CN106099061B - A kind of porous graphene/silicon composite, preparation method and lithium ion battery - Google Patents

A kind of porous graphene/silicon composite, preparation method and lithium ion battery Download PDF

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CN106099061B
CN106099061B CN201610561612.7A CN201610561612A CN106099061B CN 106099061 B CN106099061 B CN 106099061B CN 201610561612 A CN201610561612 A CN 201610561612A CN 106099061 B CN106099061 B CN 106099061B
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graphene
silicon
silicon composite
capacity
aqueous solution
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CN106099061A (en
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张可利
傅儒生
夏永高
刘兆平
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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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
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention provides a kind of preparation methods of porous graphene/silicon composite, graphene/silicon plural gel is made in hydro-thermal process first, then the aperture inside drying and processing regulation and control graphene/silicon plural gel, it is last freeze-dried, porous graphene/silicon composite is made in heat treatment, this method can also enhance the bond strength between silicon and graphene sheet layer while regulating and controlling graphene/silicon composite material aperture, it prevents peeling-off between silicon and graphene in charge and discharge process, it ensure that porous graphene/silicon composite obtained has higher reversible capacity, preferable cycle performance and high rate performance.Experiment shows lithium ion battery produced by the present invention under 0.5C multiplying powers, and first discharge specific capacity is 1325~1785mAh/g, and after recycling 200 times, specific discharge capacity is 940~1600mAh/g.

Description

A kind of porous graphene/silicon composite, preparation method and lithium ion battery
Technical field
The present invention relates to technical field of lithium ion more particularly to a kind of porous graphene/silicon composite, its preparations Method and lithium ion battery.
Background technology
Lithium ion battery is high with operating voltage, higher than energy, operating temperature range is wide, electric discharge is steady, small, quality Gently, memory-less effect and it is environmentally friendly the advantages that, therefore in portable electronic device, electric vehicle, space technology, national defence work The fields such as industry illustrate wide application prospect.
With mobile electronic equipment to high power capacity, long-life batteries demand it is growing, people are to lithium ion battery Performance more stringent requirements are proposed, and negative material is as improving lithium ion battery energy and an important factor for cycle life, Extensive research is worldwide obtained.
In the early 1990s, Sony Corporation of Japan takes the lead in developing carbon negative pole material, lithium ion battery is significantly improved Security performance and charge and discharge circulation life.However, the theoretical specific capacity of carbon negative pole material only has 372mAh/g, energy density The present requirement of various electronic equipment for consumption, especially energy storage device and electric vehicle to energy density is cannot be satisfied, therefore There is an urgent need to find a kind of negative material for the high-energy density that can replace carbon material.
Wherein, silicon based anode material with its huge lithium storage content (4200mAh/g), slightly above carbon material discharge platform And the advantages that rich reserves in the earth's crust and be concerned.However in charge and discharge process, the removal lithium embedded of silicon is reacted companion With 310% volume change, easily causes the cracking of electrode and falling off for active material, be formed simultaneously unstable solid electrolytic Matter interfacial film (SEI films), so as to cause the deterioration of electrode cycle performance and high rate performance.In addition, lower silicon materials electronics electricity Conductance and lithium ion mobility rate have also seriously affected the chemical property of silicium cathode material.
One of solution to the problems described above is synthesis of silica-base compound, with the volume expansion of buffer electrode, improves electrode Cyclical stability.Carbon material is with its excellent electric conductivity and mechanical performance and as the most commonly used material of selection.By carbon materials Material and silicon synthetic composite material not only effectively buffer volumes can expand, prevent nano silicon particles from assembling, can also improve electrode Electric conductivity obtains stable SEI films, to greatly improve the cycle performance and coulombic efficiency of silicium cathode.Wherein, graphene is with it The advantages that excellent flexible, good electron conduction, smaller density and embedding lithium ability appropriate and become silicon-carbon cathode material The optimum activity matrix of material.
Chinese patent CN201010256875.X mixes the graphene oxide of different proportion with nano silica fume, ultrasound point It dissipates, finally the graphene/silicon composite film material of self supporting structure is prepared at the mode of cake/film for suction filtration or convection drying. Although silicon particle can be dispersed in the graphene of sheet, there is certain cushioning effect to silicon volume expansion.But silicon with The bond strength of graphene is not high, and clearance space is smaller, and structure separation is easy to happen in silicon volume expansion contraction process, it is difficult to Obtain preferable cycle performance.
Invention content
In view of this, the technical problem to be solved in the present invention is to provide a kind of porous graphene/silicon composite, its system Preparation Method and lithium ion battery, porous graphene/silicon composite made from this preparation method have preferable cyclicity Energy.
The present invention provides a kind of preparation methods of porous graphene/silicon composite, include the following steps：
A1) aqueous solution of graphene oxide, nano silica fume, deionized water, surfactant and organic solvent are mixed, obtained To mixed solution；
B the mixed solution) is subjected to hydro-thermal reaction, obtains graphene/silicon plural gel；
C1) the graphene/silicon plural gel at normal pressure, 30 DEG C~90 DEG C is dried to 0.5~7h, then freezed Drying is thermally treated resulting in porous graphene/silicon composite；
Or
A2) aqueous solution of graphene oxide, nano silica fume, deionized water and surfactant are mixed, obtain mixing molten Liquid；
B the mixed solution) is subjected to hydro-thermal reaction, obtains graphene/silicon plural gel；
C2) by the graphene/silicon plural gel under 0.5~5 atmospheric pressure, 30 DEG C~90 DEG C 0.5~7h of drying, so After be freeze-dried, be heat-treated, obtain porous graphene/silicon composite.
Preferably, the mass concentration of the aqueous solution of the graphene oxide is 0.5mg/mL~7mg/mL.
Preferably, the mass ratio of the nano silica fume and graphene oxide is 1：6~5：1, the nano silica fume and surface The mass ratio of activating agent is 1：10~10：1, the volume ratio of the deionized water and organic solvent is 1：6~6：1, it is described organic The volume ratio of the aqueous solution of solvent and graphene oxide is 1：6~6：1.
Preferably, the one kind of the organic solvent in ethyl alcohol, ethylene glycol or glycerine.
Preferably, step A2) in, the nano silica fume is 1 with graphene oxide mass ratio：6~5：1, the nano-silicon The mass ratio of powder and surfactant is 1：10~10：1, the volume ratio of the aqueous solution of the deionized water and graphene oxide is 1：6~6：1.
Preferably, the temperature of the hydro-thermal reaction is 100 DEG C~200 DEG C, and the time of the hydro-thermal reaction is 2h~15h.
Preferably, step C2) in, by the graphene/silicon plural gel in 0.7~0.9 atmospheric pressure or 1.5~3 Under atmospheric pressure, then 30 DEG C~90 DEG C 0.5~7h of drying are freeze-dried, are heat-treated, it is compound to obtain porous graphene/silicon Material.
Preferably, the temperature of the heat treatment is 300 DEG C~1000 DEG C, and the time of the heat treatment is 1h~8h.
The present invention provides a kind of porous graphene/silicon composites prepared by above-mentioned preparation method.
The present invention also provides a kind of lithium ion battery, including anode, cathode, diaphragm and electrolyte, the cathode includes Porous graphene/silicon composite described above.
The present invention provides a kind of preparation methods of porous graphene/silicon composite, include the following steps：
A1) aqueous solution of graphene oxide, nano silica fume, deionized water, surfactant and organic solvent are mixed, obtained To mixed solution；B the mixed solution) is subjected to hydro-thermal reaction, obtains graphene/silicon plural gel；C1) by the graphite Alkene/silicon plural gel dries 0.5~7h at normal pressure, 30 DEG C~90 DEG C, is then freeze-dried, is thermally treated resulting in porous stone Black alkene/silicon composite；
Or
A2) aqueous solution of graphene oxide, nano silica fume, deionized water and surfactant are mixed, obtain mixing molten Liquid；B the mixed solution) is subjected to hydro-thermal reaction, obtains graphene/silicon plural gel；C2) that the graphene/silicon is compound Under 0.5~5 atmospheric pressure, then 30 DEG C~90 DEG C 0.5~7h of drying are freeze-dried, are heat-treated, obtained porous gel Graphene/silicon composite material.
The present invention is when preparing graphene/silicon plural gel, by adding organic solvent in the feed, then under normal pressure Carry out the drying and processing of specific temperature；Either by the air pressure for controlling drying and temperature, to control graphene/silicon plural gel Contraction rate be then freeze-dried again to obtain the adjustable graphene/silicon composite gel material of porosity and aperture Processing, makes the Structured cured of graphene/silicon plural gel.Porous graphene/silicon composite the hole prepared by the above method Diameter is controllable, and the bond strength of silicon and graphene is higher, and the composite material of porous structure possesses a large amount of gaps, can effectively accommodate silicon Volume expansion, without the volume change for causing composite material larger, while relatively stable SEI films can also be obtained.In addition, hole The presence in road can increase the reaction rate of removal lithium embedded, be conducive to the cycle performance and high rate performance that improve composite material, in turn It ensure that porous graphene/silicon composite obtained has preferable cycle performance and high rate performance.Experiment shows the present invention For lithium ion battery obtained under 0.5C multiplying powers, first discharge specific capacity is 1325~1785mAh/g, after recycling 200 times, electric discharge Specific capacity is 940~1600mAh/g, and capacity retention ratio is not less than 71%.
