CN106025228A - Nanocomposite loading carbon-coated SnO2 nano particles on graphene sheets and preparation method of nanocomposite - Google Patents

Nanocomposite loading carbon-coated SnO2 nano particles on graphene sheets and preparation method of nanocomposite Download PDF

Info

Publication number
CN106025228A
CN106025228A CN201610553030.4A CN201610553030A CN106025228A CN 106025228 A CN106025228 A CN 106025228A CN 201610553030 A CN201610553030 A CN 201610553030A CN 106025228 A CN106025228 A CN 106025228A
Authority
CN
China
Prior art keywords
graphene
preparation
nano
carbon
nanocomposite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201610553030.4A
Other languages
Chinese (zh)
Inventor
王雄伟
武培怡
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fudan University
Original Assignee
Fudan University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fudan University filed Critical Fudan University
Priority to CN201610553030.4A priority Critical patent/CN106025228A/en
Publication of CN106025228A publication Critical patent/CN106025228A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • 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
    • H01M4/58—Selection 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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 invention belongs to the technical field of lithium battery materials, in particular to a nanocomposite loading carbon-coated SnO2 nano particles on graphene sheets and a preparation method of the nanocomposite. Firstly a composite loading carbon-coated iron oxide on grapheme is obtained through a solvothermal reaction between ferrocene and graphene oxide, then ferric oxide nano particles in the composite are etched through acid to obtain carbon nanofoam with plenty of mesoporous structures, and then through precursor hydrolysis, mesopores are filled with SnO2 nano particles. The obtained material has very excellent lithium ion storage performance, outstanding cycling stability and excellent rate performance when being used as an anode material of a lithium battery. The method is simple to operate, relatively low in production cost and easy for batch and large-scale production, and has good industrial production bases and wide application prospects.

