CN106099061A - A kind of porous graphene/silicon composite, its preparation method and lithium ion battery - Google Patents

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

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CN106099061A
CN106099061A CN201610561612.7A CN201610561612A CN106099061A CN 106099061 A CN106099061 A CN 106099061A CN 201610561612 A CN201610561612 A CN 201610561612A CN 106099061 A CN106099061 A CN 106099061A
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graphene
silicon
pluralgel
silicon composite
present
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CN106099061B (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 invention provides the preparation method of a kind of porous graphene/silicon composite, first hydrothermal treatment consists prepares graphene/silicon pluralgel, then drying and processing regulation and control aperture within graphene/silicon pluralgel, the most freeze-dried, heat treatment prepares porous graphene/silicon composite, the method can also strengthen the bond strength between silicon and graphene sheet layer while regulation and control graphene/silicon composite aperture, prevent in charge and discharge process peeling-off between silicon and Graphene, ensure that prepared porous graphene/silicon composite has higher reversible capacity, preferably cycle performance and high rate performance.Experiment shows, the lithium ion battery that the present invention prepares is under 0.5C multiplying power, and first discharge specific capacity is 1325～1785mAh/g, and after circulating 200 times, specific discharge capacity is 940～1600mAh/g.

Description

A kind of porous graphene/silicon composite, its preparation method and lithium ion battery
Technical field
The present invention relates to technical field of lithium ion, particularly relate to a kind of porous graphene/silicon composite, it prepares Method and lithium ion battery.
Background technology
Lithium ion battery has running voltage height, specific energy height, operating temperature range width, electric discharge is steady, volume is little, quality Gently, memory-less effect and the advantage such as environmentally friendly, therefore in portable electric appts, electric automobile, space technology, national defence work The fields such as industry illustrate wide application prospect.
Along with mobile electronic equipment to high power capacity, long-life batteries demand growing, people are to lithium ion battery Performance have higher requirement, and negative material is as improving lithium ion battery energy and the key factor of cycle life, Worldwide obtain studying widely.
Early 1990s, Sony corporation of Japan takes the lead in developing carbon negative pole material, significantly improves lithium ion battery Security performance and charge and discharge circulation life.But, the theoretical specific capacity of carbon negative pole material only has 372mAh/g, its energy density Cannot meet the requirement to energy density of present various electronic equipment for consumption, especially energy storage device and electric motor car, therefore In the urgent need to finding the negative material of a kind of high-energy-density that can replace material with carbon element.
Wherein, silicon based anode material is with the discharge platform of its huge lithium storage content (4200mAh/g), slightly above material with carbon element And the advantage such as the rich reserves in the earth's crust and receive much concern.But in charge and discharge process, the removal lithium embedded reaction of silicon will companion With the change in volume of 310%, easily cause the cracking of electrode and coming off of active substance, concurrently form the solid electrolytic of instability Matter interfacial film (SEI film), thus cause the deterioration of electrode cycle performance and high rate performance.Additionally, relatively low silicon materials electronics electricity Conductance and lithium ion mobility speed have also had a strong impact on the chemical property of silicium cathode material.
One of solution to the problems described above is synthesis of silica-base complex, with the volumetric expansion of buffer electrode, improves electrode Cyclical stability.Material with carbon element becomes the most commonly used material of selection with electric conductivity and the mechanical performance of its excellence.By carbon material Material and silicon synthetic composite material, be possible not only to effective buffer volumes and expand, prevent nano silicon particles from assembling, it is also possible to improve electrode Electric conductivity, obtains stable SEI film, thus cycle performance and the coulombic efficiency of silicium cathode is greatly improved.Wherein, Graphene is with it The advantages such as excellent flexibility, good electron conduction, less density and suitable embedding lithium ability and become silicon-carbon cathode material The optimum activity matrix of material.
The graphene oxide of different proportion is mixed by Chinese patent CN201010256875.X with nano silica fume, ultrasonic point Dissipating, last sucking filtration or convection drying become the mode of cake/film to prepare the graphene/silicon composite film material of self supporting structure. Although silicon grain can be dispersed in the Graphene of lamellar, silicon volumetric expansion there is certain cushioning effect.But, silicon with The bond strength of Graphene is the highest, and clearance space is less, is susceptible to structure and separates in silicon volumetric expansion contraction process, it is difficult to Obtain preferable cycle performance.
Summary of the invention
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, this preparation method the porous graphene/silicon composite prepared has preferable cyclicity Energy.
The invention provides the preparation method of a kind of porous graphene/silicon composite, comprise the following steps:
A1) aqueous solution of graphene oxide, nano silica fume, deionized water, surfactant and organic solvent are mixed, To mixed solution；
B) described mixed solution is carried out hydro-thermal reaction, obtain graphene/silicon pluralgel；
C1) described graphene/silicon pluralgel is dried at normal pressure, 30 DEG C～90 DEG C 0.5～7h, then carries out freezing It is dried, 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) described mixed solution is carried out hydro-thermal reaction, obtain graphene/silicon pluralgel；
C2) by described graphene/silicon pluralgel under 0.5～5 atmospheric pressure, 30 DEG C～90 DEG C drying 0.5～7h, so After carry out lyophilization, heat treatment, obtain porous graphene/silicon composite.
Preferably, the mass concentration of the aqueous solution of described graphene oxide is 0.5mg/mL～7mg/mL.
Preferably, described nano silica fume is 1:6～5:1 with the mass ratio of graphene oxide, described nano silica fume and surface The mass ratio of activating agent is 1:10～10:1, and described deionized water is 1:6～6:1 with the volume ratio of organic solvent, described organic Solvent is 1:6～6:1 with the volume ratio of the aqueous solution of graphene oxide.
Preferably, described organic solvent one in ethanol, ethylene glycol or glycerol.
Preferably, step A2) in, described nano silica fume and graphene oxide mass ratio are 1:6～5:1, described nano-silicon Powder is 1:10～10:1 with the mass ratio of surfactant, and described deionized water with the volume ratio of the aqueous solution of graphene oxide is 1:6～6:1.
Preferably, the temperature of described hydro-thermal reaction is 100 DEG C～200 DEG C, and the time of described hydro-thermal reaction is 2h～15h.
Preferably, step C2) in, by described graphene/silicon pluralgel 0.7～0.9 atmospheric pressure or 1.5～3 Under atmospheric pressure, dry 0.5～7h, then carry out lyophilization, heat treatment for 30 DEG C～90 DEG C, obtain porous graphene/silicon and be combined Material.
Preferably, the temperature of described heat treatment is 300 DEG C～1000 DEG C, and the time of described heat treatment is 1h～8h.
The invention provides porous graphene/silicon composite prepared by a kind of above-mentioned preparation method.
Present invention also offers a kind of lithium ion battery, including positive pole, negative pole, barrier film and electrolyte, described negative pole includes Porous graphene/silicon composite mentioned above.
The invention provides the preparation method of a kind of porous graphene/silicon composite, comprise the following steps:
A1) aqueous solution of graphene oxide, nano silica fume, deionized water, surfactant and organic solvent are mixed, To mixed solution；B) described mixed solution is carried out hydro-thermal reaction, obtain graphene/silicon pluralgel；C1) by described graphite Alkene/silicon pluralgel dries 0.5～7h at normal pressure, 30 DEG C～90 DEG C, then carries out lyophilization, is thermally treated resulting in porous stone Ink alkene/silicon composite；
Or
A2) aqueous solution of graphene oxide, nano silica fume, deionized water and surfactant are mixed, obtain mixing molten Liquid；B) described mixed solution is carried out hydro-thermal reaction, obtain graphene/silicon pluralgel；C2) described graphene/silicon is combined Gel, under 0.5～5 atmospheric pressure, is dried 0.5～7h, is then carried out lyophilization, heat treatment, obtain porous for 30 DEG C～90 DEG C Graphene/silicon composite.
