CN108183204A - A kind of silicon nanometer sheet-graphene nanometer sheet composite material and preparation and application - Google Patents
A kind of silicon nanometer sheet-graphene nanometer sheet composite material and preparation and application Download PDFInfo
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- CN108183204A CN108183204A CN201711275277.5A CN201711275277A CN108183204A CN 108183204 A CN108183204 A CN 108183204A CN 201711275277 A CN201711275277 A CN 201711275277A CN 108183204 A CN108183204 A CN 108183204A
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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
- H01M4/364—Composites as mixtures
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- 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
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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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
- H01M4/58—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
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- 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 field of lithium ion battery material, disclose a kind of silicon nanometer sheet graphene nanometer sheet composite material and preparation and application.Graphite oxide is prepared using hummer methods, ultrasound stripping forms stannic oxide/graphene nano piece suspension in deionized water by graphite oxide；By Li13Si4Particle is added in ethyl alcohol, and reaction is stirred at room temperature, and silicon particle is obtained by filtration, and is disperseed again in ethanol, and supersound process obtains silicon nanometer sheet suspension；Then stannic oxide/graphene nano piece suspension and silicon nanometer sheet suspension are uniformly mixed, are evaporated, made annealing treatment at a temperature of vacuum condition and 600~1000 DEG C, obtain silicon nanometer sheet graphene nanometer sheet composite material.Gained silicon nanometer sheet graphene nanometer sheet composite material of the invention has big lithium storage content, good cycle, charge and discharge fast, compared with normal charge-discharge velocity, its capacity attenuation is small in the case of fast charging and discharging the advantages of.
Description
Technical field
The invention belongs to field of lithium ion battery material, and in particular to a kind of silicon nanometer sheet-graphene nanometer sheet composite wood
Material and preparation and application.
Background technology
The advantages that lithium ion battery is because of its high-energy density, high power density, long life, is that current application is most wide
General, most promising a kind of energy storage chemical cell.Although commercialization, the energy storage of lithium ion battery are just had begun from nineteen ninety
Performance still cannot meet the needs of people are growing, particularly electrical vehicular power power supply etc. need higher energy density and
On the power battery of power density.Meanwhile as the widely used power supply device of portable electronic device, lithium ion battery also needs
Its performance is continuously improved to meet the performance requirement of continuous improvement and the market demand.Therefore, high performance chargeable lithium is developed
Ion battery is still the important hot spot of current clean energy resource research and its application field, and one of crucial research direction is just
It is the negative material that research and development have more height ratio capacity, faster charge/discharge rates and longer service life cycle.
In known numerous optional negative materials of lithium ion battery, silica-base material has many advantages, such as such as suitable lithiumation
Potential (<0.5V vs.Li+/ Li), natural large storage capacity is of low cost, less toxic and mostly important protrusion theoretical specific capacity
(stable alloy phase Li15Si4Theoretical specific capacity be 3572mAh/g), thus be concerned (Szczech, J.R.et al.,
Energy&Environmental Science 2011,4,56-72).But silicon materials are in battery charge and discharge process due to notable
Volume expansion or contraction easily cause structure destroy with electrical contact fail, cause capacity occur sharp-decay.In this regard, at present for
The modification of the silicium cathode material of high power capacity mainly using nanosizing, compound, surface is modified or the methods of doping forms three-dimensional structure
Clad structure and highly conductive composite material (Su, X.et al., Advanced more stable, with buffering or protection
Energy Materials2014,4,1300882), by improving the overall mechanical properties and electric property of material, to alleviate silicon
Active material during deintercalate lithium ions because of destruction of the additional internal stress to material structure that volume expansion generates, so as to change
It is apt to its electrochemical cycle stability and displacement volume.