Description of the drawings
Fig. 1 is the SEM figures of porous graphene/silicon composite prepared by the embodiment of the present invention 1；
Fig. 2 is the SEM figures after porous graphene/silicon composite prepared by the embodiment of the present invention 1 is ground；
Fig. 3 is the cyclic curve figure of lithium ion battery prepared by the embodiment of the present invention 1~3；
Fig. 4 is specific discharge capacity curve graph of the lithium ion battery of the preparation of the embodiment of the present invention 1~3 under different multiplying；
Fig. 5 is the SEM figures of porous graphene/silicon composite prepared by the embodiment of the present invention 2；
Fig. 6 is the SEM figures after porous graphene/silicon composite prepared by the embodiment of the present invention 2 is ground；
Fig. 7 is the SEM figures of porous graphene/silicon composite prepared by the embodiment of the present invention 3；
Fig. 8 is the SEM figures after porous graphene/silicon composite prepared by the embodiment of the present invention 3 is ground；
Fig. 9 is the cyclic curve figure of lithium ion battery prepared by the embodiment of the present invention 9~11；
Figure 10 is specific discharge capacity curve of the lithium ion battery of the preparation of the embodiment of the present invention 9~11 under different multiplying Figure.
Specific implementation mode
Below in conjunction with the embodiment of the present invention, technical scheme of the present invention is clearly and completely described, it is clear that institute The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, Every other embodiment obtained by those of ordinary skill in the art without making creative efforts, belongs to this hair The range of bright protection.
The present invention provides a kind of preparation methods of porous graphene/silicon composite, include the following steps：
A1) aqueous solution of graphene oxide, nano silica fume, deionized water, surfactant and organic solvent are mixed, obtained To mixed solution；
B the mixed solution) is subjected to hydro-thermal reaction, obtains graphene/silicon plural gel；
C1) the graphene/silicon plural gel at normal pressure, 30 DEG C~90 DEG C is dried to 0.5~7h, then freezed Drying is thermally treated resulting in porous graphene/silicon composite；
Or
A2) aqueous solution of graphene oxide, nano silica fume, deionized water and surfactant are mixed, obtain mixing molten Liquid；
B the mixed solution) is subjected to hydro-thermal reaction, obtains graphene/silicon plural gel；
C2) by the graphene/silicon plural gel under 0.5~5 atmospheric pressure, 30 DEG C~90 DEG C 0.5~7h of drying, so After be freeze-dried, be heat-treated, obtain porous graphene/silicon composite.
The preparation method of porous graphene/silicon composite provided by the invention includes two schemes, by the feed Add organic solvent and graphene/silicon plural gel be made, then within specified temperatures by the graphene/silicon plural gel into Row drying；Either by the air pressure for adjusting drying and temperature, to control the contraction rate of graphene/silicon plural gel, in turn Regulate and control the aperture of plural gel and the thickness of graphene sheet layer, improves the conjugation of silicon and graphene.Finally, dry by freezing Graphene/silicon composite material that is dry and being thermally treated resulting in porous structure, this composite structure are stablized, mechanical performance and conduction Function admirable is applied to have preferable cycle performance and high rate performance in lithium ion battery.
The first above-mentioned scheme includes the following steps：
A1) aqueous solution of graphene oxide, nano silica fume, deionized water, surfactant and organic solvent are mixed, obtained To mixed solution；
B the mixed solution) is subjected to hydro-thermal reaction, obtains graphene/silicon plural gel；
C1) the graphene/silicon plural gel at normal pressure, 30 DEG C~90 DEG C is dried to 0.5~7h, then freezed Drying is thermally treated resulting in porous graphene/silicon composite.
In the present invention, the graphene oxide is preferably prepared according to Hummers methods.After obtaining graphene oxide, this hair The bright aqueous solution for being prepared to obtain graphene oxide.The present invention does not have the preparation method of the aqueous solution of the graphene oxide Special limitation, using the preparation method of aqueous solution well known to those skilled in the art.In the present invention, the oxidation stone The mass concentration of the aqueous solution of black alkene is preferably 0.5mg/mL~7mg/mL, more preferably 1mg/mL~6mg/mL.
After obtaining the aqueous solution of graphene oxide, the present invention by the aqueous solution of the graphene oxide and nano silica fume, go Ionized water, surfactant and organic solvent mixing, obtain mixed solution.
In the present invention, the surfactant is preferably nonionic surface active agent, more preferably polyvinyl pyrrole One kind in alkanone (PVP), polydiallyldimethyl ammonium chloride (PDDA) and kayexalate (PSS).The organic solvent Preferably ethyl alcohol, ethylene glycol or glycerine.The present invention, as organic solvent, is dried within specified temperatures using ethyl alcohol When, graphene/silicon plural gel contraction rate is very fast.The present invention uses ethylene glycol or glycerine as organic solvent, specific At a temperature of when being dried, graphene/silicon plural gel contraction rate is slower, be more prone to control the aperture of plural gel with And the thickness of graphene sheet layer.
The mass ratio of the nano silica fume and graphene oxide is 1：6~5：1, preferably 1：5~3：1, more preferably 1： 1；The mass ratio of the nano silica fume and surfactant is 1：10~10：1, preferably 1：5~5：1, more preferably 2：1；Institute The volume ratio for stating deionized water and organic solvent is 1：6~6：1, preferably 1：5~5：1, more preferably 1：1；It is described organic molten The volume ratio of the aqueous solution of agent and graphene oxide is 1：6~6：1, preferably 1：5~5：1, more preferably 1：1.
The present invention has no the source of used raw material components special limitation, can be general commercially available.
After obtaining mixed solution, the mixed solution is carried out hydro-thermal reaction by the present invention, and it is compound solidifying to obtain graphene/silicon Glue.In the present invention, the temperature of the hydro-thermal reaction is preferably 100 DEG C~200 DEG C；The time of the hydro-thermal reaction is preferably 2h ~15h.
Obtained graphene/silicon plural gel is dried 0.5~7h by the present invention at normal pressure, 30 DEG C~90 DEG C, is dried Composite material after dry.The time of the drying is unsuitable long, because drying time is long, graphene can be caused to reunite serious, To lose spacial framework.The present invention has no the mode of the drying special limitation, using those skilled in the art Well known drying mode.
Specifically, when organic solvent selected in raw material is ethyl alcohol, preferably drying temperature is 30 DEG C~70 DEG C, drying Time is 0.5~5h, and preferred drying temperature is 50 DEG C~60 DEG C, and drying time is 2~3.5h.When selected in raw material When organic solvent is ethylene glycol or glycerine, preferably drying temperature is 40 DEG C~90 DEG C, and drying time is 1~7h, more preferably Drying temperature is 60 DEG C~70 DEG C, and drying time is 3~6h.
Composite material after above-mentioned drying is freeze-dried, the Structured cured of graphene/silicon plural gel is made.It is described The temperature of freeze-drying is preferably -70 DEG C~-10 DEG C, and the time of the freeze-drying is preferably 1h~60h.
Composite material after freeze-drying is heat-treated, porous graphene/silicon composite is obtained, preferably in inertia It is heat-treated under atmosphere.The present invention has no the mode of the heat treatment special limitation, ripe using those skilled in the art The heat treatment mode known, present invention preferably employs annealings.The temperature of the heat treatment is preferably 300 DEG C~1000 DEG C, the time of the heat treatment is preferably 1h~8h.It is special that the present invention has no inert gas used by acquisition inert atmosphere Limitation, may be used inert gas well known to those skilled in the art.Present invention preferably employs argon gas.
Above-mentioned second scheme includes the following steps：
A2) aqueous solution of graphene oxide, nano silica fume, deionized water and surfactant are mixed, obtain mixing molten Liquid；
B the mixed solution) is subjected to hydro-thermal reaction, obtains graphene/silicon plural gel；
C2) by the graphene/silicon plural gel under 0.5~5 atmospheric pressure, 30 DEG C~90 DEG C 0.5~7h of drying, so After be freeze-dried, be heat-treated, obtain porous graphene/silicon composite.
In the present invention, the graphene oxide is preferably prepared according to Hummers methods.After obtaining graphene oxide, this hair The bright aqueous solution for being prepared to obtain graphene oxide.The present invention does not have the preparation method of the aqueous solution of the graphene oxide Special limitation, using the preparation method of aqueous solution well known to those skilled in the art.In the present invention, the oxidation stone The mass concentration of the aqueous solution of black alkene is preferably 0.5mg/mL~7mg/mL, more preferably 1mg/mL~6mg/mL.
After obtaining the aqueous solution of graphene oxide, the present invention by the aqueous solution of the graphene oxide and nano silica fume, go Ionized water and surfactant mixing, obtain mixed solution.
In the present invention, the surfactant is preferably nonionic surface active agent, preferably polyvinylpyrrolidine Ketone (PVP), polydiallyldimethyl ammonium chloride (PDDA), kayexalate (PSS).