The present invention is when preparing graphene/silicon pluralgel, by adding organic solvent in the feed, the most at ambient pressure Carry out the drying and processing of specified temp；Or the air pressure dried by control and temperature, to control graphene/silicon pluralgel Contraction rate, thus obtain porosity and aperture adjustable graphene/silicon composite gel material, carry out lyophilization the most again Process, make the Structured cured of graphene/silicon pluralgel.Porous graphene/silicon composite the hole prepared by said method Footpath is controlled, and silicon is higher with the bond strength of Graphene, and the composite of loose structure has a large amount of gap, can effectively accommodate silicon Volumetric expansion, and do not cause the change in volume that composite is bigger, relatively stable SEI film can also be obtained simultaneously.It addition, hole The existence in road can increase the reaction rate of removal lithium embedded, is conducive to improving cycle performance and the high rate performance of composite, and then Ensure that prepared porous graphene/silicon composite has preferable cycle performance and high rate performance.Experiment shows, the present invention The lithium ion battery prepared is under 0.5C multiplying power, and first discharge specific capacity is 1325～1785mAh/g, after circulating 200 times, and electric discharge Specific capacity is 940～1600mAh/g, and capability retention is not less than 71%.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the porous graphene/silicon composite of the embodiment of the present invention 1 preparation；
Fig. 2 is the SEM figure after porous graphene/silicon composite prepared by the embodiment of the present invention 1 grinds；
Fig. 3 is the cyclic curve figure of the lithium ion battery of the embodiment of the present invention 1～3 preparation；
Fig. 4 is the lithium ion battery of the embodiment of the present invention 1～3 preparation specific discharge capacity curve chart under different multiplying；
Fig. 5 is the SEM figure of the porous graphene/silicon composite of the embodiment of the present invention 2 preparation；
Fig. 6 is the SEM figure after porous graphene/silicon composite prepared by the embodiment of the present invention 2 grinds；
Fig. 7 is the SEM figure of the porous graphene/silicon composite of the embodiment of the present invention 3 preparation；
Fig. 8 is the SEM figure after porous graphene/silicon composite prepared by the embodiment of the present invention 3 grinds；
Fig. 9 is the cyclic curve figure of the lithium ion battery of the embodiment of the present invention 9～11 preparation；
Figure 10 is the lithium ion battery of the embodiment of the present invention 9～11 preparation specific discharge capacity curve under different multiplying Figure.
Detailed description of the invention
Below in conjunction with the embodiment of the present invention, technical scheme is clearly and completely described, it is clear that institute The embodiment described is only a part of embodiment of the present invention rather than whole embodiments.Based on the embodiment in the present invention, The every other embodiment that those of ordinary skill in the art are obtained under not making creative work premise, broadly falls into this The scope of bright protection.
The invention provides the preparation method of a kind of porous graphene/silicon composite, comprise the following steps:
A1) aqueous solution of graphene oxide, nano silica fume, deionized water, surfactant and organic solvent are mixed, To mixed solution；
B) described mixed solution is carried out hydro-thermal reaction, obtain graphene/silicon pluralgel；
C1) described graphene/silicon pluralgel is dried at normal pressure, 30 DEG C～90 DEG C 0.5～7h, then carries out freezing It is dried, 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) described mixed solution is carried out hydro-thermal reaction, obtain graphene/silicon pluralgel；
C2) by described graphene/silicon pluralgel under 0.5～5 atmospheric pressure, 30 DEG C～90 DEG C drying 0.5～7h, so After carry out lyophilization, heat treatment, obtain porous graphene/silicon composite.
The preparation method of porous graphene/silicon composite that the present invention provides includes two schemes, by the feed Add organic solvent and prepare graphene/silicon pluralgel, the most described graphene/silicon pluralgel is entered Row is dried；Or the air pressure dried by regulation and temperature, to control the contraction rate of graphene/silicon pluralgel, and then The aperture of regulation and control pluralgel and the thickness of graphene sheet layer, improve the conjugation of silicon and Graphene.Finally, done by freezing Dry and be thermally treated resulting in the graphene/silicon composite of loose structure, this composite structure is stable, mechanical performance and conduction Function admirable, is applied in lithium ion battery have preferable cycle performance and high rate performance.
The first scheme above-mentioned comprises the following steps:
A1) aqueous solution of graphene oxide, nano silica fume, deionized water, surfactant and organic solvent are mixed, To mixed solution；
B) described mixed solution is carried out hydro-thermal reaction, obtain graphene/silicon pluralgel；
C1) described graphene/silicon pluralgel is dried at normal pressure, 30 DEG C～90 DEG C 0.5～7h, then carries out freezing It is dried, is thermally treated resulting in porous graphene/silicon composite.
In the present invention, described graphene oxide is preferably prepared according to Hummers method.After obtaining graphene oxide, this Bright prepared the aqueous solution obtaining graphene oxide.The compound method of the aqueous solution of described graphene oxide is not had by the present invention Special restriction, uses the compound method of aqueous solution well known to those skilled in the art.In the present invention, described oxidation stone The mass concentration of the aqueous solution of ink 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 described graphene oxide and nano silica fume, go Ionized water, surfactant and organic solvent mixing, obtain mixed solution.
In the present invention, described surfactant is preferably nonionic surfactant, more preferably polyvinyl pyrrole One in alkanone (PVP), polydiallyldimethyl ammonium chloride (PDDA) and kayexalate (PSS).Described organic solvent It is preferably ethanol, ethylene glycol or glycerol.The present invention uses ethanol as organic solvent, dries within specified temperatures Time, graphene/silicon pluralgel contraction rate is very fast.The present invention use ethylene glycol or glycerol as organic solvent, specific At a temperature of when drying, graphene/silicon pluralgel contraction rate is relatively slow, be more prone to the aperture controlling pluralgel with And the thickness of graphene sheet layer.
Described nano silica fume is 1:6～5:1, preferably 1:5～3:1 with the mass ratio of graphene oxide, more preferably 1: 1；Described nano silica fume is 1:10～10:1, preferably 1:5～5:1, more preferably 2:1 with the mass ratio of surfactant；Institute The volume ratio stating deionized water and organic solvent is 1:6～6:1, preferably 1:5～5:1, more preferably 1:1；Described organic molten Agent is 1:6～6:1, preferably 1:5～5:1, more preferably 1:1 with the volume ratio of the aqueous solution of graphene oxide.
The source of the present invention raw material components to being used there is no special restriction, can be the most commercially available.
After obtaining mixed solution, described mixed solution is carried out hydro-thermal reaction by the present invention, obtains graphene/silicon compound solidifying Glue.In the present invention, the temperature of described hydro-thermal reaction is preferably 100 DEG C～200 DEG C；The time of described hydro-thermal reaction is preferably 2h ～15h.
The graphene/silicon pluralgel obtained is dried 0.5～7h at normal pressure, 30 DEG C～90 DEG C by the present invention, is dried Composite after Gan.The time of described drying is unsuitable long, because drying time is long, Graphene can be caused to reunite serious, Thus lose spacial framework.The present invention there is no special restriction to the mode of described drying, uses those skilled in the art Known to drying mode.
Concrete, when organic solvent selected in raw material is ethanol, preferably drying temperature is 30 DEG C～70 DEG C, dries 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 glycerol, preferably drying temperature is 40 DEG C～90 DEG C, and drying time is 1～7h, preferred Drying temperature is 60 DEG C～70 DEG C, and drying time is 3～6h.
Composite after above-mentioned drying is carried out lyophilization, makes the Structured cured of graphene/silicon pluralgel.Described Cryodesiccated temperature is preferably-70 DEG C～-10 DEG C, and the described cryodesiccated time is preferably 1h～60h.
Composite after lyophilization is carried out heat treatment, obtains porous graphene/silicon composite, preferably in inertia Heat treatment is carried out under atmosphere.The present invention there is no special restriction to the mode of described heat treatment, uses those skilled in the art ripe The heat treatment mode known, present invention preferably employs annealing.The temperature of described heat treatment is preferably 300 DEG C～1000 DEG C, the time of described heat treatment is preferably 1h～8h.It is special that the noble gas that acquisition inert atmosphere is used be there is no by the present invention Limit, noble gas well known to those skilled in the art can be used.Present invention preferably employs argon.
Above-mentioned first scheme comprises the following steps:
A2) aqueous solution of graphene oxide, nano silica fume, deionized water and surfactant are mixed, obtain mixing molten Liquid；
B) described mixed solution is carried out hydro-thermal reaction, obtain graphene/silicon pluralgel；
C2) by described graphene/silicon pluralgel under 0.5～5 atmospheric pressure, 30 DEG C～90 DEG C drying 0.5～7h, so After carry out lyophilization, heat treatment, obtain porous graphene/silicon composite.