Description

Carbon wraps up SnO 2 Nano composite material that nano-particle is supported on Graphene and preparation method thereof
Technical field
The invention belongs to energy storage material field, be specifically related to lithium cell cathode material of a kind of high energy storage density and cyclical stability and preparation method thereof.
Background technology
Population and quickly increasing of industry make people grow with each passing day the demand of the energy.Store the energy the most efficiently also to therefore suffer from people and pay close attention to widely and study.Lithium battery has been widely used for the driving power supply as portable electric appts, electric automobile and intelligent grid owing to having high energy storage density, length in service life and low self-discharge characteristics.But, the theoretical capacity of the most commercial lithium cell cathode material graphite is only 372 mAh g-1, and high rate performance is the most poor, is difficult to meet following electric automobile to Large Copacity, the requirement of high safety battery.Therefore to have the novel lithium battery material of more high energy storage density and high rate performance significant in research and development.
In the past ten years, various metal-oxides are widely used for studying the negative material as lithium battery, and this is owing to they have the feature of high theoretical capacity, low cost and rich content.In these metal-oxides, stannum oxide (SnO2) due to its preparation process environmental friendliness and high theoretical capacity (782 mAh g-1) it is considered as a kind of ideal material preparing high-performance lithium battery.Unfortunately, stannum oxide can produce the biggest change in volume during lithium ion intercalation and abjection, and this big change in volume can cause the broken of tin oxide nanoparticles and reunite, and ultimately results in violent capacity loss and the high rate performance of difference.On the other hand, the intrinsic conductivity of stannum oxide is the most poor, is unfavorable for the raising of its chemical property.
For solving the problems referred to above that stannum oxide exists, the most more common mainly has two schemes.The first scheme is design and the stannum oxide building various nanotopology, and such as nanotube, nanometer sheet, nano wire and nanometer box etc. reduce its structural stress, increase and contact area of electrolyte in charge and discharge process and shorten the evolving path of lithium ion.But owing to this method is still difficult to avoid that the broken of nano-particle and reunites, therefore it solves capacity attenuation big in long-term charge and discharge process with being difficult to essence.The most single nano tin dioxide is the most poor to the toleration of high current density.Another kind of more scheme is by being combined with conductive carbon matrix by nano tin dioxide, thus comes the charge-conduction ability of reinforcing material, the reunion hindering nano tin dioxide and big volumetric expansion.The composite of most of stannum oxide/carbon is directed to be supported on carbon base body Nano granules of stannic oxide, such as Graphene, CNT and unformed carbon.But, load tin oxide nano up is easier to come off and reunite due to interaction weak between matrix in charge and discharge process, thus causes quick capacity attenuation and structural deterioration.It is considered as a kind of particle agglomeration, broken and limit the effective ways that solid electrolyte interface layer is formed of preventing that nano tin dioxide carries out carbon parcel.But it there is also the shortcoming that the more graphene-based composite of charge-conduction ability is weak.Therefore merge the advantage of above two schemes to prepare the composite that the nano-particle of carbon bag stannum oxide is supported on Graphene and may have more preferable effect to solving the problems referred to above.And amorphous carbon layer is also used as cross-linking agent and makes stannum oxide closely be fixed on graphenic surface.
The present invention is based on combining the thought of above two scheme, first passes through graphene@Fe3O4@C nano composite carries out acid etch and obtains the porous carbon network containing a large amount of meso-hole structures.Then butter of tin ethanol solution is injected in porous carbon network, through hydrolysis, dries and be thermally treated resulting in final graphene@SnO2@C nano composite, it is achieved by carbon bag tin oxide nanoparticles uniform load on graphene film surface.Owing to reasonably designing and special structure, graphene@SnO2@C nano composite has high reversible capacity (at 0.2 A g as the negative material of lithium battery-1Under electric current density, the capacity of the second circle circulation is 1205 mAh g-1), (circulate the capacity after 50 times is 1005 mAh g to excellent cyclical stability-1) and good high rate performance.
Summary of the invention
It is an object of the invention to provide a kind of nano composite material being supported on Graphene as the carbon bag tin oxide nanoparticles with excellent properties of lithium cell cathode material and its preparation method and application.