Graphene is sp2The six-membered cyclic two-dimensional structure that hydridization carbon is formed, is most graphite type materials (such as zero dimension fowler
Alkene, one-dimensional nano carbon pipe, three-dimensional graphite) basic structural unit.In recent years, grapheme material because with excellent electric conductivity,
The advantages such as mechanical strength, thermal stability are in the fields such as compound energy material and energy device by favor.Wherein, by nano-silicon with
Graphene carries out effectively being compounded with to significantly improve the structural stability and electric conductivity of lithium ion battery silicon cathode material, so as to
Improve the electrochemistry specific capacitance of electrode and cycle life (Luo, J.et al., Journal of Physical Chemistry
Letters 2012,3,1824；Xia,F.et al.,Nano Letters 2015,15,6658).In order to obtain good silicon-
Graphene composite negative pole, the common preparation method reported include chemical vapour deposition technique and mechanical attrition method etc..The former
Be conducive to obtain the compound (Chinese patent CN105304884B) that micro-scale combination is closer, dispersibility is more controllable, realize
Silicon-graphene composite material for haveing excellent performance of storage lithium, but preparation process is relative complex, energy consumption and expensive；Latter process is simple, into
This is low, but simple mechanical spheroidal graphite is generally difficult to the composite wood that obtains polymolecularity, can effectively be combined in the range of nanoscale
Material system, therefore it is unable to give full play out the material advantage of each component.Therefore, be highly desirable to develop it is more convenient and easy,
Process control and effective silicon-graphene nanocomposite material preparation method have been reported and mainly include following several approach：
(1) modification of silicon nanoparticle dispersion liquid and graphene oxide dispersion mating surface is mixed or electrostatic group
Dress approach obtains silicon-graphene composite negative pole.Nano silicon particles and surface are modified by Chinese patent CN103811721B
Graphene solution mixing obtains graphene-silicon composite；Chinese patent CN104916826B modifies silane coupling agent
Silicon nanoparticle suspension mixes the graphene negative material for obtaining embedding silicon particle with graphene oxide suspension.
(2) using organic silicon source or silica as precursor, silicon is formed by processes such as reduction reaction, dispersions
The nanocomposite of grain and graphene.As Chinese patent CN102064322B discloses a kind of nano silicon particles intercalation graphene
Piece composite negative pole material is configured to tetrahydrofuran solution by anhydrous silicon tetrachloride, surfactant, naphthalene sodium and graphite oxide, leads to
It crosses 380-400 DEG C of vacuum processing, filtration washing, drying and is thermally treated resulting in.Chinese patent CN102569756B is disclosed in table
Under conditions of the activating agent of face, silica/graphene composite material is first prepared, silicon/stone is then prepared by magnesiothermic reduction reaction
Black alkene composite negative pole material.Chinese patent CN105098160B is disclosed using ethyl orthosilicate as silicon source, using coaxial quiet
Electrospinning and magnesiothermic reduction are prepared for the hollow porous silico-carbo nanofiber anode material of doped graphene.
(3) with reference to carbon coating technology, the methods of by the dispersion liquid of silicon particle and graphene by spraying or high-temperature heat treatment
Obtain silicon-graphene-carbon compound cathode materials.Chinese patent CN103050666B discloses nano-silicon, graphite microparticles are uniform
It is scattered in the dispersion liquid of graphene oxide, by being spray-dried and being heat-treated under inert protective atmosphere, has obtained one
The composite negative pole material of kind graphene coated silicon-carbon.Chinese patent 105226254B, which is disclosed, inhales nano silicon particles by electrostatic
Attached method is supported on nano graphite flakes on carbon fiber, further carrying out high temperature cabonization by coated high molecular etc. and obtaining Nano graphite
Piece-silico-carbo composite negative pole material.
These above-mentioned silicon-graphene composite negative poles all show considerable lithium storage content and cyclical stability, but
It is substantially based on isotropic nano silicon spheres particle preparation.Research shows that when the size of silicon particle is less than 10nm,
The volume change generated in charge and discharge process can be ignored substantially, and the size of above-mentioned silicon particle is in the feelings for not considering particle agglomeration
It is located at 50~100nm ranges under condition mostly, therefore the cyclical stability of prepared composite material is still far below theory target,
It is greatly limited.