In the present invention, described graphene oxide is preferably prepared according to Hummers method.After obtaining graphene oxide, this Bright prepared the aqueous solution obtaining graphene oxide.The compound method of the aqueous solution of described graphene oxide is not had by the present invention Special restriction, uses the compound method of aqueous solution well known to those skilled in the art.In the present invention, described oxidation stone The mass concentration of the aqueous solution of ink 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 described graphene oxide and nano silica fume, go Ionized water and surfactant mixing, obtain mixed solution.
In the present invention, described surfactant is preferably nonionic surfactant, preferably polyvinylpyrrolidine Ketone (PVP), polydiallyldimethyl ammonium chloride (PDDA), kayexalate (PSS).
Described nano silica fume and graphene oxide mass ratio are 1:6～5:1, preferably 1:5～3:1, more preferably 1:1； Described nano silica fume is 1:10～10:1, preferably 1:5～5:1 with the mass ratio of surfactant, more preferably 2: 1；Described Deionized water is 1:6～6:1, preferably 1:5～5:1 with the volume ratio of the aqueous solution of graphene oxide, more preferably 1: 1.
The source of the present invention raw material components to being used there is no special restriction, can be the most commercially available.
After obtaining mixed solution, described mixed solution is carried out hydro-thermal reaction by the present invention, obtains graphene/silicon compound solidifying Glue.In the present invention, the temperature of described hydro-thermal reaction is preferably 100 DEG C～200 DEG C；The time of described hydro-thermal reaction is preferably 2h ～15h.
The present invention by the graphene/silicon pluralgel that obtains more than or equal to 0.5 less than 1 atmospheric pressure or little more than 1 Dry under equal to 5 atmospheric pressure, the composite after being dried.The present invention there is no special limit to the mode dried System, uses drying mode well known to those skilled in the art.The temperature of described drying is 30 DEG C～90 DEG C, described drying Time is 0.5h～7h.
Concrete, the graphene/silicon pluralgel obtained is dried under more than or equal to 0.5 less than 1 atmospheric pressure by the present invention Dry, preferably to dry under 0.7～0.9 atmospheric pressure, graphene/silicon pluralgel contraction rate is very fast, preferably dries 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 be 2～ 3.5h.The present invention is dried under more than 1 less than or equal to 5 atmospheric pressure, preferably dries under 1.5～3 atmospheric pressure, Graphene/silicon pluralgel contraction rate is relatively slow, is more prone to control aperture and the thickness of graphene sheet layer of pluralgel, Preferably drying temperature is 40 DEG C～90 DEG C, and drying time is 1～7h；Preferred drying temperature is 60 DEG C～70 DEG C, during drying Between be 3～6h.
Air pressure that the present invention is dried by regulation and temperature, to control graphene/silicon pluralgel contraction rate, thus adjust The aperture of control pluralgel and the thickness of graphene sheet layer, improve the conjugation of silicon and Graphene.
Composite after above-mentioned drying is carried out lyophilization, makes the Structured cured of graphene/silicon pluralgel.Described Cryodesiccated temperature is preferably-70 DEG C～-10 DEG C, and the described cryodesiccated time is preferably 1h～60h.
Composite after lyophilization is carried out heat treatment, obtains porous graphene/silicon composite, preferably in inertia Heat treatment is carried out under atmosphere.The present invention there is no special restriction to the mode of described heat treatment, uses those skilled in the art ripe The heat treatment mode known, present invention preferably employs annealing.The temperature of described heat treatment is preferably 300 DEG C～1000 DEG C, the time of described heat treatment is preferably 1h～8h.It is special that the noble gas that acquisition inert atmosphere is used be there is no by the present invention Limit, noble gas well known to those skilled in the art can be used.Present invention preferably employs argon.
The invention provides porous graphene/silicon composite prepared by a kind of above-mentioned preparation method.The present invention provides Porous graphene/silicon composite includes that silicon nanoparticle and Graphene, described silicon nanoparticle are embedded in described Graphene Between lamella, form the composite of loose structure.The particle diameter of described silicon nanoparticle is preferably 100nm～120nm.The present invention The source of described nano-silicon be there is no special restriction, can make by oneself or commercially, meet nano-scale.This The bright nano silica fume preferably employing Aladdin Reagent Company.
Porous graphene/silicon composite that the present invention provides, silicon nanoparticle is higher with the conjugation of Graphene, and During the sizing mixing of later stage, the aperture of Graphene is difficult to be destroyed, it is ensured that the circulation of the lithium ion battery negative material prepared Performance, and then make lithium ion battery have preferable cycle performance.
Present invention also offers a kind of lithium ion battery, including positive pole, negative pole, barrier film and electrolyte, described negative pole includes Porous graphene/silicon composite mentioned above.
The present invention does not has special restriction to the kind of described positive pole, barrier film and electrolyte, and e.g., described positive pole can use lithium Sheet；Described barrier film can use microporous polypropylene membrane；Described electrolyte can use ethylene carbonate (EC) and dimethyl carbonate (DMC) Mixed liquor.Concrete, the present invention is by above-mentioned porous graphene/silicon composite and binding agent (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, add suitable quantity of water As dispersant furnishing slurry, then it is coated uniformly in copper foil current collector, and vacuum dried, roll-in, it is prepared as negative plate； With lithium metal for electrode, the LiPF of 1mol/L6Mixed solvent (EC: DMC=1: 1 volume ratio) be electrolyte, polypropylene is micro- Pore membrane (Celgard 2400) is barrier film, is assembled into simulated battery in the glove box of argon shield.
The present invention simulated battery to obtaining carries out constant current charge-discharge experiment, tests the cyclicity of described lithium ion battery Can, charging/discharging voltage is limited in 0.001～1.5 volt, and the electric current density of discharge and recharge is 500mA/g.Use the test of Land tester The chemical property of battery, test condition is room temperature.Test result indicate that, the lithium ion battery that the present invention prepares is in 0.5C multiplying power Under, first discharge specific capacity is 1325～1785mAh/g, and after circulating 200 times, specific discharge capacity is 940～1600mAh/g, holds Amount conservation rate is not less than 71%, has preferable cycle performance.
Meanwhile, the lithium ion battery obtained cycle performance under different multiplying is also investigated by the present invention, experiment Result shows, the lithium ion battery that the present invention provides all has higher specific capacity under 0.1C, 0.2C, 0.5C, 1C and 2C, times Rate better performances.
The invention provides the preparation method of a kind of porous graphene/silicon composite, comprise the following steps:
A1) aqueous solution of graphene oxide, nano silica fume, deionized water, surfactant and organic solvent are mixed, To mixed solution；
B) described mixed solution is carried out hydro-thermal reaction, obtain graphene/silicon pluralgel；
C1) described graphene/silicon pluralgel is dried at normal pressure, 30 DEG C～90 DEG C 0.5～7h, then carries out freezing It is dried, 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) described mixed solution is carried out hydro-thermal reaction, obtain graphene/silicon pluralgel；
C2) by described graphene/silicon pluralgel under 0.5～5 atmospheric pressure, 30 DEG C～90 DEG C drying 0.5～7h, so After carry out lyophilization, heat treatment, obtain porous graphene/silicon composite.
The present invention prepares graphene/silicon pluralgel, then in specific temperature by adding alcohols solvent in the feed With under normal pressure, described graphene/silicon pluralgel is dried；Or the air pressure dried by regulation and temperature, control stone Ink alkene/silicon pluralgel contraction rate, obtains the adjustable pluralgel in aperture, lyophilization postmenstruation and be thermally treated resulting in porous Graphene/silicon composite.This composite structure is stable, and mechanical performance and electric conductivity are excellent, Graphene and the combination of silicon Intensity is higher, is applied to lithium ion battery and has preferable cycle performance and high rate performance.Test result indicate that, the present invention prepares Lithium ion battery under 0.5C multiplying power, first discharge specific capacity is 1325～1785mAh/g, after circulating 200 times, discharge specific volume Amount is 940～1600mAh/g, and capability retention is not less than 71%, has preferable cycle performance.
In order to further illustrate the present invention, a kind of porous graphene/silicon provided the present invention below in conjunction with embodiment is multiple Condensation material, its preparation method and lithium ion battery are described in detail, but can not be understood as scope Limit.
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 is 6mg/mL, described nano silica fume with The mass ratio of graphene oxide is 1: 1, and nano silica fume is 2: 1 with the mass ratio of polyvinylpyrrolidone, deionized water and second two The volume ratio of alcohol (or glycerol) is 1: 1, and ethylene glycol (or glycerol) is 1: 1 with the volume ratio of the aqueous solution of graphene oxide；
Mixed solution is placed in reactor, 180 DEG C of hydro-thermal reactions 12h, obtains graphene/silicon pluralgel；
By graphene/silicon pluralgel at normal pressure, 60 DEG C of drying and processing 5h, then process in (-60) DEG C lyophilization 48h, finally, under an inert atmosphere, 800 DEG C of high annealing 4h, obtains porous graphene/silicon composite.