The preparation method of the composite that the carbon parcel tin oxide nanoparticles that the present invention provides is supported on Graphene, concretely comprises the following steps:
(1) graphene oxide (GO) oxidation-reduction method prepared disperses in a solvent, obtains GO dispersion liquid, and the concentration of GO is 2-10 mg/ml；
(2) 0.02 ~ 0.20 g iron containing compounds, ultrasonic dissolution, in 2 ~ 10 ml solvents, is subsequently adding the GO dispersion liquid that 2 ~ 10 ml steps (1) are prepared, ultrasonic 15 ~ 60 min, makes dispersed, add 0.1 ~ 1 ml hydrogen peroxide；
(3) mixed liquor that step (2) obtains is transferred in autoclave pressure, is placed in 150 ~ 250 DEG C of baking ovens reaction 2 ~ 36 h；After naturally cooling to room temperature, feed liquid is taken out, with dehydrated alcohol centrifuge washing 3 ~ 10 times；Then reactant is placed in 2 ~ 24 h in 50 ~ 120 DEG C of baking ovens dry；
(4) powder taking 0.1 ~ 1 g drying is placed in tube furnace, heats to 350 ~ 700 DEG C under nitrogen protection, is incubated 1 ~ 6 h, obtains nano composite material, be designated as graphene@Fe3O4@C；
(5) 0.02 ~ 0.5 g graphene@Fe is weighed3O4@C joins in the hydrochloric acid solution that 50 ~ 150 ml concentration are 0.5 ~ 5 M, stirs reaction 2 ~ 12 h, obtain the porous carbon network of sandwich-like, be designated as MCF at 25 ~ 80 DEG C；
(6) 0.02 ~ 0.2 g MCF ultrasonic disperse is weighed at the SnCl that concentration is 0.05 ~ 0.5 g/ml2In the solution of-ethanol, at 25 ~ 60 DEG C, stir 2 ~ 8 h, centrifugation by washing with alcohol once；It is subsequently adding 2 ~ 5 ml ammonia and inspires hydrolysis, keep reaction 20 ~ 120 min, reaction to wash 2 ~ 6 times by centrifugal method after terminating；The material after above-mentioned process is re-dispersed into the SnCl of same concentrations again2In the solution of-ethanol, processed by the step identical with first time, obtain the material of secondary hydrolysis；After drying at 40 ~ 100 DEG C, material is placed in tube furnace under nitrogen protection and is warming up to 300 ~ 700 DEG C, be incubated 1 ~ 3 h, obtain final material, be designated as graphene@SnO2@C。
In the present invention, solvent used in step (1), step (2) is the one in acetone, oxolane, DMF, or the most several mixture.
In the present invention, iron containing compounds used in step (2) is the one in iron acetate, ferrocene, carbonyl iron.
The nano composite material that is supported on graphite of carbon bag tin oxide nanoparticles that the present invention provides, be by presoma diffusion is injected in the mesoporous carbon network of preparation in advance and through hydrolysis subsequently, dry and be thermally treated resulting in the composite at graphenic surface uniform load carbon bag tin oxide nanoparticles.Introducing of Graphene promotes the dispersion of nano-particle primarily as a kind of supporter and improves the charge-conduction ability of material.The reunion in charge and discharge process of the parcel of the agraphitic carbon the most not only inhibited oxidation tin particles, broken, it is also possible to effectively to reduce the change in volume of granules of stannic oxide, granules of stannic oxide can also be made tightly to be pinned at matrix surface as cross-linking agent simultaneously.
The present invention is easy to operate, and preparation condition is simple, and production cost is low, it is easy to mass, large-scale production, has the application prospect that good industrialized production is basic and wide.
Accompanying drawing explanation
Fig. 1 .graphene@Fe3O4The scanning electron microscope diagram of@C nano composite and transmission electron microscope figure.
Fig. 2. the scanning electron microscope diagram of MFC.
Fig. 3. the transmission electron microscope figure of MFC.
Fig. 4. graphene SnO2@C nano composite scanning electron microscope diagram and transmission electron microscope figure.
Fig. 5. graphene SnO2@C nano composite is 200 mA g in electric current density-1Under charge and discharge cycles stability diagram.
Fig. 6. graphene SnO2@C nano composite charge-discharge magnification performance under different electric current densities.
Fig. 7. the scanning electron microscope diagram of the graphene Fe3O4 C nano composite obtained in the case of hydrogen peroxide addition is less.
Fig. 8. ferrocene addition is 0.05 The MCF transmission electron microscope figure that during g, acid etch obtains.
Detailed description of the invention
Further describing the preparation method of nano composite material and catalysis thereof and absorption property that the present invention ultra-thin carbon nickel coat nano-crystalline granule is supported on Graphene by the following examples, this embodiment is merely possible to provide explanation rather than limit the present invention.
Embodiment 1
(1) graphene oxide (GO) oxidation-reduction method prepared disperses in acetone, obtains this solvent dispersions of GO, and the concentration of GO is 2 mg/ml；
(2) weighing 0.07 g ferrocene ultrasonic dissolution in 5 ml acetone, be subsequently adding the GO dispersion liquid of preparation in 5 ml steps (1), ultrasonic 30 min make dispersed, add 0.35 ml hydrogen peroxide；
(3) mixed liquor obtained in step (2) is transferred in autoclave pressure, is placed in 210 DEG C of baking ovens and reacts 12 h；After naturally cooling to room temperature, by feed liquid taking-up dehydrated alcohol centrifuge washing 3 times；Then reactant is placed in 12 h in 60 DEG C of baking ovens dry；