The nano silica fume is 1 with graphene oxide mass ratio：6~5：1, preferably 1：5~3：1, more preferably 1：1； The mass ratio of the nano silica fume and surfactant is 1：10~10：1, preferably 1：5~5：1, more preferably 2: 1；It is described The volume ratio of the aqueous solution of deionized water and graphene oxide is 1：6~6：1, preferably 1：5~5：1, more preferably 1: 1.
The present invention has no the source of used raw material components special limitation, can be general commercially available.
After obtaining mixed solution, the mixed solution is carried out hydro-thermal reaction by the present invention, and it is compound solidifying to obtain graphene/silicon Glue.In the present invention, the temperature of the hydro-thermal reaction is preferably 100 DEG C~200 DEG C；The time of the hydro-thermal reaction is preferably 2h ~15h.
The present invention is by obtained graphene/silicon plural gel less than 1 atmospheric pressure or small more than 1 more than or equal to 0.5 It is dried under equal to 5 atmospheric pressure, the composite material after being dried.The present invention has no the mode of drying special limit System, using drying mode well known to those skilled in the art.The temperature of the drying is 30 DEG C~90 DEG C, the drying Time is 0.5h~7h.
Specifically, the present invention dries obtained graphene/silicon plural gel in the case where being less than 1 atmospheric pressure more than or equal to 0.5 It is dry, it is preferably dried under 0.7~0.9 atmospheric pressure, graphene/silicon plural gel contraction rate is very fast, preferably drying temperature Degree is 30 DEG C~70 DEG C, and drying time is 0.5~5h；Preferred drying temperature is 50 DEG C~60 DEG C, drying time is 2~ 3.5h.The present invention is dried in the case where being less than or equal to 5 atmospheric pressure more than 1, is preferably dried under 1.5~3 atmospheric pressure, Graphene/silicon plural gel contraction rate is slower, is more prone to control the aperture of plural gel and the thickness of graphene sheet layer, It is preferred that drying temperature is 40 DEG C~90 DEG C, drying time is 1~7h；Preferred drying temperature is 60 DEG C~70 DEG C, when drying Between be 3~6h.
The present invention is by adjusting the air pressure dried and temperature, to control graphene/silicon plural gel contraction rate, to adjust The aperture of plural gel and the thickness of graphene sheet layer are controlled, the conjugation of silicon and graphene is improved.
Composite material after above-mentioned drying is freeze-dried, the Structured cured of graphene/silicon plural gel is made.It is described The temperature of freeze-drying is preferably -70 DEG C~-10 DEG C, and the time of the freeze-drying is preferably 1h~60h.
Composite material after freeze-drying is heat-treated, porous graphene/silicon composite is obtained, preferably in inertia It is heat-treated under atmosphere.The present invention has no the mode of the heat treatment special limitation, ripe using those skilled in the art The heat treatment mode known, present invention preferably employs annealings.The temperature of the heat treatment is preferably 300 DEG C~1000 DEG C, the time of the heat treatment is preferably 1h~8h.It is special that the present invention has no inert gas used by acquisition inert atmosphere Limitation, may be used inert gas well known to those skilled in the art.Present invention preferably employs argon gas.
The present invention provides a kind of porous graphene/silicon composites prepared by above-mentioned preparation method.It is provided by the invention Porous graphene/silicon composite includes silicon nanoparticle and graphene, and the silicon nanoparticle is embedded in the graphene Between lamella, the composite material of porous structure is formed.The grain size of the silicon nanoparticle is preferably 100nm~120nm.The present invention Special limitation is had no to the source of the nano-silicon, can make by oneself or commercially, meets nano-scale.This hair The bright nano silica fume for preferably using Aladdin Reagent Company.
The conjugation of porous graphene/silicon composite provided by the invention, silicon nanoparticle and graphene is higher, and During the sizing mixing of later stage, the aperture of graphene is not easy to be destroyed, and ensure that the cycle of lithium ion battery negative material obtained Performance, so that lithium ion battery has preferable cycle performance.
The present invention also provides a kind of lithium ion battery, including anode, cathode, diaphragm and electrolyte, the cathode includes Porous graphene/silicon composite described above.
The present invention does not have special limitation to the type of the anode, diaphragm and electrolyte, and e.g., lithium can be used in the anode Piece；Microporous polypropylene membrane can be used in the diaphragm；Ethylene carbonate (EC) and dimethyl carbonate (DMC) can be used in the electrolyte Mixed liquor.Specifically, the present invention is by above-mentioned porous graphene/silicon composite and binder (butadiene-styrene rubber (SBR): carboxylic first Base sodium cellulosate (CMC)=3: 7 mass ratio), conductive agent Super P according to 80: 10: 10 weight ratio mix, be added suitable quantity of water It is tuned into slurry as dispersant, is then coated uniformly in copper foil current collector, and vacuum dried, roll-in, is prepared into negative plate； It is to electrode, the LiPF of 1mol/L with lithium metal6Mixed solvent (EC: DMC=1: 1 volume ratio) be electrolyte, polypropylene is micro- Pore membrane (Celgard 2400) is diaphragm, and simulated battery is assembled into the glove box of argon gas protection.
The present invention carries out constant current charge-discharge experiment to obtained simulated battery, tests the cyclicity of the lithium ion battery Can, charging/discharging voltage is limited in 0.001~1.5 volt, and the current density of charge and discharge is 500mA/g.It is tested using Land testers The chemical property of battery, test condition are room temperature.The experimental results showed that lithium ion battery produced by the present invention is in 0.5C multiplying powers Under, first discharge specific capacity is 1325~1785mAh/g, and after recycling 200 times, specific discharge capacity is 940~1600mAh/g, is held It measures conservation rate and is not less than 71%, there is preferable cycle performance.
Meanwhile cycle performance of the present invention also to obtained lithium ion battery under different multiplying is investigated, and is tested The result shows that lithium ion battery provided by the invention all has higher specific capacity at 0.1C, 0.2C, 0.5C, 1C and 2C, times Rate better performances.
The present invention provides a kind of preparation methods of porous graphene/silicon composite, include the following steps：
A1) aqueous solution of graphene oxide, nano silica fume, deionized water, surfactant and organic solvent are mixed, obtained To mixed solution；
B the mixed solution) is subjected to hydro-thermal reaction, obtains graphene/silicon plural gel；
C1) the graphene/silicon plural gel at normal pressure, 30 DEG C~90 DEG C is dried to 0.5~7h, then freezed Drying is thermally treated resulting in porous graphene/silicon composite；
Or
A2) aqueous solution of graphene oxide, nano silica fume, deionized water and surfactant are mixed, obtain mixing molten Liquid；
B the mixed solution) is subjected to hydro-thermal reaction, obtains graphene/silicon plural gel；
C2) by the graphene/silicon plural gel under 0.5~5 atmospheric pressure, 30 DEG C~90 DEG C 0.5~7h of drying, so After be freeze-dried, be heat-treated, obtain porous graphene/silicon composite.
Graphene/silicon plural gel is made by adding alcohols solvent in the feed in the present invention, then in specific temperature The graphene/silicon plural gel is dried under normal pressure；Either by the air pressure for adjusting drying and temperature, stone is controlled Black alkene/silicon plural gel contraction rate obtains the adjustable plural gel in aperture, and postmenstruation is freeze-dried and is thermally treated resulting in porous Graphene/silicon composite material.The composite structure is stablized, and mechanical performance and electric conductivity are excellent, the combination of graphene and silicon Intensity is higher, and being applied to lithium ion battery has preferable cycle performance and high rate performance.The experimental results showed that the present invention is made Lithium ion battery under 0.5C multiplying powers, first discharge specific capacity be 1325~1785mAh/g, cycle 200 times after, discharge specific volume Amount is 940~1600mAh/g, and capacity retention ratio is not less than 71%, has preferable cycle performance.
In order to further illustrate the present invention, multiple to a kind of porous graphene/silicon provided by the invention with reference to embodiments Condensation material, preparation method and lithium ion battery are described in detail, but cannot be understood as to the scope of the present invention It limits.
Embodiment 1
By the aqueous solution of graphene oxide and nano silica fume, deionized water, polyvinylpyrrolidone and ethylene glycol (or the third three Alcohol) mixing, obtain mixed solution.Wherein, the mass concentration of the aqueous solution of graphene oxide be 6mg/mL, the nano silica fume with The mass ratio of graphene oxide is 1: 1, and the mass ratio of nano silica fume and polyvinylpyrrolidone is 2: 1, deionized water and second two The volume ratio of alcohol (or glycerine) is 1: 1, and the volume ratio of ethylene glycol (or glycerine) and the aqueous solution of graphene oxide is 1: 1；
Mixed solution is placed in reaction kettle, 180 DEG C of hydro-thermal reaction 12h obtain graphene/silicon plural gel；
By graphene/silicon plural gel in normal pressure, 60 DEG C of drying and processing 5h, then in (- 60) DEG C freeze-drying process 48h finally under an inert atmosphere, 800 DEG C of high annealing 4h, obtains porous graphene/silicon composite.