Invention content
In place of above shortcoming and defect of the existing technology, primary and foremost purpose of the invention is that providing a kind of silicon receives
The preparation method of rice piece-graphene nanometer sheet composite material.
Another object of the present invention is to provide a kind of silicon nanometer sheet-graphene nano being prepared by the above method
Piece composite material.
It is still another object of the present invention to provide above-mentioned silicon nanometer sheet-graphene nanometer sheet composite material as lithium-ion electric
The application of pond negative material.
The object of the invention is achieved through the following technical solutions：
A kind of preparation method of silicon nanometer sheet-graphene nanometer sheet composite material, including following preparation process：
(1) graphene oxide suspension is prepared：Graphite oxide is prepared using hummer methods, by graphite oxide in deionized water
Middle ultrasound, which peels off, forms stannic oxide/graphene nano piece suspension；
(2) silicon nanometer sheet suspension is prepared：By silicon lithium alloy (Li13Si4) particle is added in ethyl alcohol, it is stirred at room temperature anti-
Should, silicon particle is obtained by filtration, disperses again in ethanol, supersound process obtains silicon nanometer sheet suspension；
(3) silicon nanometer sheet-graphene nanometer sheet composite material is prepared：Stannic oxide/graphene nano piece obtained by step (1) is hanged
Silicon nanometer sheet suspension obtained by supernatant liquid and step (2) is uniformly mixed, and is evaporated, then in vacuum condition and 600~1000 DEG C
At a temperature of make annealing treatment, obtain silicon nanometer sheet-graphene nanometer sheet composite material.
Preferably, hummer methods described in step (1) prepare graphite oxide and are as follows：In the condition of ice-water bath
Under, graphite is added in the concentrated sulfuric acid and the mixed liquor of concentrated phosphoric acid, is stirred evenly, then adds in potassium permanganate, is warming up to 50 DEG C
It is stirred to react in the mixture that ice water and hydrogen peroxide solution are poured into after for 24 hours, reactant is cooled to room temperature, centrifuges, solid
Product is washed, dry, obtains graphite oxide.The mass ratio of the graphite and potassium permanganate is preferably 1:2；The concentrated sulfuric acid
Addition is (60~120) mL/g graphite；The volume ratio of the ice water and hydrogen peroxide solution is (120~400):(10~30)；
The washing refers to be washed with dilute hydrochloric acid, is then washed with deionized to neutrality；The drying refers to that vacuum is done at 50 DEG C
Dry removing moisture and other volatile matters.
Preferably, the mass concentration of stannic oxide/graphene nano piece suspension described in step (1) is 1.0mg/mL.
Step adds in Li described in (2)13Si4The speed of particle is had to slowly, because of ethyl alcohol and Li13Si4In reaction process
Highly exothermic, control reacting liquid temperature is less than 40 DEG C.Preferably, the time being stirred to react is 90~150min, more preferably
For 120min.
Preferably, the power being ultrasonically treated described in step (2) is 60~100W, more preferably 80W.
Preferably, the mass concentration of silicon nanometer sheet suspension described in step (2) is 0.5mg/mL.
Preferably, the mass ratio that stannic oxide/graphene nano piece is mixed with silicon nanometer sheet described in step (3) is 9:1~1:9,
More preferably 1:1.
Preferably, the temperature made annealing treatment described in step (3) is 700 DEG C.
A kind of silicon nanometer sheet-graphene nanometer sheet composite material, is prepared by the above method.
Above-mentioned silicon nanometer sheet-application of the graphene nanometer sheet composite material as lithium ion battery negative material.