Porous graphene/the silicon composite obtained is scanned electron-microscope scanning analysis by the present invention, result such as Fig. 1 and 2 Shown in.Fig. 1 is the SEM figure of the porous graphene/silicon composite of the embodiment of the present invention 1 preparation, as seen from Figure 1, and this Porous graphene/the silicon composite of bright offer is loose structure.Fig. 2 is to be combined by porous graphene/silicon that the present invention obtains Sample SEM after material grinds schemes, and as seen from Figure 2, the porous graphene/silicon composite after grinding is for many Pore structure.
The present invention is by above-mentioned porous graphene/silicon composite and binding agent (SBR: CMC=3: 7 mass ratio), conductive agent Super P mixes according to the weight ratio of 80: 10: 10, and addition suitable quantity of water, as dispersant furnishing slurry, is then coated uniformly on copper On paper tinsel collector and vacuum dried, roll-in, is prepared as negative plate；With lithium metal for electrode, the LiPF of 1mol/L6Mixed Bonding solvent (EC: DMC=1: 1 volume ratio) is electrolyte, and microporous polypropylene membrane (Celgard 2400) is barrier film, in argon shield Glove box in be assembled into simulated battery.By the simulated battery that is assembled in Land tester (Wuhan Xin Nuo Electronics Co., Ltd.) On carry out constant current charge-discharge test, charging/discharging voltage interval is 0.001～1.5V, and the electric current density of discharge and recharge is 500mA g-1, Obtain its cycle performance curve as shown in Figure 3.
Test result indicate that, lithium ion battery first discharge specific capacity under 0.5C multiplying power that the present invention provides all is not less than 1785mAh/g, after cycle charge-discharge 200 times, capability retention is not less than 89%, has preferable cycle performance.Have preferably Cycle performance.
Meanwhile, the lithium ion battery obtained discharge cycles performance under different multiplying is also investigated by the present invention, As shown in Figure 4.Test result indicate that, the lithium ion battery that the present invention provides all has under 0.1C, 0.2C, 0.5C, 1C and 2C Higher specific capacity, after 0.1C circulates 10 times, capacity is that after 2124mAh/g, 0.2C circulate 10 times, capacity is 1934mAh/g, 0.5C After circulating 10 times, capacity is that after 1734mAh/g, 1C circulate 10 times, capacity is still to be not less than after 1509mAh/g, 2C circulate 10 times 1244mAh/g, high rate performance is preferable.
Embodiment 2
By the aqueous solution of graphene oxide and nano silica fume, deionized water, polydiallyldimethyl ammonium chloride and ethylene glycol (or Glycerol) mixing, obtain mixed solution.Wherein, the mass concentration of the aqueous solution of graphene oxide is 0.5mg/mL, described nanometer The mass ratio of silica flour and graphene oxide is 5:1, and nano silica fume is 10:1 with the mass ratio of polydiallyldimethyl ammonium chloride, go from Sub-water is 1:6 with the volume ratio of ethylene glycol (or glycerol), the body of the aqueous solution of ethylene glycol (or glycerol) and graphene oxide Long-pending ratio is 6:1；
Mixed solution is placed in reactor, 200 DEG C of hydro-thermal reactions 2h, obtains graphene/silicon pluralgel；
By graphene/silicon pluralgel at normal pressure, 90 DEG C of drying and processing 0.5h, then process in (-70) DEG C lyophilization 1h, finally, under an inert atmosphere, 1000 DEG C of high annealing 1h, obtains porous graphene/silicon composite.
Porous graphene/the silicon composite obtained is scanned electron-microscope scanning analysis by the present invention, result such as Fig. 5 and 6 Shown in.Fig. 5 is the SEM figure of the porous graphene/silicon composite of the embodiment of the present invention 2 preparation, as seen from Figure 5, and this Porous graphene/the silicon composite of bright offer is loose structure.Fig. 6 be the embodiment of the present invention 2 is obtained porous graphene/ Sample SEM after silicon composite grinds schemes, as seen from Figure 6, and the porous graphene after grinding/silicon composite wood Material is loose structure.
The present invention is by above-mentioned porous graphene/silicon composite and binding agent (SBR:CMC=3:7 mass ratio), conductive agent Super P mixes according to the weight ratio of 80:10:10, and addition suitable quantity of water, as dispersant furnishing slurry, is then coated uniformly on copper On paper tinsel collector and vacuum dried, roll-in, is prepared as negative plate；With lithium metal for electrode, the LiPF of 1mol/L6Mixed Bonding solvent (EC: DMC=1:1 volume ratio) is electrolyte, and microporous polypropylene membrane (Celgard 2400) is barrier film, in argon shield Glove box in be assembled into simulated battery.By the simulated battery that is assembled in Land tester (Wuhan Xin Nuo Electronics Co., Ltd.) On carry out constant current charge-discharge test, charging/discharging voltage interval is 0.001～1.5V, and the electric current density of discharge and recharge is 500mA g-1, Obtain its cycle performance curve as shown in Figure 3.
Test result indicate that, lithium ion battery first discharge specific capacity under 0.5C multiplying power that the present invention provides is 1330mAh/g, after cycle charge-discharge 200 times, capability retention is not less than 72%, has preferable cycle performance.
Meanwhile, the lithium ion battery obtained discharge cycles performance under different multiplying is also investigated by the present invention, As shown in Figure 4.Test result indicate that, the lithium ion battery that the present invention provides all has under 0.1C, 0.2C, 0.5C, 1C and 2C Higher specific capacity, after 0.1C circulates 10 times, capacity is that after 1613mAh/g, 0.2C circulate 10 times, capacity is 1501mAh/g, 0.5C After circulating 10 times, capacity is that after 1328mAh/g, 1C circulate 10 times, capacity is still to be not less than after 1214mAh/g, 2C circulate 10 times 1030mAh/g, high rate performance is 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 is 7mg/mL, described nano silica fume with The mass ratio of graphene oxide is 1:6, and nano silica fume is 1:10 with the mass ratio of kayexalate, deionized water and second two The volume ratio of alcohol (or glycerol) is 6:1, and ethylene glycol (or glycerol) is 1:6 with the volume ratio of the aqueous solution of graphene oxide；
Mixed solution is placed in reactor, 100 DEG C of hydro-thermal reactions 15h, obtains graphene/silicon pluralgel；
By graphene/silicon pluralgel at normal pressure, 30 DEG C of drying and processing 7h, then process in (-10) DEG C lyophilization 60h, finally, under an inert atmosphere, 300 DEG C of high annealing 8h, obtains porous graphene/silicon composite.
Porous graphene/the silicon composite obtained is scanned electron-microscope scanning analysis by the present invention, result such as Fig. 7 and 8 Shown in.Fig. 7 is the SEM figure of the porous graphene/silicon composite of the embodiment of the present invention 3 preparation, as seen from Figure 7, and this Porous graphene/the silicon composite of bright offer is loose structure.Fig. 8 be the embodiment of the present invention 3 is obtained porous graphene/ Sample SEM after silicon composite grinds schemes, as seen from Figure 8, and the porous graphene after grinding/silicon composite wood Material is loose structure.
The present invention is by above-mentioned porous graphene/silicon composite and binding agent (SBR:CMC=3:7 mass ratio), conductive agent Super P mixes according to the weight ratio of 80:10:10, and addition suitable quantity of water, as dispersant furnishing slurry, is then coated uniformly on copper On paper tinsel collector and vacuum dried, roll-in, is prepared as negative plate；With lithium metal for electrode, the LiPF of 1mol/L6Mixed Bonding solvent (EC: DMC=1:1 volume ratio) is electrolyte, and microporous polypropylene membrane (Celgard 2400) is barrier film, in argon shield Glove box in be assembled into simulated battery.By the simulated battery that is assembled in Land tester (Wuhan Xin Nuo Electronics Co., Ltd.) On carry out constant current charge-discharge test, charging/discharging voltage interval is 0.001～1.5V, and the electric current density of discharge and recharge is 500mA g-1, Obtain its cycle performance curve as shown in Figure 3.