Obtained porous graphene/silicon composite is scanned electron-microscope scanning analysis by the present invention, as a result such as Fig. 1 and 2 It is shown.Fig. 1 is the SEM figures of porous graphene/silicon composite prepared by the embodiment of the present invention 1, as seen from Figure 1, this hair Porous graphene/silicon composite of bright offer is porous structure.Fig. 2 is that the porous graphene/silicon of the invention obtained is compound Sample SEM after material is ground schemes, and as seen from Figure 2, porous graphene/silicon composite after grinding is more Pore structure.
The present invention is by above-mentioned porous graphene/silicon composite and binder (SBR: CMC=3: 7 mass ratio), conductive agent Super P are mixed according to 80: 10: 10 weight ratio, and suitable quantity of water is added and is tuned into slurry as dispersant, is then coated uniformly on copper On foil collector, and vacuum dried, roll-in, it is prepared into negative plate；It is to electrode, the LiPF of 1mol/L with lithium metal6It is mixed Bonding solvent (EC: DMC=1: 1 volume ratio) is electrolyte, and microporous polypropylene membrane (Celgard 2400) is diaphragm, is protected in argon gas Glove box in be assembled into simulated battery.By the simulated battery being assembled into Land testers (Wuhan Xin Nuo Electronics Co., Ltd.s) Upper carry out constant current charge-discharge test, charging/discharging voltage section are 0.001~1.5V, and the current density of charge and discharge is 500mA g-1, It is as shown in Figure 3 to obtain its cycle performance curve.
The experimental results showed that lithium ion battery provided by the invention first discharge specific capacity under 0.5C multiplying powers is not less than 1785mAh/g, after cycle charge-discharge 200 times, capacity retention ratio is not less than 89%, has preferable cycle performance.With preferable Cycle performance.
Meanwhile discharge cycle performance of the present invention also to obtained lithium ion battery under different multiplying is investigated, As shown in Figure 4.The experimental results showed that lithium ion battery provided by the invention all has at 0.1C, 0.2C, 0.5C, 1C and 2C Higher specific capacity, capacity is 2124mAh/g after 0.1C is recycled 10 times, and capacity is 1934mAh/g, 0.5C after 0.2C is recycled 10 times Capacity is 1734mAh/g after recycling 10 times, and capacity is 1509mAh/g after 1C is recycled 10 times, and 2C is still not less than after recycling 10 times 1244mAh/g, high rate performance are preferable.
Embodiment 2
By the aqueous solution of graphene oxide and nano silica fume, deionized water, polydiallyldimethyl ammonium chloride and ethylene glycol (or Glycerine) mixing, obtain mixed solution.Wherein, the mass concentration of the aqueous solution of graphene oxide is 0.5mg/mL, the nanometer The mass ratio of silica flour and graphene oxide is 5：1, the mass ratio of nano silica fume and polydiallyldimethyl ammonium chloride is 10：1, go from The volume ratio of sub- water and ethylene glycol (or glycerine) is 1：6, the body of ethylene glycol (or glycerine) and the aqueous solution of graphene oxide Product is than being 6：1；
Mixed solution is placed in reaction kettle, 200 DEG C of hydro-thermal reaction 2h obtain graphene/silicon plural gel；
By graphene/silicon plural gel in normal pressure, 90 DEG C of drying and processing 0.5h, then in (- 70) DEG C freeze-drying process 1h finally under an inert atmosphere, 1000 DEG C of high annealing 1h, obtains porous graphene/silicon composite.
Obtained porous graphene/silicon composite is scanned electron-microscope scanning analysis by the present invention, as a result such as Figures 5 and 6 It is shown.Fig. 5 is the SEM figures of porous graphene/silicon composite prepared by the embodiment of the present invention 2, as seen from Figure 5, this hair Porous graphene/silicon composite of bright offer is porous structure.Fig. 6 be the embodiment of the present invention 2 is obtained porous graphene/ Sample SEM after silicon composite is ground schemes, as seen from Figure 6, porous graphene/silicon composite wood after grinding Material is porous structure.
The present invention is by above-mentioned porous graphene/silicon composite and binder (SBR：CMC=3：7 mass ratioes), conductive agent Super P are according to 80：10：10 weight ratio mixing, is added suitable quantity of water and is tuned into slurry as dispersant, be then coated uniformly on copper On foil collector, and vacuum dried, roll-in, it is prepared into negative plate；It is to electrode, the LiPF of 1mol/L with lithium metal6It is mixed Bonding solvent (EC: DMC=1:1 volume ratio) it is electrolyte, microporous polypropylene membrane (Celgard 2400) is diaphragm, is protected in argon gas Glove box in be assembled into simulated battery.By the simulated battery being assembled into Land testers (Wuhan Xin Nuo Electronics Co., Ltd.s) Upper carry out constant current charge-discharge test, charging/discharging voltage section are 0.001~1.5V, and the current density of charge and discharge is 500mA g-1, It is as shown in Figure 3 to obtain its cycle performance curve.
The experimental results showed that lithium ion battery provided by the invention first discharge specific capacity under 0.5C multiplying powers is 1330mAh/g, after cycle charge-discharge 200 times, capacity retention ratio is not less than 72%, has preferable cycle performance.
Meanwhile discharge cycle performance of the present invention also to obtained lithium ion battery under different multiplying is investigated, As shown in Figure 4.The experimental results showed that lithium ion battery provided by the invention all has at 0.1C, 0.2C, 0.5C, 1C and 2C Higher specific capacity, capacity is 1613mAh/g after 0.1C is recycled 10 times, and capacity is 1501mAh/g, 0.5C after 0.2C is recycled 10 times Capacity is 1328mAh/g after recycling 10 times, and capacity is 1214mAh/g after 1C is recycled 10 times, and 2C is still not less than after recycling 10 times 1030mAh/g, high rate performance are preferable.
Embodiment 3
By the aqueous solution of graphene oxide and nano silica fume, deionized water, kayexalate and ethylene glycol (or the third three Alcohol) mixing, obtain mixed solution.Wherein, the mass concentration of the aqueous solution of graphene oxide be 7mg/mL, the nano silica fume with The mass ratio of graphene oxide is 1：6, the mass ratio of nano silica fume and kayexalate is 1：10, deionized water and second two The volume ratio of alcohol (or glycerine) is 6：1, the volume ratio of the aqueous solution of ethylene glycol (or glycerine) and graphene oxide is 1：6；
Mixed solution is placed in reaction kettle, 100 DEG C of hydro-thermal reaction 15h obtain graphene/silicon plural gel；
By graphene/silicon plural gel in normal pressure, 30 DEG C of drying and processing 7h, then in (- 10) DEG C freeze-drying process 60h finally under an inert atmosphere, 300 DEG C of high annealing 8h, obtains porous graphene/silicon composite.
Obtained porous graphene/silicon composite is scanned electron-microscope scanning analysis by the present invention, as a result such as Fig. 7 and 8 It is shown.Fig. 7 is the SEM figures of porous graphene/silicon composite prepared by the embodiment of the present invention 3, as seen from Figure 7, this hair Porous graphene/silicon composite of bright offer is porous structure.Fig. 8 be the embodiment of the present invention 3 is obtained porous graphene/ Sample SEM after silicon composite is ground schemes, as seen from Figure 8, porous graphene/silicon composite wood after grinding Material is porous structure.
The present invention is by above-mentioned porous graphene/silicon composite and binder (SBR：CMC=3：7 mass ratioes), conductive agent Super P are according to 80：10：10 weight ratio mixing, is added suitable quantity of water and is tuned into slurry as dispersant, be then coated uniformly on copper On foil collector, and vacuum dried, roll-in, it is prepared into negative plate；It is to electrode, the LiPF of 1mol/L with lithium metal6It is mixed Bonding solvent (EC: DMC=1:1 volume ratio) it is electrolyte, microporous polypropylene membrane (Celgard 2400) is diaphragm, is protected in argon gas Glove box in be assembled into simulated battery.By the simulated battery being assembled into Land testers (Wuhan Xin Nuo Electronics Co., Ltd.s) Upper carry out constant current charge-discharge test, charging/discharging voltage section are 0.001~1.5V, and the current density of charge and discharge is 500mA g-1, It is as shown in Figure 3 to obtain its cycle performance curve.
The experimental results showed that lithium ion battery provided by the invention first discharge specific capacity under 0.5C multiplying powers is 1590mAh/g, after cycle charge-discharge 200 times, capacity retention ratio is not less than 76%, has preferable cycle performance.
Meanwhile discharge cycle performance of the present invention also to obtained lithium ion battery under different multiplying is investigated, As shown in Figure 4.The experimental results showed that lithium ion battery provided by the invention all has at 0.1C, 0.2C, 0.5C, 1C and 2C Higher specific capacity, capacity is 1892mAh/g after 0.1C is recycled 10 times, and capacity is 1748mAh/g, 0.5C after 0.2C is recycled 10 times Capacity is 1560mAh/g after recycling 10 times, and capacity is 1358mAh/g after 1C is recycled 10 times, and 2C is still not less than after recycling 10 times 1157mAh/g, high rate performance are preferable.