The principle of the present invention is：By Li13Si4Particle is added in ethyl alcohol, Li13Si4Lithium and ethanol synthesis in particle, production
Raw hydrogen obtains the silicon particle after chemical reaction etching, then filters, disperse to be ultrasonically treated in ethanol again, obtain thickness
Unformed silicon nanometer sheet suspension less than 5nm.Silicon nanometer sheet suspension with stannic oxide/graphene nano piece suspension is mixed, is stirred
It mixes uniformly, is then evaporated this mixed liquor to obtain the composite material of silicon nanometer sheet-stannic oxide/graphene nano piece stacked in multi-layers.Finally
It is made annealing treatment by vacuum high-temperature, obtains the composite material (as shown in Figure 1) of silicon nanometer sheet-graphene nanometer sheet stacked in multi-layers.
The deoxidation of surface of graphene oxide oxygen-containing functional group is converted into reproducibility graphene oxide, and unformed during the high temperature anneal
Silicon nanometer sheet is converted into crystal type silicon nanometer sheet, it is even more important that by the high temperature anneal, graphene nano lamella and silicon
What is combined between nanoscale twins will be even closer, and the mechanical stability of composite material is more preferable.In silicon nanometer sheet-graphene nanometer sheet
In composite material, the thickness of silicon nanometer sheet is less than 5nm, according to the literature, in the case that the size of silicon particle is less than 10nm,
Its volume change in charge and discharge process can almost be ignored, and therefore, silicon nanometer sheet is in charge and discharge process in the composite material
Middle volume change is very small.Since silicon nanometer sheet is stacked with graphene nanometer sheet in composite material, the stone of high mechanical strength
Black alkene nanometer sheet can effectively buffer the volume change of silicon nanometer sheet to a certain extent, so as to further mitigate charge and discharge
The unfavorable factor that silicon nanometer sheet is brought due to volume change in journey, silicon nanometer sheet-graphene nanometer sheet composite material has
Excellent cyclical stability.It is worth noting that for pure silicon material or other silicon-grapheme materials, silicon nanometer
The piece conductive network structure more stable with the structure structure easy to implement that graphene nanometer sheet is stacked with, therefore, silicon nanometer sheet-
Graphene nanometer sheet composite material has excellent big multiplying power discharging property.
The present invention preparation method and gained composite material has the following advantages that and advantageous effect：
Gained silicon nanometer sheet-graphene nanometer sheet composite material of the invention has big lithium storage content, good cycle, charge and discharge
It is electric fast, compared with normal charge-discharge velocity, its capacity attenuation is small in the case of quick charge-discharge the advantages of.
Description of the drawings
Fig. 1 is the structure diagram that silicon nanometer sheet-graphene nanometer sheet composite material prepared by the present invention stacks layer by layer.
Fig. 2 is the powder diagram (XRD) of 1 gained silicon nanometer sheet of embodiment-graphene nanometer sheet composite material.
Fig. 3 is the thermogravimetric curve figure of 1 gained silicon nanometer sheet of embodiment-graphene nanometer sheet composite material.
Fig. 4 is 1 gained silicon nanometer sheet of embodiment-graphene nanometer sheet composite material in 0.01~3.0V, 200mA/g electric currents
First charge-discharge curve graph under density.
Fig. 5 is 1 gained silicon nanometer sheet of embodiment/graphene nanometer sheet composite material in 0.01~3.0V, 200mA/g electric currents
Cycle performance curve graph under density.
Fig. 6 is 2 gained silicon nanometer sheet of embodiment-graphene nanometer sheet composite material in 0.01~3.0V, 200mA/g electric currents
Cycle performance curve graph under density.
Fig. 7 is 3 gained silicon nanometer sheet of embodiment-graphene nanometer sheet composite material in 0.01~3.0V, 200mA/g electric currents
Cycle performance curve graph under density.
Fig. 8 be 3 gained silicon nanometer sheet of embodiment-graphene nanometer sheet composite material in 0.01~3.0V, different electric currents are close
Cycle performance curve graph under degree.