(4) powder taking 0.5 g drying is placed in tube furnace, heats to 500 DEG C under nitrogen protection, is incubated 2 h, obtain final nano composite material, is designated as graphene@Fe3O4@C；
(5) 0.25 g graphene@Fe is weighed3O4@C joins in the hydrochloric acid solution that 100 ml concentration are 2 M, and at 50 DEG C, stirring reaction 12 h, obtain the porous carbon network of sandwich-like, be designated as taking MCF；
(6) 0.05 g MCF ultrasonic disperse is weighed at the SnCl that concentration is 0.1 g/ml2In the solution of-ethanol, at 25 DEG C, stir 6 h, centrifugation by washing with alcohol once；Being subsequently adding 2 ml ammonia and inspire hydrolysis, keep reaction 30 min, reaction is washed 4 times by centrifugal method after terminating；The material after above-mentioned process is re-dispersed into the SnCl of same concentrations again2In the solution of-ethanol, processed by the step identical with first time, obtain the material of secondary hydrolysis.After drying at 60 DEG C, material is placed in tube furnace under nitrogen protection and is warming up to 350 DEG C, be incubated 1 ~ 3 h, obtain final material, be designated as graphene@SnO2@C。
Carbon bag Fe as can see from Figure 13O4Nano-particle homoepitaxial on the surface of graphene nanometer sheet, it can clearly be seen that Fe from high-resolution transmission plot3O4Particle surface has been coated with one layer of thin carbon-coating really.After acidity etches away ferrum oxide, by Fig. 2 it can be seen that graphenic surface the most fully remains mesoporous carbon structure, the enhancing of electronics permeability also illustrates Fe3O4It is dissolved.Can more be can be visually seen by the transmission plot of Fig. 3, graphenic surface is intensive is loaded with substantial amounts of mesoporous carbon equably, the size of carbon pores and Fe3O4Consistent。Electronic Speculum figure such as Fig. 4 of SnO2 nano-particle is inserted, it can be seen that SnO with mesoporous carbon network for matrix2Crystal grain is the most successfully filled in mesoporous carbon.Fig. 5 shows the graphene@SnO obtained2@C is at 200 mA g-1There is under electric current density the cyclical stability of excellence.The reversible capacity of the second circle is up to 1205 mAh g-1, after 50 circulations, capacity still has 1005 mAh g-1.In addition this material also has preferable high rate performance, at 1.2 A g-1Electric current density under can keep 725 mAh g-1The capacity twice of graphite electrode theoretical capacity (be commercial), and return to, during charging under low current, there is good capacity recovery.
Embodiment 2
(1) graphene oxide (GO) oxidation-reduction method prepared disperses in acetone, obtains this solvent dispersions of GO, and the concentration of GO is 2 mg/ml；
(2) weighing 0.07 g ferrocene ultrasonic dissolution at 5 ml acetone, be subsequently adding the GO dispersion liquid of preparation in 5 ml steps (1), ultrasonic 30 min make dispersed, are not added with hydrogen peroxide；
(3) mixed liquor obtained in step (2) is transferred in autoclave pressure, is placed in 210 DEG C of baking ovens and reacts 12 h；After naturally cooling to room temperature, by feed liquid taking-up dehydrated alcohol centrifuge washing 3 times；Then reactant is placed in 12 h in 60 DEG C of baking ovens dry；
(4) powder taking 0.5 g drying is placed in tube furnace, heats to 500 DEG C under nitrogen protection, is incubated 2 h, obtain final nano composite material, is designated as graphene@Fe3O4@C；
(5) 0.25 g graphene@Fe is weighed3O4@C joins in the hydrochloric acid solution that 100 ml concentration are 2 M, and at 50 DEG C, stirring reaction 12 h, obtain the porous carbon network of sandwich-like, be designated as taking MCF；
(6) 0.05 g MCF ultrasonic disperse is weighed at the SnCl that concentration is 0.1 g/ml2In the solution of-ethanol, at 25 DEG C, stir 6 h, centrifugation by washing with alcohol once；Being subsequently adding 2 ml ammonia and inspire hydrolysis, keep reaction 30 min, reaction is washed 4 times by centrifugal method after terminating；The material after above-mentioned process is re-dispersed into the SnCl of same concentrations again2In the solution of-ethanol, processed by the step identical with first time, obtain the material of secondary hydrolysis.After drying at 60 DEG C, material is placed in tube furnace under nitrogen protection and is warming up to 350 DEG C, be incubated 1 ~ 3 h, obtain final material, be designated as graphene@SnO2@C。
Fig. 7 shows that not adding hydrogen peroxide obtains graphene@Fe3O4The carbon bag Fe of graphenic surface load in@C composite3O4Nano-particle is more of a relatively loose and uneven.
Embodiment 3
(1) graphene oxide (GO) oxidation-reduction method prepared disperses in acetone, obtains this solvent dispersions of GO, and the concentration of GO is 2 mg/ml；
(2) weighing 0.05 g ferrocene ultrasonic dissolution at 5 ml acetone, be subsequently adding the GO dispersion liquid of preparation in 5 ml steps (1), ultrasonic 30 min make dispersed, add 0.25 ml hydrogen peroxide；