Embodiment 4
By the aqueous solution of graphene oxide and nano silica fume, deionized water, polyvinylpyrrolidone and ethylene glycol (or the third three Alcohol) mixing, obtain mixed solution.Wherein, the mass concentration of the aqueous solution of graphene oxide be 1mg/mL, the nano silica fume with The mass ratio of graphene oxide is 1：5, the mass ratio of nano silica fume and polyvinylpyrrolidone is 1：5, deionized water and second two The volume ratio of alcohol (or glycerine) is 5：1, the volume ratio of the aqueous solution of ethylene glycol (or glycerine) and graphene oxide is 1：5；
Mixed solution is placed in reaction kettle, 120 DEG C of hydro-thermal reaction 8h obtain graphene/silicon plural gel；
By graphene/silicon plural gel in normal pressure, 70 DEG C of drying and processing 4h, then in (- 40) DEG C freeze-drying process 36h finally under an inert atmosphere, 500 DEG C of high annealing 6h, obtains porous graphene/silicon composite.
The present invention is by above-mentioned porous graphene/silicon composite and binder (SBR：CMC=3：7 mass ratioes), conductive agent Super P are according to 80：10：10 weight ratio mixing, is added suitable quantity of water and is tuned into slurry as dispersant, be then coated uniformly on copper On foil collector, and vacuum dried, roll-in, it is prepared into negative plate；It is to electrode, the LiPF of 1mol/L with lithium metal6It is mixed Bonding solvent (EC: DMC=1:1 volume ratio) it is electrolyte, microporous polypropylene membrane (Celgard 2400) is diaphragm, is protected in argon gas Glove box in be assembled into simulated battery.By the simulated battery being assembled into Land testers (Wuhan Xin Nuo Electronics Co., Ltd.s) Upper carry out constant current charge-discharge test, charging/discharging voltage section are 0.001~1.5V, and the current density of charge and discharge is 500mA g-1。
The experimental results showed that lithium ion battery provided by the invention first discharge specific capacity under 0.5C multiplying powers is 1750mAh/g, after cycle charge-discharge 200 times, capacity retention ratio is not less than 82%.
Meanwhile discharge cycle performance of the present invention also to obtained lithium ion battery under different multiplying is investigated. The experimental results showed that lithium ion battery provided by the invention all has higher specific volume at 0.1C, 0.2C, 0.5C, 1C and 2C Amount, capacity is 1922mAh/g after 0.1C is recycled 10 times, and capacity is 1835mAh/g after 0.2C is recycled 10 times, after 0.5C is recycled 10 times Capacity is 1660mAh/g, and capacity is 1485mAh/g after 1C is recycled 10 times, and 2C is still not less than 1250mAh/g after recycling 10 times.
Embodiment 5
The aqueous solution of graphene oxide is mixed with nano silica fume, deionized water, polyvinylpyrrolidone and ethyl alcohol, is obtained Mixed solution.Wherein, the mass concentration of the aqueous solution of graphene oxide is 6mg/mL, the nano silica fume and graphene oxide Mass ratio is 1：1, the mass ratio of nano silica fume and polyvinylpyrrolidone is 2：1, the volume ratio of deionized water and ethyl alcohol is 1： 1, the volume ratio of the aqueous solution of ethyl alcohol and graphene oxide is 1：1；
Mixed solution is placed in reaction kettle, 180 DEG C of hydro-thermal reaction 12h obtain graphene/silicon plural gel；
By graphene/silicon plural gel in normal pressure, 60 DEG C of drying and processing 2h, then in (- 60) DEG C freeze-drying process 48h finally under an inert atmosphere, 800 DEG C of high annealing 4h, obtains porous graphene/silicon composite.
The present invention is by above-mentioned porous graphene/silicon composite and binder (SBR：CMC=3：7 mass ratioes), conductive agent Super P are according to 80：10：10 weight ratio mixing, is added suitable quantity of water and is tuned into slurry as dispersant, be then coated uniformly on copper On foil collector, and vacuum dried, roll-in, it is prepared into negative plate；It is to electrode, the LiPF of 1mol/L with lithium metal6It is mixed Bonding solvent (EC: DMC=1:1 volume ratio) it is electrolyte, microporous polypropylene membrane (Celgard 2400) is diaphragm, is protected in argon gas Glove box in be assembled into simulated battery.By the simulated battery being assembled into Land testers (Wuhan Xin Nuo Electronics Co., Ltd.s) Upper carry out constant current charge-discharge test, charging/discharging voltage section are 0.001~1.5V, and the current density of charge and discharge is 500mA g-1。
The experimental results showed that lithium ion battery provided by the invention first discharge specific capacity under 0.5C multiplying powers is 1630mAh/g, after cycle charge-discharge 200 times, capacity retention ratio is not less than 80%, has preferable cycle performance.
Meanwhile discharge cycle performance of the present invention also to obtained lithium ion battery under different multiplying is investigated. The experimental results showed that lithium ion battery provided by the invention all has higher specific volume at 0.1C, 0.2C, 0.5C, 1C and 2C Amount, capacity is 2010mAh/g after 0.1C is recycled 10 times, and capacity is 1825mAh/g after 0.2C is recycled 10 times, after 0.5C is recycled 10 times Capacity is 1621mAh/g, and capacity is 1486mAh/g after 1C is recycled 10 times, and 2C is still not less than 1124mAh/g after recycling 10 times, High rate performance is preferable.
Embodiment 6
The aqueous solution of graphene oxide is mixed with nano silica fume, deionized water, polydiallyldimethyl ammonium chloride and ethyl alcohol, Obtain mixed solution.Wherein, the mass concentration of the aqueous solution of graphene oxide is 0.5mg/mL, the nano silica fume and oxidation stone The mass ratio of black alkene is 5：1, the mass ratio of nano silica fume and polydiallyldimethyl ammonium chloride is 10：1, deionized water and ethyl alcohol Volume ratio is 1：6, the volume ratio of the aqueous solution of ethyl alcohol and graphene oxide is 6：1；
Mixed solution is placed in reaction kettle, 200 DEG C of hydro-thermal reaction 2h obtain graphene/silicon plural gel；
By graphene/silicon plural gel in normal pressure, 90 DEG C of drying and processing 0.5h, then in (- 70) DEG C freeze-drying process 1h finally under an inert atmosphere, 1000 DEG C of high annealing 1h, obtains porous graphene/silicon composite.
The present invention is by above-mentioned porous graphene/silicon composite and binder (SBR：CMC=3：7 mass ratioes), conductive agent Super P are according to 80：10：10 weight ratio mixing, is added suitable quantity of water and is tuned into slurry as dispersant, be then coated uniformly on copper On foil collector, and vacuum dried, roll-in, it is prepared into negative plate；It is to electrode, the LiPF of 1mol/L with lithium metal6It is mixed Bonding solvent (EC: DMC=1:1 volume ratio) it is electrolyte, microporous polypropylene membrane (Celgard 2400) is diaphragm, is protected in argon gas Glove box in be assembled into simulated battery.By the simulated battery being assembled into Land testers (Wuhan Xin Nuo Electronics Co., Ltd.s) Upper carry out constant current charge-discharge test, charging/discharging voltage section are 0.001~1.5V, and the current density of charge and discharge is 500mA g-1。
The experimental results showed that lithium ion battery provided by the invention first discharge specific capacity under 0.5C multiplying powers is 1325mAh/g, after cycle charge-discharge 200 times, capacity retention ratio is not less than 71%, has preferable cycle performance.
Meanwhile discharge cycle performance of the present invention also to obtained lithium ion battery under different multiplying is investigated. The experimental results showed that lithium ion battery provided by the invention all has higher specific volume at 0.1C, 0.2C, 0.5C, 1C and 2C Amount, capacity is 1612mAh/g after 0.1C is recycled 10 times, and capacity is 1500mAh/g after 0.2C is recycled 10 times, after 0.5C is recycled 10 times Capacity is 1322mAh/g, and capacity is 1212mAh/g after 1C is recycled 10 times, and 2C is still not less than 1025mAh/g after recycling 10 times.
Embodiment 7
The aqueous solution of graphene oxide is mixed with nano silica fume, deionized water, kayexalate and ethyl alcohol, is obtained Mixed solution.Wherein, the mass concentration of the aqueous solution of graphene oxide is 7mg/mL, the nano silica fume and graphene oxide Mass ratio is 1：6, the mass ratio of nano silica fume and kayexalate is 1：10, the volume ratio of deionized water and ethyl alcohol is 6： 1, the volume ratio of the aqueous solution of ethyl alcohol and graphene oxide is 1：6；
Mixed solution is placed in reaction kettle, 100 DEG C of hydro-thermal reaction 15h obtain graphene/silicon plural gel；
By graphene/silicon plural gel in normal pressure, 30 DEG C of drying and processing 7h, then in (- 10) DEG C freeze-drying process 60h finally under an inert atmosphere, 300 DEG C of high annealing 8h, obtains porous graphene/silicon composite.