Specific embodiment
With reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
Embodiment 1
A kind of preparation method of silicon nanometer sheet-graphene nanometer sheet composite material of the present embodiment, specific preparation process is such as
Under：
(1) 3.0g graphite is added in the 360mL concentrated sulfuric acids and the mixture of 40mL concentrated phosphoric acids, is cooled down in ice-water bath.It is non-
Often slowly 6.0 grams of potassium permanganate are added in the mixture.All caution of operation control speed, carries out very slow.
Then reactant is heated to 50 DEG C, and mechanical agitation is for 24 hours.Reactant is cooled to room temperature and be poured slowly into ice (400mL) with
In the mixture of 30% hydrogen peroxide of 30mL.The solution is centrifuged, and is washed with 500mL 5%HCl, Ran Houyong
It is 7 or so that deionized water, which is washed to pH value, and obtained product is dried in vacuo at 50 DEG C and obtains graphite oxide to remove water.It weighs
Suitable graphite oxide is distributed in deionized water, and ultrasound 30 minutes, the stannic oxide/graphene nano piece for being configured to 1.0mg/mL hangs
Supernatant liquid.
(2) at room temperature, 2.0g Li are added in into 500mL ethyl alcohol13Si4Particle, charging rate is slow, controls solution temperature
Degree after particle is added completely into, is stirred to react 120min, is re-dispersed into after filtering in suitable ethyl alcohol less than 40 DEG C, 80W ultrasounds
Processing 60 minutes is configured to the silicon nanometer sheet suspension of 0.5mg/mL.
(3) by the silicon nanometer of the stannic oxide/graphene nano piece suspension of the 1.0mg/mL of 200mL and the 0.5mg/mL of 400mL
Piece suspension mixes, and stirs evenly, and 50 DEG C are evaporated, and it is compound that the lower 700 DEG C of processing 2h of vacuum obtains silicon nanometer sheet-graphene nanometer sheet
Material.
The powder diagram (XRD) of silicon nanometer sheet-graphene nanometer sheet composite material is as shown in Figure 2 obtained by the present embodiment.
The XRD test results of Fig. 2 show to contain silicon and graphene in composite material simultaneously.(instrument used in XRD analysis is the general analysis in Beijing
All purpose instrument Co., Ltd XD-2 types X-ray diffractometer (XRD), the crystal phase structure of final product prepared by characterization.Test condition
For Cu targets, K α radiation, 36kV, 30mA, 0.02 ° of step width, 10~80 ° of scanning range.Sample is placed in sample stage groove pressure for powder
It is flat, directly detect).
The thermogravimetric curve figure of silicon nanometer sheet-graphene nanometer sheet composite material is as shown in Figure 3 obtained by the present embodiment.Thermogravimetric is surveyed
It takes temperature bright, the content of graphene is about 35wt.% in silicon nanometer sheet-graphene nanometer sheet composite material.
The electrochemical property test of silicon nanometer sheet-graphene nanometer sheet composite material obtained by the present embodiment：
By silicon nanometer sheet-graphene nanometer sheet composite material of preparation and conductive carbon black, binding agent Vingon
(PVDF) in mass ratio 8:1:1 mixing, adds appropriate N-Methyl pyrrolidone (NMP) and stirs evenly, be applied on copper foil,
It is dried at 90 DEG C in vacuum drying oven, silicon nanometer sheet-graphene nanometer sheet composite electrode piece is obtained in sheet-punching machine top shear blade.It will
The electrode obtained is as cathode, and metal lithium sheet is anode, and electrolyte is contains 1M LiPF6/ (EC+DMC) (volume ratios 1:1) it mixes
Zoarium system, diaphragm are microporous polypropylene membrane (Celgard 2400), and 2032 types are assembled into the glove box full of argon gas (Ar)
Button cell.Charge-discharge performance test is carried out with the new Weir Electronics Co., Ltd. BTS51800 battery test systems in Shenzhen.It fills
BTS51800 battery test system of the instrument for new Weir Electronics Co., Ltd. of Shenzhen used in discharge test, model CT-
3008W carries out electro-chemical test in 0.01~3.0V voltage ranges.