(3) mixed liquor obtained in step (2) is transferred in autoclave pressure, is placed in 210 DEG C of baking ovens and reacts 12 h；After naturally cooling to room temperature, by feed liquid taking-up dehydrated alcohol centrifuge washing 3 times；Then reactant is placed in 12 h in 60 DEG C of baking ovens dry；
(4) powder taking 0.5 g drying is placed in tube furnace, heats to 500 DEG C under nitrogen protection, is incubated 2 h, obtain final nano composite material, is designated as graphene@Fe3O4@C；
(5) 0.25 g graphene@Fe is weighed3O4@C joins in the hydrochloric acid solution that 100 ml concentration are 2 M, and at 50 DEG C, stirring reaction 12 h, obtain the porous carbon network of sandwich-like, be designated as taking MCF；
(6) 0.05 g MCF ultrasonic disperse is weighed at the SnCl that concentration is 0.1 g/ml2In the solution of-ethanol, at 25 DEG C, stir 6 h, centrifugation by washing with alcohol once；Being subsequently adding 2 ml ammonia and inspire hydrolysis, keep reaction 30 min, reaction is washed 4 times by centrifugal method after terminating；The material after above-mentioned process is re-dispersed into the SnCl of same concentrations again2In the solution of-ethanol, processed by the step identical with first time, obtain the material of secondary hydrolysis.After drying at 60 DEG C, material is placed in tube furnace under nitrogen protection and is warming up to 350 DEG C, be incubated 1 ~ 3 h, obtain final material, be designated as graphene@SnO2@C。
Fig. 8 shows, when ferrocene addition is 0.05 g, the mesoporous carbon of the MCF area load that etching obtains is the most sparse.
Embodiment 4
(1) graphene oxide (GO) oxidation-reduction method prepared disperses in acetone, obtains this solvent dispersions of GO, and the concentration of GO is 2 mg/ml；
(2) weighing 0.03 g ferrocene ultrasonic dissolution at 5 ml acetone, be subsequently adding the GO dispersion liquid of preparation in 5 ml steps (1), ultrasonic 30 min make dispersed, add 0.15ml hydrogen peroxide；
(3) mixed liquor obtained in step (2) is transferred in autoclave pressure, is placed in 210 DEG C of baking ovens and reacts 12 h；After naturally cooling to room temperature, by feed liquid taking-up dehydrated alcohol centrifuge washing 3 times；Then reactant is placed in 12 h in 60 DEG C of baking ovens dry；
(4) powder taking 0.5 g drying is placed in tube furnace, heats to 500 DEG C under nitrogen protection, is incubated 2 h, obtain final nano composite material, is designated as graphene@Fe3O4@C；
(5) 0.25 g graphene@Fe is weighed3O4@C joins in the hydrochloric acid solution that 100 ml concentration are 2 M, and at 50 DEG C, stirring reaction 12 h, obtain the porous carbon network of sandwich-like, be designated as taking MCF；
(6) 0.05 g MCF ultrasonic disperse is weighed at the SnCl that concentration is 0.1 g/ml2In the solution of-ethanol, at 25 DEG C, stir 6 h, centrifugation by washing with alcohol once；Being subsequently adding 2 ml ammonia and inspire hydrolysis, keep reaction 30 min, reaction is washed 4 times by centrifugal method after terminating；The material after above-mentioned process is re-dispersed into the SnCl of same concentrations again2In the solution of-ethanol, processed by the step identical with first time, obtain the material of secondary hydrolysis.After drying at 60 DEG C, material is placed in tube furnace under nitrogen protection and is warming up to 350 DEG C, be incubated 1 ~ 3 h, obtain final material, be designated as graphene@SnO2@C。
Embodiment 5
(1) in graphene oxide (GO) dispersion acetone oxidation-reduction method prepared, obtaining this solvent dispersions of GO, the concentration of GO is 2 mg/ml；
(2) weighing 0.07 g ferrocene ultrasonic dissolution in 5 ml acetone, be subsequently adding the GO dispersion liquid of preparation in 5 ml steps (1), ultrasonic 30 min make dispersed, add 0.35 ml hydrogen peroxide；
(3) mixed liquor obtained in step (2) is transferred in autoclave pressure, is placed in 210 DEG C of baking ovens and reacts 12 h；After naturally cooling to room temperature, by feed liquid taking-up dehydrated alcohol centrifuge washing 3 times；Then reactant is placed in 12 h in 60 DEG C of baking ovens dry；
(4) powder taking 0.5 g drying is placed in tube furnace, heats to 500 DEG C under nitrogen protection, is incubated 2 h, obtain final nano composite material, is designated as graphene@Fe3O4@C；
(5) 0.25 g graphene@Fe is weighed3O4@C joins in the hydrochloric acid solution that 100 ml concentration are 2 M, and at 25 DEG C, stirring reaction 12 h, obtain the porous carbon network of sandwich-like, be designated as taking MCF；
(6) 0.05 g MCF ultrasonic disperse is weighed at the SnCl that concentration is 0.1 g/ml2In the solution of-ethanol, at 25 DEG C, stir 6 h, centrifugation by washing with alcohol once；Being subsequently adding 2 ml ammonia and inspire hydrolysis, keep reaction 30 min, reaction is washed 4 times by centrifugal method after terminating；The material after above-mentioned process is re-dispersed into the SnCl of same concentrations again2In the solution of-ethanol, processed by the step identical with first time, obtain the material of secondary hydrolysis.After drying at 60 DEG C, material is placed in tube furnace under nitrogen protection and is warming up to 350 DEG C, be incubated 1 ~ 3 h, obtain final material, be designated as graphene@SnO2@C。
Material prepared by above-described embodiment, has chemical property similar to Example 1.