The present invention is by above-mentioned porous graphene/silicon composite and binder (SBR：CMC=3：7 mass ratioes), conductive agent Super P are according to 80：10：10 weight ratio mixing, is added suitable quantity of water and is tuned into slurry as dispersant, be then coated uniformly on copper On foil collector, and vacuum dried, roll-in, it is prepared into negative plate；It is to electrode, the LiPF of 1mol/L with lithium metal6It is mixed Bonding solvent (EC: DMC=1:1 volume ratio) it is electrolyte, microporous polypropylene membrane (Celgard 2400) is diaphragm, is protected in argon gas Glove box in be assembled into simulated battery.By the simulated battery being assembled into Land testers (Wuhan Xin Nuo Electronics Co., Ltd.s) Upper carry out constant current charge-discharge test, charging/discharging voltage section are 0.001~1.5V, and the current density of charge and discharge is 500mA g-1。
The experimental results showed that lithium ion provided by the invention battery first discharge specific capacity under 0.5C multiplying powers is 1585mAh/g, after cycle charge-discharge 200 times, capacity retention ratio is not less than 75%.
Meanwhile discharge cycle performance of the present invention also to obtained lithium ion battery under different multiplying is investigated. The experimental results showed that lithium ion battery provided by the invention all has higher specific volume at 0.1C, 0.2C, 0.5C, 1C and 2C Amount, capacity is 1885mAh/g after 0.1C is recycled 10 times, and capacity is 1710mAh/g after 0.2C is recycled 10 times, after 0.5C is recycled 10 times Capacity is 1510mAh/g, and capacity is 1330mAh/g after 1C is recycled 10 times, and 2C is still not less than 1123mAh/g after recycling 10 times.
Embodiment 8
The aqueous solution of graphene oxide is mixed with nano silica fume, deionized water, polyvinylpyrrolidone and ethyl alcohol, is obtained Mixed solution.Wherein, the mass concentration of the aqueous solution of graphene oxide is 1mg/mL, the nano silica fume and graphene oxide Mass ratio is 1：5, the mass ratio of nano silica fume and polyvinylpyrrolidone is 1：5, the volume ratio of deionized water and ethyl alcohol is 5： 1, the volume ratio of the aqueous solution of ethyl alcohol and graphene oxide is 1：5；
Mixed solution is placed in reaction kettle, 120 DEG C of hydro-thermal reaction 8h obtain graphene/silicon plural gel；
By graphene/silicon plural gel in normal pressure, 50 DEG C of drying and processing 3.5h, then in (- 40) DEG C freeze-drying process 36h finally under an inert atmosphere, 500 DEG C of high annealing 6h, obtains porous graphene/silicon composite.
The present invention is by above-mentioned porous graphene/silicon composite and binder (SBR：CMC=3：7 mass ratioes), conductive agent Super P are according to 80：10：10 weight ratio mixing, is added suitable quantity of water and is tuned into slurry as dispersant, be then coated uniformly on copper On foil collector, and vacuum dried, roll-in, it is prepared into negative plate；It is to electrode, the LiPF of 1mol/L with lithium metal6It is mixed Bonding solvent (EC: DMC=1:1 volume ratio) it is electrolyte, microporous polypropylene membrane (Celgard 2400) is diaphragm, is protected in argon gas Glove box in be assembled into simulated battery.By the simulated battery being assembled into Land testers (Wuhan Xin Nuo Electronics Co., Ltd.s) Upper carry out constant current charge-discharge test, charging/discharging voltage section are 0.001~1.5V, and the current density of charge and discharge is 500mA g-1。
The experimental results showed that lithium ion battery provided by the invention first discharge specific capacity under 0.5C multiplying powers is 1610mAh/g, after cycle charge-discharge 200 times, capacity retention ratio is not less than 79%.
Meanwhile discharge cycle performance of the present invention also to obtained lithium ion battery under different multiplying is investigated. The experimental results showed that lithium ion battery provided by the invention all has higher specific volume at 0.1C, 0.2C, 0.5C, 1C and 2C Amount, capacity is 1900mAh/g after 0.1C is recycled 10 times, and capacity is 1695mAh/g after 0.2C is recycled 10 times, after 0.5C is recycled 10 times Capacity is 1489mAh/g, and capacity is 1296mAh/g after 1C is recycled 10 times, and 2C is still not less than 1220mAh/g after recycling 10 times.
Embodiment 9
The aqueous solution of graphene oxide is mixed with nano silica fume, deionized water and polyvinylpyrrolidone, is mixed Solution.Wherein, the mass concentration of the aqueous solution of graphene oxide is 6mg/mL, the quality of the nano silica fume and graphene oxide Than being 1：1, the mass ratio of nano silica fume and polyvinylpyrrolidone is 2：1, the aqueous solution of deionized water and graphene oxide Volume ratio is 1：1；
Mixed solution is placed in reaction kettle, 180 DEG C of hydro-thermal reaction 12h obtain graphene/silicon plural gel；
By graphene/silicon plural gel under 2 atmospheric pressure, 65 DEG C of drying and processing 3h, then in (- 60) DEG C freeze-drying 48h is handled, finally, under an inert atmosphere, 800 DEG C of high annealing 4h, obtains porous graphene/silicon composite.
The present invention is by above-mentioned porous graphene/silicon composite and binder (SBR：CMC=3：7 mass ratioes), conductive agent Super P are according to 80：10：10 weight ratio mixing, is added suitable quantity of water and is tuned into slurry as dispersant, be then coated uniformly on copper On foil collector, and vacuum dried, roll-in, it is prepared into negative plate；It is to electrode, the LiPF of 1mol/L with lithium metal6It is mixed Bonding solvent (EC: DMC=1:1 volume ratio) it is electrolyte, microporous polypropylene membrane (Celgard 2400) is diaphragm, is protected in argon gas Glove box in be assembled into simulated battery.By the simulated battery being assembled into Land testers (Wuhan Xin Nuo Electronics Co., Ltd.s) Upper carry out constant current charge-discharge test, charging/discharging voltage section are 0.001~1.5V, and the current density of charge and discharge is 500mA g-1, It is as shown in Figure 9 to obtain its cycle performance curve.
The experimental results showed that lithium ion battery provided by the invention first discharge specific capacity under 0.5C multiplying powers is 1715mAh/g, after cycle charge-discharge 200 times, capacity retention ratio is not less than 90%.
Meanwhile discharge cycle performance of the present invention also to obtained lithium ion battery under different multiplying is investigated, As shown in Figure 10.The experimental results showed that lithium ion battery provided by the invention all has at 0.1C, 0.2C, 0.5C, 1C and 2C Higher specific capacity, capacity is 2203mAh/g after 0.1C is recycled 10 times, and capacity is 1941mAh/g, 0.5C after 0.2C is recycled 10 times Capacity is 1710mAh/g after recycling 10 times, and capacity is 1514mAh/g after 1C is recycled 10 times, and 2C is still not less than after recycling 10 times 1230mAh/g。
Embodiment 10
The aqueous solution of graphene oxide is mixed with nano silica fume, deionized water and polydiallyldimethyl ammonium chloride, is obtained Mixed solution.Wherein, the mass concentration of the aqueous solution of graphene oxide is 0.5mg/mL, the nano silica fume and graphene oxide Mass ratio be 5：1, the mass ratio of nano silica fume and polydiallyldimethyl ammonium chloride is 10：1, deionized water and graphene oxide Aqueous solution volume ratio be 6：1；
Mixed solution is placed in reaction kettle, 200 DEG C of hydro-thermal reaction 2h obtain graphene/silicon plural gel；
By graphene/silicon plural gel under 5 atmospheric pressure, 30 DEG C of drying and processing 7h, then in (- 70) DEG C freeze-drying 1h is handled, finally, under an inert atmosphere, 1000 DEG C of high annealing 1h, obtains porous graphene/silicon composite.
The present invention is by above-mentioned porous graphene/silicon composite and binder (SBR：CMC=3：7 mass ratioes), conductive agent Super P are according to 80：10：10 weight ratio mixing, is added suitable quantity of water and is tuned into slurry as dispersant, be then coated uniformly on copper On foil collector, and vacuum dried, roll-in, it is prepared into negative plate；It is to electrode, the LiPF of 1mol/L with lithium metal6It is mixed Bonding solvent (EC: DMC=1:1 volume ratio) it is electrolyte, microporous polypropylene membrane (Celgard 2400) is diaphragm, is protected in argon gas Glove box in be assembled into simulated battery.By the simulated battery being assembled into Land testers (Wuhan Xin Nuo Electronics Co., Ltd.s) Upper carry out constant current charge-discharge test, charging/discharging voltage section are 0.001~1.5V, and the current density of charge and discharge is 500mA g-1, It is as shown in Figure 9 to obtain its cycle performance curve.
The experimental results showed that lithium ion battery provided by the invention first discharge specific capacity under 0.5C multiplying powers is 1335mAh/g, after cycle charge-discharge 200 times, capacity retention ratio is not less than 72%.
