfur is wrapped up in.
10. the preparation method of the lithium-sulfur cell cathode material described in claim 9, it is characterized in that, the silicon/silicon dioxide nano composite material that arbitrary to sulfur and claims 1 to 3 described porous carbon bag is wrapped up in is mixed, subsequently the mixture formed is sequentially carried out grinding and heating, prepares described lithium-sulfur cell cathode material.
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