Claims (5)

1. a carbon parcel SnO2The preparation method of the nano composite material that nano-particle is supported on graphene film, it is characterised in that concretely comprise the following steps:
(1) graphene oxide oxidation-reduction method prepared disperses in a solvent, obtains graphene oxide dispersion, and the concentration of graphene oxide is 2-10 mg/ml；
(2) 0.02 ~ 0.20 g iron containing compounds, ultrasonic dissolution, in 2 ~ 10 ml solvents, is subsequently adding the graphene oxide dispersion that 2 ~ 10 ml steps (1) are prepared, ultrasonic 15 ~ 60 min, makes dispersed, add 0.1 ~ 1 ml hydrogen peroxide；
(3) mixed liquor that step (2) obtains is transferred in autoclave pressure, is placed in 150 ~ 250 DEG C of baking ovens reaction 2 ~ 36 h；After naturally cooling to room temperature, feed liquid is taken out, with dehydrated alcohol centrifuge washing 3 ~ 10 times；Then reactant is placed in 2 ~ 24 h in 50 ~ 120 DEG C of baking ovens dry；
(4) powder taking 0.1 ~ 1 g drying is placed in tube furnace, heats to 350 ~ 700 DEG C under nitrogen protection, is incubated 1 ~ 6 h, obtains nano composite material, be designated as graphene@Fe3O4@C；
(5) 0.02 ~ 0.5 g graphene@Fe is weighed3O4@C joins in the hydrochloric acid solution that 50 ~ 150 ml concentration are 0.5 ~ 5 M, stirs reaction 2 ~ 12 h, obtain the porous carbon network of sandwich-like, be designated as MCF at 25 ~ 80 DEG C；
(6) 0.02 ~ 0.2 g MCF ultrasonic disperse is weighed at the SnCl that concentration is 0.05 ~ 0.5 g/ml2In the solution of-ethanol, at 25 ~ 60 DEG C, stir 2 ~ 8 h, centrifugation by washing with alcohol once；It is subsequently adding 2 ~ 5 ml ammonia and inspires hydrolysis, keep reaction 20 ~ 120 min, reaction to wash 2 ~ 6 times by centrifugal method after terminating；The material after above-mentioned process is re-dispersed into the SnCl of same concentrations again2In the solution of-ethanol, processed by the step identical with first time, obtain the material of secondary hydrolysis；Again after drying at 40 ~ 100 DEG C, material is placed in tube furnace under nitrogen protection and is warming up to 300 ~ 700 DEG C, be incubated 1 ~ 3 h, obtain final material, be designated as graphene@SnO2@C。
Preparation method the most according to claim 1, it is characterised in that solvent used in step (1), step (2) is the one in acetone, oxolane, DMF, or the most several mixture.
Preparation method the most according to claim 1, it is characterised in that iron containing compounds used in step (2) is the one in iron acetate, ferrocene, carbonyl iron.
4. the carbon bag SnO that a kind is prepared by one of claim 1-3 preparation method2The nano composite material of nano-particle load Graphene.
5. carbon bag SnO as claimed in claim 42The application on electrode material of lithium battery of the nano composite material of nano-particle load Graphene.
CN201610553030.4A 2016-07-14 2016-07-14 Nanocomposite loading carbon-coated SnO2 nano particles on graphene sheets and preparation method of nanocomposite Pending CN106025228A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610553030.4A CN106025228A (en) 2016-07-14 2016-07-14 Nanocomposite loading carbon-coated SnO2 nano particles on graphene sheets and preparation method of nanocomposite