Meanwhile discharge cycle performance of the present invention also to obtained lithium ion battery under different multiplying is investigated, As shown in Figure 10.The experimental results showed that lithium ion battery provided by the invention all has at 0.1C, 0.2C, 0.5C, 1C and 2C Higher specific capacity, capacity is 1568mAh/g after 0.1C is recycled 10 times, and capacity is 1507mAh/g, 0.5C after 0.2C is recycled 10 times Capacity is 1330mAh/g after recycling 10 times, and capacity is 1222mAh/g after 1C is recycled 10 times, and 2C is still not less than after recycling 10 times 1028mAh/g。
Embodiment 11
The aqueous solution of graphene oxide is mixed with nano silica fume, deionized water and kayexalate, is mixed Solution.Wherein, the mass concentration of the aqueous solution of graphene oxide is 7mg/mL, the quality of the nano silica fume and graphene oxide Than being 1：6, the mass ratio of nano silica fume and kayexalate is 1：10, the aqueous solution of deionized water and graphene oxide Volume ratio is 1：6；
Mixed solution is placed in reaction kettle, 100 DEG C of hydro-thermal reaction 15h obtain graphene/silicon plural gel；
By graphene/silicon plural gel under 3 atmospheric pressure, 90 DEG C of drying and processing 0.5h, then in (- 10), DEG C freezing is dry Dry processing 60h finally under an inert atmosphere, 300 DEG C of high annealing 8h, obtains porous graphene/silicon composite.
The present invention is by above-mentioned porous graphene/silicon composite and binder (SBR：CMC=3：7 mass ratioes), conductive agent Super P are according to 80：10：10 weight ratio mixing, is added suitable quantity of water and is tuned into slurry as dispersant, be then coated uniformly on copper On foil collector, and vacuum dried, roll-in, it is prepared into negative plate；It is to electrode, the LiPF of 1mol/L with lithium metal6It is mixed Bonding solvent (EC: DMC=1:1 volume ratio) it is electrolyte, microporous polypropylene membrane (Celgard 2400) is diaphragm, is protected in argon gas Glove box in be assembled into simulated battery.By the simulated battery being assembled into Land testers (Wuhan Xin Nuo Electronics Co., Ltd.s) Upper carry out constant current charge-discharge test, charging/discharging voltage section are 0.001~1.5V, and the current density of charge and discharge is 500mA g-1, It is as shown in Figure 9 to obtain its cycle performance curve.
The experimental results showed that lithium ion battery provided by the invention first discharge specific capacity under 0.5C multiplying powers is 1554mAh/g, after cycle charge-discharge 200 times, capacity retention ratio is not less than 78%.
Meanwhile discharge cycle performance of the present invention also to obtained lithium ion battery under different multiplying is investigated, As shown in Figure 10.The experimental results showed that lithium ion battery provided by the invention all has at 0.1C, 0.2C, 0.5C, 1C and 2C Higher specific capacity, capacity is 1855mAh/g after 0.1C is recycled 10 times, and capacity is 1683mAh/g, 0.5C after 0.2C is recycled 10 times Capacity is 1530mAh/g after recycling 10 times, and capacity is 1342mAh/g after 1C is recycled 10 times, and 2C is still not less than after recycling 10 times 1157mAh/g。
Embodiment 12
The aqueous solution of graphene oxide is mixed with nano silica fume, deionized water and polyvinylpyrrolidone, is mixed Solution.Wherein, the mass concentration of the aqueous solution of graphene oxide is 1mg/mL, the quality of the nano silica fume and graphene oxide Than being 1：5, the mass ratio of nano silica fume and polyvinylpyrrolidone is 1：5, the aqueous solution of deionized water and graphene oxide Volume ratio is 1：5；
Mixed solution is placed in reaction kettle, 120 DEG C of hydro-thermal reaction 8h obtain graphene/silicon plural gel；
By graphene/silicon plural gel under 1.5 atmospheric pressure, 70 DEG C of drying and processing 2h, then in (- 40), DEG C freezing is dry Dry processing 36h finally under an inert atmosphere, 500 DEG C of high annealing 6h, obtains porous graphene/silicon composite.
The present invention is by above-mentioned porous graphene/silicon composite and binder (SBR：CMC=3：7 mass ratioes), conductive agent Super P are according to 80：10：10 weight ratio mixing, is added suitable quantity of water and is tuned into slurry as dispersant, be then coated uniformly on copper On foil collector, and vacuum dried, roll-in, it is prepared into negative plate；It is to electrode, the LiPF of 1mol/L with lithium metal6It is mixed Bonding solvent (EC: DMC=1:1 volume ratio) it is electrolyte, microporous polypropylene membrane (Celgard 2400) is diaphragm, is protected in argon gas Glove box in be assembled into simulated battery.By the simulated battery being assembled into Land testers (Wuhan Xin Nuo Electronics Co., Ltd.s) Upper carry out constant current charge-discharge test, charging/discharging voltage section are 0.001~1.5V, and the current density of charge and discharge is 500mA g-1。
The experimental results showed that lithium ion battery provided by the invention first discharge specific capacity under 0.5C multiplying powers is 1700mAh/g, after cycle charge-discharge 200 times, capacity retention ratio is not less than 88%.
Meanwhile discharge cycle performance of the present invention also to obtained lithium ion battery under different multiplying is investigated. The experimental results showed that lithium ion battery provided by the invention all has higher specific volume at 0.1C, 0.2C, 0.5C, 1C and 2C Amount, capacity is 2085mAh/g after 0.1C is recycled 10 times, and capacity is 1802mAh/g after 0.2C is recycled 10 times, after 0.5C is recycled 10 times Capacity is 1662mAh/g, and capacity is 1406mAh/g after 1C is recycled 10 times, and 2C is still not less than 1227mAh/g after recycling 10 times.
Embodiment 13
The aqueous solution of graphene oxide is mixed with nano silica fume, deionized water and polyvinylpyrrolidone, is mixed Solution.Wherein, the mass concentration of the aqueous solution of graphene oxide is 6mg/mL, the quality of the nano silica fume and graphene oxide Than being 1：1, the mass ratio of nano silica fume and polyvinylpyrrolidone is 2：1, the aqueous solution of deionized water and graphene oxide Volume ratio is 1：1；
Mixed solution is placed in reaction kettle, 180 DEG C of hydro-thermal reaction 12h obtain graphene/silicon plural gel；
By graphene/silicon plural gel under 0.7 atmospheric pressure, 50 DEG C of drying and processing 3h, then in (- 60), DEG C freezing is dry Dry processing 48h finally under an inert atmosphere, 800 DEG C of high annealing 4h, obtains porous graphene/silicon composite.
The present invention is by above-mentioned porous graphene/silicon composite and binder (SBR：CMC=3：7 mass ratioes), conductive agent Super P are according to 80：10：10 weight ratio mixing, is added suitable quantity of water and is tuned into slurry as dispersant, be then coated uniformly on copper On foil collector, and vacuum dried, roll-in, it is prepared into negative plate；It is to electrode, the LiPF of 1mol/L with lithium metal6It is mixed Bonding solvent (EC: DMC=1:1 volume ratio) it is electrolyte, microporous polypropylene membrane (Celgard 2400) is diaphragm, is protected in argon gas Glove box in be assembled into simulated battery.By the simulated battery being assembled into Land testers (Wuhan Xin Nuo Electronics Co., Ltd.s) Upper carry out constant current charge-discharge test, charging/discharging voltage section are 0.001~1.5V, and the current density of charge and discharge is 500mA g-1。
The experimental results showed that lithium ion battery provided by the invention first discharge specific capacity under 0.5C multiplying powers is 1735mAh/g, after cycle charge-discharge 200 times, capacity retention ratio is not less than 90%.
Meanwhile discharge cycle performance of the present invention also to obtained lithium ion battery under different multiplying is investigated. The experimental results showed that lithium ion battery provided by the invention all has higher specific volume at 0.1C, 0.2C, 0.5C, 1C and 2C Amount, capacity is 2203mAh/g after 0.1C is recycled 10 times, and capacity is 1941mAh/g after 0.2C is recycled 10 times, after 0.5C is recycled 10 times Capacity is 1732mAh/g, and capacity is 1514mAh/g after 1C is recycled 10 times, and 2C is still not less than 1230mAh/g after recycling 10 times.
Embodiment 14
The aqueous solution of graphene oxide is mixed with nano silica fume, deionized water and polydiallyldimethyl ammonium chloride, is obtained Mixed solution.Wherein, the mass concentration of the aqueous solution of graphene oxide is 0.5mg/mL, the nano silica fume and graphene oxide Mass ratio be 5：1, the mass ratio of nano silica fume and polydiallyldimethyl ammonium chloride is 10：1, deionized water and graphene oxide Aqueous solution volume ratio be 6：1；
Mixed solution is placed in reaction kettle, 200 DEG C of hydro-thermal reaction 2h obtain graphene/silicon plural gel；
By graphene/silicon plural gel under 0.6 atmospheric pressure, 60 DEG C of drying and processing 1h, then in (- 70), DEG C freezing is dry Dry processing 1h finally under an inert atmosphere, 1000 DEG C of high annealing 1h, obtains porous graphene/silicon composite.