Test result indicate that, lithium ion battery first discharge specific capacity under 0.5C multiplying power that the present invention provides is 1590mAh/g, after cycle charge-discharge 200 times, capability retention is not less than 76%, has preferable cycle performance.
Meanwhile, the lithium ion battery obtained discharge cycles performance under different multiplying is also investigated by the present invention, As shown in Figure 4.Test result indicate that, the lithium ion battery that the present invention provides all has under 0.1C, 0.2C, 0.5C, 1C and 2C Higher specific capacity, after 0.1C circulates 10 times, capacity is that after 1892mAh/g, 0.2C circulate 10 times, capacity is 1748mAh/g, 0.5C After circulating 10 times, capacity is that after 1560mAh/g, 1C circulate 10 times, capacity is still to be not less than after 1358mAh/g, 2C circulate 10 times 1157mAh/g, high rate performance is 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 is 1mg/mL, described nano silica fume with The mass ratio of graphene oxide is 1:5, and nano silica fume is 1:5 with the mass ratio of polyvinylpyrrolidone, deionized water and second two The volume ratio of alcohol (or glycerol) is 5:1, and ethylene glycol (or glycerol) is 1:5 with the volume ratio of the aqueous solution of graphene oxide；
Mixed solution is placed in reactor, 120 DEG C of hydro-thermal reactions 8h, obtains graphene/silicon pluralgel；
By graphene/silicon pluralgel at normal pressure, 70 DEG C of drying and processing 4h, then process in (-40) DEG C lyophilization 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 binding agent (SBR:CMC=3:7 mass ratio), conductive agent Super P mixes according to the weight ratio of 80:10:10, and addition suitable quantity of water, as dispersant furnishing slurry, is then coated uniformly on copper On paper tinsel collector and vacuum dried, roll-in, is prepared as negative plate；With lithium metal for electrode, the LiPF of 1mol/L6Mixed Bonding solvent (EC: DMC=1:1 volume ratio) is electrolyte, and microporous polypropylene membrane (Celgard 2400) is barrier film, in argon shield Glove box in be assembled into simulated battery.By the simulated battery that is assembled in Land tester (Wuhan Xin Nuo Electronics Co., Ltd.) On carry out constant current charge-discharge test, charging/discharging voltage interval is 0.001～1.5V, and the electric current density of discharge and recharge is 500mA g-1。
Test result indicate that, lithium ion battery first discharge specific capacity under 0.5C multiplying power that the present invention provides is 1750mAh/g, after cycle charge-discharge 200 times, capability retention is not less than 82%.
Meanwhile, the lithium ion battery obtained discharge cycles performance under different multiplying is also investigated by the present invention. Test result indicate that, the lithium ion battery that the present invention provides all has higher specific volume under 0.1C, 0.2C, 0.5C, 1C and 2C Amount, after 0.1C circulates 10 times, capacity is that after 1922mAh/g, 0.2C circulate 10 times, capacity is after 1835mAh/g, 0.5C circulate 10 times Capacity is that after 1660mAh/g, 1C circulate 10 times, capacity is still not less than 1250mAh/g after 1485mAh/g, 2C circulate 10 times.
Embodiment 5
The aqueous solution of graphene oxide is mixed with nano silica fume, deionized water, polyvinylpyrrolidone and ethanol, obtains Mixed solution.Wherein, the mass concentration of the aqueous solution of graphene oxide is 6mg/mL, described nano silica fume and graphene oxide Mass ratio is 1:1, and nano silica fume is 2:1 with the mass ratio of polyvinylpyrrolidone, and deionized water is 1 with the volume ratio of ethanol: 1, ethanol is 1:1 with the volume ratio of the aqueous solution of graphene oxide；
Mixed solution is placed in reactor, 180 DEG C of hydro-thermal reactions 12h, obtains graphene/silicon pluralgel；
By graphene/silicon pluralgel at normal pressure, 60 DEG C of drying and processing 2h, then process in (-60) DEG C lyophilization 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 binding agent (SBR:CMC=3:7 mass ratio), conductive agent Super P mixes according to the weight ratio of 80:10:10, and addition suitable quantity of water, as dispersant furnishing slurry, is then coated uniformly on copper On paper tinsel collector and vacuum dried, roll-in, is prepared as negative plate；With lithium metal for electrode, the LiPF of 1mol/L6Mixed Bonding solvent (EC: DMC=1:1 volume ratio) is electrolyte, and microporous polypropylene membrane (Celgard 2400) is barrier film, in argon shield Glove box in be assembled into simulated battery.By the simulated battery that is assembled in Land tester (Wuhan Xin Nuo Electronics Co., Ltd.) On carry out constant current charge-discharge test, charging/discharging voltage interval is 0.001～1.5V, and the electric current density of discharge and recharge is 500mA g-1。
Test result indicate that, lithium ion battery first discharge specific capacity under 0.5C multiplying power that the present invention provides is 1630mAh/g, after cycle charge-discharge 200 times, capability retention is not less than 80%, has preferable cycle performance.
Meanwhile, the lithium ion battery obtained discharge cycles performance under different multiplying is also investigated by the present invention. Test result indicate that, the lithium ion battery that the present invention provides all has higher specific volume under 0.1C, 0.2C, 0.5C, 1C and 2C Amount, after 0.1C circulates 10 times, capacity is that after 2010mAh/g, 0.2C circulate 10 times, capacity is after 1825mAh/g, 0.5C circulate 10 times Capacity is that after 1621mAh/g, 1C circulate 10 times, capacity is still not less than 1124mAh/g after 1486mAh/g, 2C circulate 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 ethanol, Obtain mixed solution.Wherein, the mass concentration of the aqueous solution of graphene oxide is 0.5mg/mL, described nano silica fume and oxidation stone The mass ratio of ink alkene is 5:1, and nano silica fume is 10:1 with the mass ratio of polydiallyldimethyl ammonium chloride, deionized water and ethanol Volume ratio is 1:6, and ethanol is 6:1 with the volume ratio of the aqueous solution of graphene oxide；
Mixed solution is placed in reactor, 200 DEG C of hydro-thermal reactions 2h, obtains graphene/silicon pluralgel；
By graphene/silicon pluralgel at normal pressure, 90 DEG C of drying and processing 0.5h, then process in (-70) DEG C lyophilization 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 binding agent (SBR:CMC=3:7 mass ratio), conductive agent Super P mixes according to the weight ratio of 80:10:10, and addition suitable quantity of water, as dispersant furnishing slurry, is then coated uniformly on copper On paper tinsel collector and vacuum dried, roll-in, is prepared as negative plate；With lithium metal for electrode, the LiPF of 1mol/L6Mixed Bonding solvent (EC: DMC=1:1 volume ratio) is electrolyte, and microporous polypropylene membrane (Celgard 2400) is barrier film, in argon shield Glove box in be assembled into simulated battery.By the simulated battery that is assembled in Land tester (Wuhan Xin Nuo Electronics Co., Ltd.) On carry out constant current charge-discharge test, charging/discharging voltage interval is 0.001～1.5V, and the electric current density of discharge and recharge is 500mA g-1。
Test result indicate that, lithium ion battery first discharge specific capacity under 0.5C multiplying power that the present invention provides is 1325mAh/g, after cycle charge-discharge 200 times, capability retention is not less than 71%, has preferable cycle performance.
Meanwhile, the lithium ion battery obtained discharge cycles performance under different multiplying is also investigated by the present invention. Test result indicate that, the lithium ion battery that the present invention provides all has higher specific volume under 0.1C, 0.2C, 0.5C, 1C and 2C Amount, after 0.1C circulates 10 times, capacity is that after 1612mAh/g, 0.2C circulate 10 times, capacity is after 1500mAh/g, 0.5C circulate 10 times Capacity is that after 1322mAh/g, 1C circulate 10 times, capacity is still not less than 1025mAh/g after 1212mAh/g, 2C circulate 10 times.