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610553030.4A CN106025228A (en) 2016-07-14 2016-07-14 Nanocomposite loading carbon-coated SnO2 nano particles on graphene sheets and preparation method of nanocomposite

Publications (1)

Publication Number Publication Date
CN106025228A true CN106025228A (en) 2016-10-12

Family

ID=57118624

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610553030.4A Pending CN106025228A (en) 2016-07-14 2016-07-14 Nanocomposite loading carbon-coated SnO2 nano particles on graphene sheets and preparation method of nanocomposite

Country Status (1)

Country Link
CN (1) CN106025228A (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108346789A (en) * 2018-02-05 2018-07-31 东南大学 Multiconductor nucleocapsid cavity structure anode material of lithium-ion battery and preparation method thereof
CN108717974A (en) * 2018-06-07 2018-10-30 深圳市梅莎新能源科技有限公司 A kind of preparation method of lithium ion battery material
CN108722352A (en) * 2018-05-25 2018-11-02 陕西凯蓝环保科技有限公司 A kind of macropore carbon based material and preparation method thereof of absorption environment carbon monoxide
CN108807882A (en) * 2018-05-24 2018-11-13 江西师范大学 A kind of Fe with porous octahedral structure2O3/Fe3O4The preparation method of@C/G composite materials
CN109616626A (en) * 2018-11-15 2019-04-12 上海海事大学 A kind of low temperature magnanimity preparation method that carbon coated ferriferrous oxide is nanocrystalline
CN109755570A (en) * 2017-11-06 2019-05-14 北京碳阳科技有限公司 Three-dimensional combination electrode material and preparation method thereof, electrode and energy storage device
CN111333056A (en) * 2020-02-22 2020-06-26 山西大学 Porous graphene and preparation method under magnetic field environment
US11728486B1 (en) 2022-07-27 2023-08-15 Jing Wang Electrode materials prepared by nanoporous carbon composite technology

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104269536A (en) * 2014-09-25 2015-01-07 天津大学 Graphene-loaded spherical carbon-cladded iron oxide composite material and preparation method of composite material
CN104916828A (en) * 2015-04-16 2015-09-16 中国人民解放军国防科学技术大学 Three dimensional graphene/hollow carbon sphere/sulfur composite material, preparation method thereof, and application in lithium-sulfur batteries
CN105006560A (en) * 2014-12-19 2015-10-28 上海杉杉科技有限公司 Nano-SnO2 graphene composite material for lithium ion battery and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104269536A (en) * 2014-09-25 2015-01-07 天津大学 Graphene-loaded spherical carbon-cladded iron oxide composite material and preparation method of composite material
CN105006560A (en) * 2014-12-19 2015-10-28 上海杉杉科技有限公司 Nano-SnO2 graphene composite material for lithium ion battery and preparation method thereof
CN104916828A (en) * 2015-04-16 2015-09-16 中国人民解放军国防科学技术大学 Three dimensional graphene/hollow carbon sphere/sulfur composite material, preparation method thereof, and application in lithium-sulfur batteries

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
YUCONG JIAO ET AL.: ""Fabrication of three-dimensionally interconnected nanoparticle superlattices and their lithium-ion storage properties"", 《NATURE COMMUNICATIONS》 *
ZEHUI ZHANG ET AL.: ""Synthesis of graphene@ Fe3O4@C core-shell nanosheets for high-performance lithium ion batteries"", 《JOURNAL OF MATERIALS CHEMISTRY A》 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109755570A (en) * 2017-11-06 2019-05-14 北京碳阳科技有限公司 Three-dimensional combination electrode material and preparation method thereof, electrode and energy storage device
CN108346789A (en) * 2018-02-05 2018-07-31 东南大学 Multiconductor nucleocapsid cavity structure anode material of lithium-ion battery and preparation method thereof
CN108807882A (en) * 2018-05-24 2018-11-13 江西师范大学 A kind of Fe with porous octahedral structure2O3/Fe3O4The preparation method of@C/G composite materials
CN108807882B (en) * 2018-05-24 2022-04-26 江西师范大学 Fe with porous octahedral structure2O3/Fe3O4Preparation method of @ C/G composite material
CN108722352A (en) * 2018-05-25 2018-11-02 陕西凯蓝环保科技有限公司 A kind of macropore carbon based material and preparation method thereof of absorption environment carbon monoxide
CN108722352B (en) * 2018-05-25 2020-12-18 陕西凯蓝环保科技有限公司 Macroporous carbon-based material for adsorbing environmental carbon monoxide and preparation method thereof
CN108717974A (en) * 2018-06-07 2018-10-30 深圳市梅莎新能源科技有限公司 A kind of preparation method of lithium ion battery material
CN109616626A (en) * 2018-11-15 2019-04-12 上海海事大学 A kind of low temperature magnanimity preparation method that carbon coated ferriferrous oxide is nanocrystalline
CN109616626B (en) * 2018-11-15 2022-02-15 上海海事大学 Low-temperature macro preparation method of carbon-coated ferroferric oxide nanocrystal
CN111333056A (en) * 2020-02-22 2020-06-26 山西大学 Porous graphene and preparation method under magnetic field environment
US11728486B1 (en) 2022-07-27 2023-08-15 Jing Wang Electrode materials prepared by nanoporous carbon composite technology