Gained silicon nanometer sheet-graphene nanometer sheet composite material is under 0.01~3.0V, 200mA/g current densities after tested
First charge-discharge curve graph and cycle performance curve graph respectively as shown in Figure 4 and Figure 5.It can be seen that the material from Figure 4 and 5
First discharge specific capacity reaches 2746mAh/g under 0.01~3.0V, 200mA/g current densities, by 43 cycle electric discharge ratios
Capacity maintains 1500mAh/g, has preferable electrochemistry cycle performance.
Embodiment 2
A kind of preparation method of silicon nanometer sheet-graphene nanometer sheet composite material of the present embodiment, specific preparation process is such as
Under：
Step (1) and (2) are the same as embodiment 1.
(3) by the silicon nanometer of the stannic oxide/graphene nano piece suspension of the 1.0mg/mL of 400mL and the 0.5mg/mL of 200mL
Piece suspension mixes, and stirs evenly, and 50 DEG C are evaporated, and it is compound that the lower 750 DEG C of processing 2h of vacuum obtains silicon nanometer sheet-graphene nanometer sheet
Material.
Silicon nanometer sheet-graphene nanometer sheet composite material is in 0.01~3.0V, 200mA/g current densities obtained by the present embodiment
Under cycle performance curve graph it is as shown in Figure 6.As can be seen from Figure 6 the material is in 0.01~3.0V, 200mA/g current densities
Under first discharge specific capacity reach 1673.5mAh/g, by 50 times cycle after specific discharge capacity maintain 816mAh/g, show
The material has preferable cyclical stability.
Embodiment 3
A kind of preparation method of silicon nanometer sheet-graphene nanometer sheet composite material of the present embodiment, specific preparation process is such as
Under：
Step (1) and (2) are the same as embodiment 1.
(3) by the silicon nanometer of the stannic oxide/graphene nano piece suspension of the 1.0mg/mL of 200mL and the 0.5mg/mL of 200mL
Piece suspension mixes, and stirs evenly, and 50 DEG C are evaporated, and it is compound that the lower 750 DEG C of processing 2h of vacuum obtains silicon nanometer sheet-graphene nanometer sheet
Material.
Silicon nanometer sheet-graphene nanometer sheet composite material is in 0.01~3.0V, 200mA/g current densities obtained by the present embodiment
Under cycle performance curve graph it is as shown in Figure 7.As can be seen from Figure 7 the material is in 0.01~3.0V, 200mA/g current densities
Under first discharge specific capacity reach 1673.5mAh/g, by 50 times cycle after specific discharge capacity maintain 816mAh/g, show
The material has preferable cyclical stability.Its cycle performance curve graph such as Fig. 8 under 0.01~3.0V, different current densities
It is shown.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of silicon nanometer sheet-graphene nanometer sheet composite material, it is characterised in that including following preparation process：
(1) graphene oxide suspension is prepared：Graphite oxide is prepared using hummer methods, graphite oxide is surpassed in deionized water
Sound peels off to form stannic oxide/graphene nano piece suspension；
(2) silicon nanometer sheet suspension is prepared：By Li13Si4Particle is added in ethyl alcohol, and reaction is stirred at room temperature, silicon is obtained by filtration
Grain disperses in ethanol again, and supersound process obtains silicon nanometer sheet suspension；
(3) silicon nanometer sheet-graphene nanometer sheet composite material is prepared：By stannic oxide/graphene nano piece suspension obtained by step (1)
It is uniformly mixed, is evaporated, then in vacuum condition and 600~1000 DEG C of temperature with step (2) gained silicon nanometer sheet suspension
Lower annealing obtains silicon nanometer sheet-graphene nanometer sheet composite material.