Embodiment 7
The aqueous solution of graphene oxide is mixed with nano silica fume, deionized water, kayexalate and ethanol, obtains Mixed solution.Wherein, the mass concentration of the aqueous solution of graphene oxide is 7mg/mL, described nano silica fume and graphene oxide Mass ratio is 1:6, and nano silica fume is 1:10 with the mass ratio of kayexalate, and deionized water is 6 with the volume ratio of ethanol: 1, ethanol is 1:6 with the volume ratio of the aqueous solution of graphene oxide；
Mixed solution is placed in reactor, 100 DEG C of hydro-thermal reactions 15h, obtains graphene/silicon pluralgel；
By graphene/silicon pluralgel at normal pressure, 30 DEG C of drying and processing 7h, then process in (-10) DEG C lyophilization 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 binding agent (SBR:CMC=3:7 mass ratio), conductive agent Super P mixes according to the weight ratio of 80:10:10, and addition suitable quantity of water, as dispersant furnishing slurry, is then coated uniformly on copper On paper tinsel collector and vacuum dried, roll-in, is prepared as negative plate；With lithium metal for electrode, the LiPF of 1mol/L6Mixed Bonding solvent (EC: DMC=1:1 volume ratio) is electrolyte, and microporous polypropylene membrane (Celgard 2400) is barrier film, in argon shield Glove box in be assembled into simulated battery.By the simulated battery that is assembled in Land tester (Wuhan Xin Nuo Electronics Co., Ltd.) On carry out constant current charge-discharge test, charging/discharging voltage interval is 0.001～1.5V, and the electric current density of discharge and recharge is 500mA g-1。
Test result indicate that, lithium ion battery first discharge specific capacity under 0.5C multiplying power that the present invention provides is 1585mAh/g, after cycle charge-discharge 200 times, capability retention is not less than 75%.
Meanwhile, the lithium ion battery obtained discharge cycles performance under different multiplying is also investigated by the present invention. Test result indicate that, the lithium ion battery that the present invention provides all has higher specific volume under 0.1C, 0.2C, 0.5C, 1C and 2C Amount, after 0.1C circulates 10 times, capacity is that after 1885mAh/g, 0.2C circulate 10 times, capacity is after 1710mAh/g, 0.5C circulate 10 times Capacity is that after 1510mAh/g, 1C circulate 10 times, capacity is still not less than 1123mAh/g after 1330mAh/g, 2C circulate 10 times.
Embodiment 8
The aqueous solution of graphene oxide is mixed with nano silica fume, deionized water, polyvinylpyrrolidone and ethanol, obtains Mixed solution.Wherein, the mass concentration of the aqueous solution of graphene oxide is 1mg/mL, described nano silica fume and graphene oxide Mass ratio is 1:5, and nano silica fume is 1:5 with the mass ratio of polyvinylpyrrolidone, and deionized water is 5 with the volume ratio of ethanol: 1, ethanol is 1:5 with the volume ratio of the aqueous solution of graphene oxide；
Mixed solution is placed in reactor, 120 DEG C of hydro-thermal reactions 8h, obtains graphene/silicon pluralgel；
By graphene/silicon pluralgel at normal pressure, 50 DEG C of drying and processing 3.5h, then process in (-40) DEG C lyophilization 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 binding agent (SBR:CMC=3:7 mass ratio), conductive agent Super P mixes according to the weight ratio of 80:10:10, and addition suitable quantity of water, as dispersant furnishing slurry, is then coated uniformly on copper On paper tinsel collector and vacuum dried, roll-in, is prepared as negative plate；With lithium metal for electrode, the LiPF of 1mol/L6Mixed Bonding solvent (EC: DMC=1:1 volume ratio) is electrolyte, and microporous polypropylene membrane (Celgard 2400) is barrier film, in argon shield Glove box in be assembled into simulated battery.By the simulated battery that is assembled in Land tester (Wuhan Xin Nuo Electronics Co., Ltd.) On carry out constant current charge-discharge test, charging/discharging voltage interval is 0.001～1.5V, and the electric current density of discharge and recharge is 500mA g-1。
Test result indicate that, lithium ion battery first discharge specific capacity under 0.5C multiplying power that the present invention provides is 1610mAh/g, after cycle charge-discharge 200 times, capability retention is not less than 79%.
Meanwhile, the lithium ion battery obtained discharge cycles performance under different multiplying is also investigated by the present invention. Test result indicate that, the lithium ion battery that the present invention provides all has higher specific volume under 0.1C, 0.2C, 0.5C, 1C and 2C Amount, after 0.1C circulates 10 times, capacity is that after 1900mAh/g, 0.2C circulate 10 times, capacity is after 1695mAh/g, 0.5C circulate 10 times Capacity is that after 1489mAh/g, 1C circulate 10 times, capacity is still not less than 1220mAh/g after 1296mAh/g, 2C circulate 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, described nano silica fume and the quality of graphene oxide It is 2:1 than the mass ratio for 1:1, nano silica fume and polyvinylpyrrolidone, the aqueous solution of deionized water and graphene oxide Volume ratio is 1:1；
Mixed solution is placed in reactor, 180 DEG C of hydro-thermal reactions 12h, obtains graphene/silicon pluralgel；
By graphene/silicon pluralgel under 2 atmospheric pressure, 65 DEG C of drying and processing 3h, then in (-60) DEG C lyophilization Process 48h, finally, under an inert atmosphere, 800 DEG C of high annealing 4h, obtain porous graphene/silicon composite.
The present invention is by above-mentioned porous graphene/silicon composite and binding agent (SBR:CMC=3:7 mass ratio), conductive agent Super P mixes according to the weight ratio of 80:10:10, and addition suitable quantity of water, as dispersant furnishing slurry, is then coated uniformly on copper On paper tinsel collector and vacuum dried, roll-in, is prepared as negative plate；With lithium metal for electrode, the LiPF of 1mol/L6Mixed Bonding solvent (EC: DMC=1:1 volume ratio) is electrolyte, and microporous polypropylene membrane (Celgard 2400) is barrier film, in argon shield Glove box in be assembled into simulated battery.By the simulated battery that is assembled in Land tester (Wuhan Xin Nuo Electronics Co., Ltd.) On carry out constant current charge-discharge test, charging/discharging voltage interval is 0.001～1.5V, and the electric current density of discharge and recharge is 500mA g-1, Obtain its cycle performance curve as shown in Figure 9.
Test result indicate that, lithium ion battery first discharge specific capacity under 0.5C multiplying power that the present invention provides is 1715mAh/g, after cycle charge-discharge 200 times, capability retention is not less than 90%.
Meanwhile, the lithium ion battery obtained discharge cycles performance under different multiplying is also investigated by the present invention, As shown in Figure 10.Test result indicate that, the lithium ion battery that the present invention provides all has under 0.1C, 0.2C, 0.5C, 1C and 2C Higher specific capacity, after 0.1C circulates 10 times, capacity is that after 2203mAh/g, 0.2C circulate 10 times, capacity is 1941mAh/g, 0.5C After circulating 10 times, capacity is that after 1710mAh/g, 1C circulate 10 times, capacity is still to be not less than after 1514mAh/g, 2C circulate 10 times 1230mAh/g。
Embodiment 10
The aqueous solution of graphene oxide is mixed with nano silica fume, deionized water and polydiallyldimethyl ammonium chloride, obtains Mixed solution.Wherein, the mass concentration of the aqueous solution of graphene oxide is 0.5mg/mL, described 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 The volume ratio of aqueous solution be 6:1；
Mixed solution is placed in reactor, 200 DEG C of hydro-thermal reactions 2h, obtains graphene/silicon pluralgel；
By graphene/silicon pluralgel under 5 atmospheric pressure, 30 DEG C of drying and processing 7h, then in (-70) DEG C lyophilization Process 1h, finally, under an inert atmosphere, 1000 DEG C of high annealing 1h, obtain porous graphene/silicon composite.
The present invention is by above-mentioned porous graphene/silicon composite and binding agent (SBR:CMC=3:7 mass ratio), conductive agent Super P mixes according to the weight ratio of 80:10:10, and addition suitable quantity of water, as dispersant furnishing slurry, is then coated uniformly on copper On paper tinsel collector and vacuum dried, roll-in, is prepared as negative plate；With lithium metal for electrode, the LiPF of 1mol/L6Mixed Bonding solvent (EC: DMC=1:1 volume ratio) is electrolyte, and microporous polypropylene membrane (Celgard 2400) is barrier film, in argon shield Glove box in be assembled into simulated battery.By the simulated battery that is assembled in Land tester (Wuhan Xin Nuo Electronics Co., Ltd.) On carry out constant current charge-discharge test, charging/discharging voltage interval is 0.001～1.5V, and the electric current density of discharge and recharge is 500mA g-1, Obtain its cycle performance curve as shown in Figure 9.
Test result indicate that, lithium ion battery first discharge specific capacity under 0.5C multiplying power that the present invention provides is 1335mAh/g, after cycle charge-discharge 200 times, capability retention is not less than 72%.