Similar Documents

Publication Publication Date Title
CN106025228A (en) Nanocomposite loading carbon-coated SnO2 nano particles on graphene sheets and preparation method of nanocomposite
He et al. N-doped carbon coated LiTi2 (PO4) 3 as superior anode using PANi as carbon and nitrogen bi-sources for aqueous lithium ion battery
Zhang et al. Graphene–encapsulated selenium/polyaniline core–shell nanowires with enhanced electrochemical performance for Li–Se batteries
Ni et al. Nano-Li4Ti5O12 anchored on carbon nanotubes by liquid phase deposition as anode material for high rate lithium-ion batteries
CN102568855B (en) Carbon material-loading manganese dioxide nanowire array composite and method for producing same
Yao et al. Yolk–shell NiS x@ C nanosheets as K-ion battery anodes with high rate capability and ultralong cycle life
KR20170003646A (en) Nitrogen-doped graphene coated nano-sulfur anode composite material, and preparation method and application thereof
CN111180714B (en) Carbon/molybdenum dioxide/silicon/carbon composite material, battery cathode comprising same and lithium ion battery
Wang et al. Structure interlacing and pore engineering of Zn2GeO4 nanofibers for achieving high capacity and rate capability as an anode material of lithium ion batteries
CN105390687A (en) High-performance three-dimensional carbon nanotube composite negative electrode material, preparation method therefor and application thereof
CN108400297B (en) Silicon-based lithium ion battery cathode material and preparation method thereof
CN110838583B (en) Carbon nanotube/M-phase vanadium dioxide composite structure, preparation method thereof and application thereof in water-based zinc ion battery
YongJian et al. A high-quality aqueous graphene conductive slurry applied in anode of lithium-ion batteries
CN106058179A (en) Preparation method of carbon nanotube/silica/carbon composite cathode material
Tian et al. The sandwiched buffer zone enables porous SnO2@ C micro-/nanospheres to toward high-performance lithium-ion battery anodes
CN106058206A (en) Composite material of flower-like carbon-loaded MoS2 nanoparticles and preparation method and application thereof
Su et al. Effects of conductive additives on the percolation networks and rheological properties of LiMn0. 7Fe0. 3PO4 suspensions for lithium slurry battery
Wang et al. Size-dependent capacitive behavior of homogeneous MnO nanoparticles on carbon cloth as electrodes for symmetric solid-state supercapacitors with high performance
CN103078120B (en) Ferrous silicate lithium ion battery cathode material with hierarchical structure and preparation method
CN108123136A (en) Lead carbon battery composite negative pole additive and lead carbon battery cathode and preparation and application
Fan et al. Construction of high performance N-doped carbon coated LiMn0. 8Fe0. 2PO4 nanocrystal cathode for lithium-ion batteries
Zhan et al. Facile approach to prepare FeP2/P/C nanofiber heterostructure via electrospinning as highly performance self-supporting anode for Li/Na ion batteries
Wang et al. A cage compound precursor-derived Sb/Sb 2 O 4/Fe 3 C nanocomposite anchored on reduced graphene oxide as an anode for potassium ion batteries
CN112786869B (en) Preparation method of ferric oxide/spiral carbon nanofiber composite anode material
CN108314010B (en) Flame-method-modified carbon nanotube and preparation method and application thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20161012