The present invention is by above-mentioned porous graphene/silicon composite and binder (SBR：CMC=3：7 mass ratioes), conductive agent Super P are according to 80：10：10 weight ratio mixing, is added suitable quantity of water and is tuned into slurry as dispersant, be then coated uniformly on copper On foil collector, and vacuum dried, roll-in, it is prepared into negative plate；It is to electrode, the LiPF of 1mol/L with lithium metal6It is mixed Bonding solvent (EC: DMC=1:1 volume ratio) it is electrolyte, microporous polypropylene membrane (Celgard 2400) is diaphragm, is protected in argon gas Glove box in be assembled into simulated battery.By the simulated battery being assembled into Land testers (Wuhan Xin Nuo Electronics Co., Ltd.s) Upper carry out constant current charge-discharge test, charging/discharging voltage section are 0.001~1.5V, and the current density of charge and discharge is 500mA g-1。
The experimental results showed that lithium ion battery provided by the invention first discharge specific capacity under 0.5C multiplying powers is 1335mAh/g, after cycle charge-discharge 200 times, capacity retention ratio is not less than 72%.
Meanwhile discharge cycle performance of the present invention also to obtained lithium ion battery under different multiplying is investigated. The experimental results showed that lithium ion battery provided by the invention all has higher specific volume at 0.1C, 0.2C, 0.5C, 1C and 2C Amount, capacity is 1568mAh/g after 0.1C is recycled 10 times, and capacity is 1507mAh/g after 0.2C is recycled 10 times, after 0.5C is recycled 10 times Capacity is 1328mAh/g, and capacity is 1222mAh/g after 1C is recycled 10 times, and 2C is still not less than 1028mAh/g after recycling 10 times.
Embodiment 15
The aqueous solution of graphene oxide is mixed with nano silica fume, deionized water and kayexalate, is mixed Solution.Wherein, the mass concentration of the aqueous solution of graphene oxide is 7mg/mL, the quality of the nano silica fume and graphene oxide Than being 1：6, the mass ratio of nano silica fume and kayexalate is 1：10, the aqueous solution of deionized water and graphene oxide Volume ratio is 1：6；
Mixed solution is placed in reaction kettle, 100 DEG C of hydro-thermal reaction 15h obtain graphene/silicon plural gel；
By graphene/silicon plural gel under 0.5 atmospheric pressure, 30 DEG C of drying and processing 2h, then in (- 10), DEG C freezing is dry Dry processing 60h finally under an inert atmosphere, 300 DEG C of high annealing 8h, obtains porous graphene/silicon composite.
The present invention is by above-mentioned porous graphene/silicon composite and binder (SBR：CMC=3：7 mass ratioes), conductive agent Super P are according to 80：10：10 weight ratio mixing, is added suitable quantity of water and is tuned into slurry as dispersant, be then coated uniformly on copper On foil collector, and vacuum dried, roll-in, it is prepared into negative plate；It is to electrode, the LiPF of 1mol/L with lithium metal6It is mixed Bonding solvent (EC: DMC=1:1 volume ratio) it is electrolyte, microporous polypropylene membrane (Celgard 2400) is diaphragm, is protected in argon gas Glove box in be assembled into simulated battery.By the simulated battery being assembled into Land testers (Wuhan Xin Nuo Electronics Co., Ltd.s) Upper carry out constant current charge-discharge test, charging/discharging voltage section are 0.001~1.5V, and the current density of charge and discharge is 500mA g-1。
The experimental results showed that lithium ion battery provided by the invention first discharge specific capacity under 0.5C multiplying powers is 1554mAh/g, after cycle charge-discharge 200 times, capacity retention ratio is not less than 78%.
Meanwhile discharge cycle performance of the present invention also to obtained lithium ion battery under different multiplying is investigated. The experimental results showed that lithium ion battery provided by the invention all has higher specific volume at 0.1C, 0.2C, 0.5C, 1C and 2C Amount, capacity is 1855mAh/g after 0.1C is recycled 10 times, and capacity is 1683mAh/g after 0.2C is recycled 10 times, after 0.5C is recycled 10 times Capacity is 1530mAh/g, and capacity is 1342mAh/g after 1C is recycled 10 times, and 2C is still not less than 1157mAh/g after recycling 10 times.
Embodiment 16
The aqueous solution of graphene oxide is mixed with nano silica fume, deionized water and polyvinylpyrrolidone, is mixed Solution.Wherein, the mass concentration of the aqueous solution of graphene oxide is 1mg/mL, the quality of the nano silica fume and graphene oxide Than being 1：5, the mass ratio of nano silica fume and polyvinylpyrrolidone is 1：5, the aqueous solution of deionized water and graphene oxide Volume ratio is 1：5；
Mixed solution is placed in reaction kettle, 120 DEG C of hydro-thermal reaction 8h obtain graphene/silicon plural gel；
By graphene/silicon plural gel under 0.9 atmospheric pressure, 90 DEG C of drying and processing 0.5h, then in (- 40) DEG C freezing It is dried 36h, finally, under an inert atmosphere, 500 DEG C of high annealing 6h, obtains porous graphene/silicon composite.
The present invention is by above-mentioned porous graphene/silicon composite and binder (SBR：CMC=3：7 mass ratioes), conductive agent Super P are according to 80：10：10 weight ratio mixing, is added suitable quantity of water and is tuned into slurry as dispersant, be then coated uniformly on copper On foil collector, and vacuum dried, roll-in, it is prepared into negative plate；It is to electrode, the LiPF of 1mol/L with lithium metal6It is mixed Bonding solvent (EC: DMC=1:1 volume ratio) it is electrolyte, microporous polypropylene membrane (Celgard 2400) is diaphragm, is protected in argon gas Glove box in be assembled into simulated battery.By the simulated battery being assembled into Land testers (Wuhan Xin Nuo Electronics Co., Ltd.s) Upper carry out constant current charge-discharge test, charging/discharging voltage section are 0.001~1.5V, and the current density of charge and discharge is 500mA g-1。
The experimental results showed that lithium ion battery provided by the invention first discharge specific capacity under 0.5C multiplying powers is 1700mAh/g, after cycle charge-discharge 200 times, capacity retention ratio is not less than 88%.
Meanwhile discharge cycle performance of the present invention also to obtained lithium ion battery under different multiplying is investigated. The experimental results showed that lithium ion battery provided by the invention all has higher specific volume at 0.1C, 0.2C, 0.5C, 1C and 2C Amount, capacity is 2085mAh/g after 0.1C is recycled 10 times, and capacity is 1802mAh/g after 0.2C is recycled 10 times, after 0.5C is recycled 10 times Capacity is 1662mAh/g, and capacity is 1406mAh/g after 1C is recycled 10 times, and 2C is still not less than 1227mAh/g after recycling 10 times.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to those skilled in the art, as defined herein General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one The widest range caused.

Claims (8)

1. a kind of preparation method of porous graphene/silicon composite, which is characterized in that include the following steps：
A1) aqueous solution of graphene oxide, nano silica fume, deionized water, surfactant and organic solvent are mixed, mixed Close solution；
B the mixed solution) is subjected to hydro-thermal reaction, obtains graphene/silicon plural gel；
C1) the graphene/silicon plural gel at normal pressure, 30 DEG C~90 DEG C is dried to 0.5~7h, it is dry then to carry out freezing It is dry, be thermally treated resulting in porous graphene/silicon composite；
The one kind of the organic solvent in ethyl alcohol, ethylene glycol or glycerine；
Or
A2) aqueous solution of graphene oxide, nano silica fume, deionized water and surfactant are mixed, obtain mixed solution；
B the mixed solution) is subjected to hydro-thermal reaction, obtains graphene/silicon plural gel；
C2) by the graphene/silicon plural gel under 0.7~0.9 atmospheric pressure or 1.5~3 atmospheric pressure, 30 DEG C~90 DEG C 0.5~7h is dried, is then freeze-dried, is heat-treated, obtain porous graphene/silicon composite.
2. preparation method according to claim 1, which is characterized in that the mass concentration of the aqueous solution of the graphene oxide For 0.5mg/mL~7mg/mL.
3. preparation method according to claim 1, which is characterized in that step A1) in, the nano silica fume and graphite oxide The mass ratio of alkene is 1：6~5：1, the mass ratio of the nano silica fume and surfactant is 1：10~10：1, the deionization The volume ratio of water and organic solvent is 1：6~6：1, the volume ratio of the aqueous solution of the organic solvent and graphene oxide is 1：6 ~6：1.
4. preparation method according to claim 1, which is characterized in that step A2) in, the nano silica fume and graphite oxide Alkene mass ratio is 1：6~5：1, the mass ratio of the nano silica fume and surfactant is 1：10~10：1, the deionized water Volume ratio with the aqueous solution of graphene oxide is 1：6~6：1.
5. preparation method according to claim 1, which is characterized in that the temperature of the hydro-thermal reaction is 100 DEG C~200 DEG C, the time of the hydro-thermal reaction is 2h~15h.
6. preparation method according to claim 1, which is characterized in that the temperature of the heat treatment is 300 DEG C~1000 DEG C, The time of the heat treatment is 1h~8h.
7. porous graphene/silicon composite prepared by claim 1~6 any one preparation method.
8. a kind of lithium ion battery, including anode, cathode, diaphragm and electrolyte, which is characterized in that the cathode includes that right is wanted Seek porous graphene/silicon composite described in 7.
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