Meanwhile, the lithium ion battery obtained discharge cycles performance under different multiplying is also investigated by the present invention, As shown in Figure 10.Test result indicate that, the lithium ion battery that the present invention provides all has under 0.1C, 0.2C, 0.5C, 1C and 2C Higher specific capacity, after 0.1C circulates 10 times, capacity is that after 1568mAh/g, 0.2C circulate 10 times, capacity is 1507mAh/g, 0.5C After circulating 10 times, capacity is that after 1330mAh/g, 1C circulate 10 times, capacity is still to be not less than after 1222mAh/g, 2C circulate 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, described nano silica fume and the quality of graphene oxide It is 1:10 than the mass ratio for 1:6, nano silica fume and kayexalate, the aqueous solution of deionized water and graphene oxide Volume ratio is 1:6；
Mixed solution is placed in reactor, 100 DEG C of hydro-thermal reactions 15h, obtains graphene/silicon pluralgel；
By graphene/silicon pluralgel under 3 atmospheric pressure, 90 DEG C of drying and processing 0.5h, then do in (-10) DEG C freezing Dry 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 binding agent (SBR:CMC=3:7 mass ratio), conductive agent Super P mixes according to the weight ratio of 80:10:10, and addition suitable quantity of water, as dispersant furnishing slurry, is then coated uniformly on copper On paper tinsel collector and vacuum dried, roll-in, is prepared as negative plate；With lithium metal for electrode, the LiPF of 1mol/L6Mixed Bonding solvent (EC: DMC=1:1 volume ratio) is electrolyte, and microporous polypropylene membrane (Celgard 2400) is barrier film, in argon shield Glove box in be assembled into simulated battery.By the simulated battery that is assembled in Land tester (Wuhan Xin Nuo Electronics Co., Ltd.) On carry out constant current charge-discharge test, charging/discharging voltage interval is 0.001～1.5V, and the electric current density of discharge and recharge is 500mA g-1, Obtain its cycle performance curve as shown in Figure 9.
Test result indicate that, lithium ion battery first discharge specific capacity under 0.5C multiplying power that the present invention provides is 1554mAh/g, after cycle charge-discharge 200 times, capability retention is not less than 78%.
Meanwhile, the lithium ion battery obtained discharge cycles performance under different multiplying is also investigated by the present invention, As shown in Figure 10.Test result indicate that, the lithium ion battery that the present invention provides all has under 0.1C, 0.2C, 0.5C, 1C and 2C Higher specific capacity, after 0.1C circulates 10 times, capacity is that after 1855mAh/g, 0.2C circulate 10 times, capacity is 1683mAh/g, 0.5C After circulating 10 times, capacity is that after 1530mAh/g, 1C circulate 10 times, capacity is still to be not less than after 1342mAh/g, 2C circulate 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, described nano silica fume and the quality of graphene oxide It is 1:5 than the mass ratio for 1:5, nano silica fume and polyvinylpyrrolidone, the aqueous solution of deionized water and graphene oxide Volume ratio is 1:5；
Mixed solution is placed in reactor, 120 DEG C of hydro-thermal reactions 8h, obtains graphene/silicon pluralgel；
By graphene/silicon pluralgel under 1.5 atmospheric pressure, 70 DEG C of drying and processing 2h, then do in (-40) DEG C freezing Dry 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 binding agent (SBR:CMC=3:7 mass ratio), conductive agent Super P mixes according to the weight ratio of 80:10:10, and addition suitable quantity of water, as dispersant furnishing slurry, is then coated uniformly on copper On paper tinsel collector and vacuum dried, roll-in, is prepared as negative plate；With lithium metal for electrode, the LiPF of 1mol/L6Mixed Bonding solvent (EC: DMC=1:1 volume ratio) is electrolyte, and microporous polypropylene membrane (Celgard 2400) is barrier film, in argon shield Glove box in be assembled into simulated battery.By the simulated battery that is assembled in Land tester (Wuhan Xin Nuo Electronics Co., Ltd.) On carry out constant current charge-discharge test, charging/discharging voltage interval is 0.001～1.5V, and the electric current density of discharge and recharge is 500mA g-1。
Test result indicate that, lithium ion battery first discharge specific capacity under 0.5C multiplying power that the present invention provides is 1700mAh/g, after cycle charge-discharge 200 times, capability retention is not less than 88%.
Meanwhile, the lithium ion battery obtained discharge cycles performance under different multiplying is also investigated by the present invention. Test result indicate that, the lithium ion battery that the present invention provides all has higher specific volume under 0.1C, 0.2C, 0.5C, 1C and 2C Amount, after 0.1C circulates 10 times, capacity is that after 2085mAh/g, 0.2C circulate 10 times, capacity is after 1802mAh/g, 0.5C circulate 10 times Capacity is that after 1662mAh/g, 1C circulate 10 times, capacity is still not less than 1227mAh/g after 1406mAh/g, 2C circulate 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, described nano silica fume and the quality of graphene oxide It is 2:1 than the mass ratio for 1:1, nano silica fume and polyvinylpyrrolidone, the aqueous solution of deionized water and graphene oxide Volume ratio is 1:1；
Mixed solution is placed in reactor, 180 DEG C of hydro-thermal reactions 12h, obtains graphene/silicon pluralgel；
By graphene/silicon pluralgel under 0.7 atmospheric pressure, 50 DEG C of drying and processing 3h, then do in (-60) DEG C freezing Dry 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 binding agent (SBR:CMC=3:7 mass ratio), conductive agent Super P mixes according to the weight ratio of 80:10:10, and addition suitable quantity of water, as dispersant furnishing slurry, is then coated uniformly on copper On paper tinsel collector and vacuum dried, roll-in, is prepared as negative plate；With lithium metal for electrode, the LiPF of 1mol/L6Mixed Bonding solvent (EC: DMC=1:1 volume ratio) is electrolyte, and microporous polypropylene membrane (Celgard 2400) is barrier film, in argon shield Glove box in be assembled into simulated battery.By the simulated battery that is assembled in Land tester (Wuhan Xin Nuo Electronics Co., Ltd.) On carry out constant current charge-discharge test, charging/discharging voltage interval is 0.001～1.5V, and the electric current density of discharge and recharge is 500mA g-1。
Test result indicate that, lithium ion battery first discharge specific capacity under 0.5C multiplying power that the present invention provides is 1735mAh/g, after cycle charge-discharge 200 times, capability retention is not less than 90%.
Meanwhile, the lithium ion battery obtained discharge cycles performance under different multiplying is also investigated by the present invention. Test result indicate that, the lithium ion battery that the present invention provides all has higher specific volume under 0.1C, 0.2C, 0.5C, 1C and 2C Amount, after 0.1C circulates 10 times, capacity is that after 2203mAh/g, 0.2C circulate 10 times, capacity is after 1941mAh/g, 0.5C circulate 10 times Capacity is that after 1732mAh/g, 1C circulate 10 times, capacity is still not less than 1230mAh/g after 1514mAh/g, 2C circulate 10 times.
Embodiment 14
The aqueous solution of graphene oxide is mixed with nano silica fume, deionized water and polydiallyldimethyl ammonium chloride, obtains Mixed solution.Wherein, the mass concentration of the aqueous solution of graphene oxide is 0.5mg/mL, described 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 The volume ratio of aqueous solution be 6:1；
Mixed solution is placed in reactor, 200 DEG C of hydro-thermal reactions 2h, obtains graphene/silicon pluralgel；
By graphene/silicon pluralgel under 0.6 atmospheric pressure, 60 DEG C of drying and processing 1h, then do in (-70) DEG C freezing Dry 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 binding agent (SBR:CMC=3:7 mass ratio), conductive agent Super P mixes according to the weight ratio of 80:10:10, and addition suitable quantity of water, as dispersant furnishing slurry, is then coated uniformly on copper On paper tinsel collector and vacuum dried, roll-in, is prepared as negative plate；With lithium metal for electrode, the LiPF of 1mol/L6Mixed Bonding solvent (EC: DMC=1:1 volume ratio) is electrolyte, and microporous polypropylene membrane (Celgard 2400) is barrier film, in argon shield Glove box in be assembled into simulated battery.By the simulated battery that is assembled in Land tester (Wuhan Xin Nuo Electronics Co., Ltd.) On carry out constant current charge-discharge test, charging/discharging voltage interval is 0.001～1.5V, and the electric current density of discharge and recharge is 500mA g-1。
Test result indicate that, lithium ion battery first discharge specific capacity under 0.5C multiplying power that the present invention provides is 1335mAh/g, after cycle charge-discharge 200 times, capability retention is not less than 72%.