2. a kind of preparation method of silicon nanometer sheet-graphene nanometer sheet composite material according to claim 1, feature exist
The hummer methods described in step (1) prepare graphite oxide and are as follows：Under conditions of ice-water bath, graphite is added in
It into the concentrated sulfuric acid and the mixed liquor of concentrated phosphoric acid, stirs evenly, then adds in potassium permanganate, be warming up to 50 DEG C and be stirred to react for 24 hours, it will
Reactant is poured into after being cooled to room temperature in the mixture of ice water and hydrogen peroxide solution, is centrifuged, and solid product is washed, dry
It is dry, obtain graphite oxide.
3. a kind of preparation method of silicon nanometer sheet-graphene nanometer sheet composite material according to claim 2, feature exist
In：The mass ratio of the graphite and potassium permanganate is 1:2；The addition of the concentrated sulfuric acid is (60~120) mL/g graphite；It is described
The volume ratio of ice water and hydrogen peroxide solution is (120~400):(10~30)；The washing refers to be washed with dilute hydrochloric acid, Ran Houyong
Deionized water is washed to neutrality；The drying refers to that vacuum drying removes moisture and other volatile matters at 50 DEG C.
4. a kind of preparation method of silicon nanometer sheet-graphene nanometer sheet composite material according to claim 1, feature exist
In：The mass concentration of stannic oxide/graphene nano piece suspension described in step (1) is 1.0mg/mL.
5. a kind of preparation method of silicon nanometer sheet-graphene nanometer sheet composite material according to claim 1, feature exist
In：Step adds in Li described in (2)13Si4Reacting liquid temperature is controlled to be less than 40 DEG C during particle；The time being stirred to react is 90
~150min；The power of the supersound process is 60~100W.
6. a kind of preparation method of silicon nanometer sheet-graphene nanometer sheet composite material according to claim 1, feature exist
In：The mass concentration of silicon nanometer sheet suspension described in step (2) is 0.5mg/mL.
7. a kind of preparation method of silicon nanometer sheet-graphene nanometer sheet composite material according to claim 1, feature exist
In：The mass ratio that stannic oxide/graphene nano piece is mixed with silicon nanometer sheet described in step (3) is 9:1~1:9.
8. a kind of preparation method of silicon nanometer sheet-graphene nanometer sheet composite material according to claim 1, feature exist
In：The temperature made annealing treatment described in step (3) is 700 DEG C.
9. a kind of silicon nanometer sheet-graphene nanometer sheet composite material, it is characterised in that：By described in any one of claim 1~8
Method be prepared.
10. a kind of silicon nanometer sheet-graphene nanometer sheet composite material described in claim 9 is as lithium ion battery negative material
Application.
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| CN113363442A (en) * | 2021-06-09 | 2021-09-07 | 孙仲振 | Silicon-carbon composite negative electrode material of lithium ion battery and preparation method thereof |
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| CN109378457A (en) * | 2018-10-16 | 2019-02-22 | 周昊宸 | A kind of high compacted density porous silicon chip/carbon compound cathode materials and preparation method |
| CN109742363A (en) * | 2019-01-08 | 2019-05-10 | 圣盟（廊坊）新材料研究院有限公司 | One kind may be implemented graphene and closely coats SiO negative materials and preparation method thereof |
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| CN112289983A (en) * | 2020-09-18 | 2021-01-29 | 合肥国轩高科动力能源有限公司 | SiO (silicon dioxide)x-MWCNTs/C core-shell composite anode material and preparation method and application thereof |
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| CN113363442B (en) * | 2021-06-09 | 2022-05-20 | 孙仲振 | Silicon-carbon composite negative electrode material of lithium ion battery and preparation method thereof |
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Application publication date: 20180619 |