Meanwhile, the lithium ion battery obtained discharge cycles performance under different multiplying is also investigated by the present invention. Test result indicate that, the lithium ion battery that the present invention provides all has higher specific volume under 0.1C, 0.2C, 0.5C, 1C and 2C Amount, after 0.1C circulates 10 times, capacity is that after 1568mAh/g, 0.2C circulate 10 times, capacity is after 1507mAh/g, 0.5C circulate 10 times Capacity is that after 1328mAh/g, 1C circulate 10 times, capacity is still not less than 1028mAh/g after 1222mAh/g, 2C circulate 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, described nano silica fume and the quality of graphene oxide It is 1:10 than the mass ratio for 1:6, nano silica fume and kayexalate, the aqueous solution of deionized water and graphene oxide Volume ratio is 1:6；
Mixed solution is placed in reactor, 100 DEG C of hydro-thermal reactions 15h, obtains graphene/silicon pluralgel；
By graphene/silicon pluralgel under 0.5 atmospheric pressure, 30 DEG C of drying and processing 2h, then do in (-10) DEG C freezing Dry 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 binding agent (SBR:CMC=3:7 mass ratio), conductive agent Super P mixes according to the weight ratio of 80:10:10, and addition suitable quantity of water, as dispersant furnishing slurry, is then coated uniformly on copper On paper tinsel collector and vacuum dried, roll-in, is prepared as negative plate；With lithium metal for electrode, the LiPF of 1mol/L6Mixed Bonding solvent (EC: DMC=1:1 volume ratio) is electrolyte, and microporous polypropylene membrane (Celgard 2400) is barrier film, in argon shield Glove box in be assembled into simulated battery.By the simulated battery that is assembled in Land tester (Wuhan Xin Nuo Electronics Co., Ltd.) On carry out constant current charge-discharge test, charging/discharging voltage interval is 0.001～1.5V, and the electric current density of discharge and recharge is 500mA g-1。
Test result indicate that, lithium ion battery first discharge specific capacity under 0.5C multiplying power that the present invention provides is 1554mAh/g, after cycle charge-discharge 200 times, capability retention is not less than 78%.
Meanwhile, the lithium ion battery obtained discharge cycles performance under different multiplying is also investigated by the present invention. Test result indicate that, the lithium ion battery that the present invention provides all has higher specific volume under 0.1C, 0.2C, 0.5C, 1C and 2C Amount, after 0.1C circulates 10 times, capacity is that after 1855mAh/g, 0.2C circulate 10 times, capacity is after 1683mAh/g, 0.5C circulate 10 times Capacity is that after 1530mAh/g, 1C circulate 10 times, capacity is still not less than 1157mAh/g after 1342mAh/g, 2C circulate 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, described nano silica fume and the quality of graphene oxide It is 1:5 than the mass ratio for 1:5, nano silica fume and polyvinylpyrrolidone, the aqueous solution of deionized water and graphene oxide Volume ratio is 1:5；
Mixed solution is placed in reactor, 120 DEG C of hydro-thermal reactions 8h, obtains graphene/silicon pluralgel；
By graphene/silicon pluralgel under 0.9 atmospheric pressure, 90 DEG C of drying and processing 0.5h, then in (-40) DEG C freezing 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 binding agent (SBR:CMC=3:7 mass ratio), conductive agent Super P mixes according to the weight ratio of 80:10:10, and addition suitable quantity of water, as dispersant furnishing slurry, is then coated uniformly on copper On paper tinsel collector and vacuum dried, roll-in, is prepared as negative plate；With lithium metal for electrode, the LiPF of 1mol/L6Mixed Bonding solvent (EC: DMC=1:1 volume ratio) is electrolyte, and microporous polypropylene membrane (Celgard 2400) is barrier film, in argon shield Glove box in be assembled into simulated battery.By the simulated battery that is assembled in Land tester (Wuhan Xin Nuo Electronics Co., Ltd.) On carry out constant current charge-discharge test, charging/discharging voltage interval is 0.001～1.5V, and the electric current density of discharge and recharge is 500mA g-1。
Test result indicate that, lithium ion battery first discharge specific capacity under 0.5C multiplying power that the present invention provides is 1700mAh/g, after cycle charge-discharge 200 times, capability retention is not less than 88%.
Meanwhile, the lithium ion battery obtained discharge cycles performance under different multiplying is also investigated by the present invention. Test result indicate that, the lithium ion battery that the present invention provides all has higher specific volume under 0.1C, 0.2C, 0.5C, 1C and 2C Amount, after 0.1C circulates 10 times, capacity is that after 2085mAh/g, 0.2C circulate 10 times, capacity is after 1802mAh/g, 0.5C circulate 10 times Capacity is that after 1662mAh/g, 1C circulate 10 times, capacity is still not less than 1227mAh/g after 1406mAh/g, 2C circulate 10 times.
Described above to the disclosed embodiments, makes professional and technical personnel in the field be capable of or uses the present invention. Multiple amendment to these embodiments will be apparent from for those skilled in the art, as defined herein General Principle can realize without departing from the spirit or scope of the present invention in other embodiments.Therefore, the present invention It is not intended to be limited to the embodiments shown herein, and is to fit to and principles disclosed herein and features of novelty phase one The widest scope caused.

Claims (10)

1. the preparation method of porous graphene/silicon composite, it is characterised in that comprise the following steps:
A1) aqueous solution of graphene oxide, nano silica fume, deionized water, surfactant and organic solvent are mixed, mixed Close solution；
B) described mixed solution is carried out hydro-thermal reaction, obtain graphene/silicon pluralgel；
C1) described graphene/silicon pluralgel is dried at normal pressure, 30 DEG C～90 DEG C 0.5～7h, then carries out freezing dry Dry, be 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 mixed solution；
B) described mixed solution is carried out hydro-thermal reaction, obtain graphene/silicon pluralgel；
C2) by described graphene/silicon pluralgel under 0.5～5 atmospheric pressure, dry 0.5～7h, then enter for 30 DEG C～90 DEG C Row lyophilization, heat treatment, obtain porous graphene/silicon composite.
Preparation method the most according to claim 1, it is characterised in that the mass concentration of the aqueous solution of described graphene oxide For 0.5mg/mL～7mg/mL.
Preparation method the most according to claim 1, it is characterised in that step A1) in, described nano silica fume and graphite oxide The mass ratio of alkene is 1:6～5:1, and described nano silica fume is 1:10～10:1 with the mass ratio of surfactant, described deionization Water is 1:6～6:1 with the volume ratio of organic solvent, and described organic solvent is 1:6 with the volume ratio of the aqueous solution of graphene oxide ～6:1.
Preparation method the most according to claim 1, it is characterised in that described organic solvent is selected from ethanol, ethylene glycol or third One in triol.
Preparation method the most according to claim 1, it is characterised in that step A2) in, described nano silica fume and graphite oxide Alkene mass ratio is 1:6～5:1, and described nano silica fume is 1:10～10:1 with the mass ratio of surfactant, described deionized water It is 1:6～6:1 with the volume ratio of the aqueous solution of graphene oxide.
Preparation method the most according to claim 1, it is characterised in that the temperature of described hydro-thermal reaction is 100 DEG C～200 DEG C, the time of described hydro-thermal reaction is 2h～15h.
Preparation method the most according to claim 1, it is characterised in that step C2) in, by compound for described graphene/silicon solidifying Glue, under 0.7～0.9 atmospheric pressure or 1.5～3 atmospheric pressure, dries 0.5～7h for 30 DEG C～90 DEG C, then carries out freezing dry Dry, heat treatment, obtains porous graphene/silicon composite.
Preparation method the most according to claim 1, it is characterised in that the temperature of described heat treatment is 300 DEG C～1000 DEG C, The time of described heat treatment is 1h～8h.
9. porous graphene/silicon composite that prepared by claim 1～8 any one preparation method.
10. a lithium ion battery, including positive pole, negative pole, barrier film and electrolyte, it is characterised in that described negative pole includes right Require the porous graphene/silicon composite described in 9.
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CN114613970A (en) * 2022-03-30 2022-06-10 新乡学院 Preparation method of silicon-carbon two-dimensional layered composite electrode material
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