CN105762360A - Graphene-silicon-coated composite negative electrode material and preparing method and application thereof - Google Patents
Graphene-silicon-coated composite negative electrode material and preparing method and application thereof Download PDFInfo
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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Abstract
The invention provides a graphene-silicon-coated composite negative electrode material and a preparing method and application thereof.The graphene-silicon-coated composite negative electrode material comprises a cavity structure formed by graphene and nanometer silicon particles coated with the cavity structure, the particle size of the nanometer silicon particles is 1 nm-100 nm, and the weight percent of the nanometer silicon particles is 5%-95%.The preparing method includes the steps that graphene oxide and silica powder are dispersed into deionized water, and the mixture is mixed to be even under the ultrasonic condition and subjected to frozen drying; the frozen-dried product is subjected to aftertreatment to obtain the graphene-silicon-coated composite negative electrode material.The negative electrode material can be applied to a lithium ion battery.The graphene-silicon-coated composite negative electrode material has the advantages that the synthesized pea-shaped graphene-silicon-coated composite negative electrode material is applied to the lithium ion battery, the first discharging capacity is up to 3,215 mAh/g, the first coulombic efficiency is 74%, and the excellent cycling performance and the excellent rate performance are shown.
Description
Technical field
The present invention relates to a kind of graphene coated silicon composite cathode material and its preparation method and application, belong to new energy materials and preparation field thereof.
Background technology
Silicon materials are because the theoretical lithium storage content (4140mAh/g) of its superelevation and rich in natural resources, it is considered as that the most potential replacement graphite becomes a new generation's lithium ion battery negative material, to meet growing portable electronic, electric vehicle and the renewable energy storage urgent needs to higher energy density and more power density.
But silicon grain (forms Li in lithiumationxAnd the process of de-lithium (again becoming simple substance Si) can occur serious powder phenomenon-tion form molecule Si).Additionally the electric conductivity of silicon grain is relatively poor, forms more discontinuous little granule and cause that electric conductivity weakens further after efflorescence.These phenomenons eventually result in capacity and cycle life all sharp-decays of battery.Volumetric expansion and poor electric conductivity become the Main Bottleneck hindering silicium cathode Materials.
In order to overcome this phenomenon, to improve the utilization rate of silicon materials, scientists has done substantial amounts of research.The work of many initiatives shows, by regulating and controlling the silicon materials of synthesis special appearance, or can be effectively improved the battery performance of silicium cathode material at silicon face coated with conductive cushion.If XiaolinLi is at Nat.Commun.2014, the mesoporous silicon sponge that 5,4105 deliver, it is possible to effectively cushioning the volumetric expansion of silicon, this material can discharge the capacity of 750mAh/g, under the electric current density of 1A/g after 1,000 times circulate, capability retention is up to 80%.And ChaofengZhang etc. is at Carbon, the fibrous silicon-carbon composite material of core-shell structure of 2014,72,169-175 upper reports, after circulating 200 times under the multiplying power of 0.3C, still have the capacity of 860mAh/g.For another example ZaileiZhang etc. are at Angew.Chem.Int.Ed.2014, and the structure continuous print porous carbon silicon composite of 53,5165-5169 upper reports, capacity is up to 1500mAh/g.
Compared to other carbonaceous materials, Graphene makes it show the performances such as more excellent electricity, calorifics and mechanics due to the atomic layer structure of its uniqueness.Itself has again the double theoretical capacity in graphite (744mAh/g).Result of study shows, by certain way, Graphene and silicon compound to be obtained the electrode material that performance is more excellent.And this also becomes one of heat subject of research at present.The preparation method of silicon/graphene composite material mainly has spray drying method, CVD, hydro-thermal method, suction method etc..JingboChang etc. utilize the method for alternately dip coated Si and Graphene on nickel screen to obtain Si/ graphene composite material, when multiplying power is up to 10C, still have the capacity of 700mAh/g.In addition, CVD is also had can to obtain the composite of excellent performance.But these methods operate more complicated, and cost is higher, though the composite excellent performance obtained, the theoretical capacity of distance silicon also has relatively larger gap.
Summary of the invention
For defect of the prior art, it is an object of the invention to the deficiency overcoming above-mentioned prior art to exist, it is provided that a kind of Semen Pisi sativi shape graphene coated silicon composite cathode material and preparation method thereof.Semen Pisi sativi shape graphene coated silicon composite provided by the invention has the high feature with good cycling stability of capacity；Its preparation method is simple and easy to do, and productivity is high, is suitable for large-scale industrial production.
The present invention is achieved by the following technical solutions:
First aspect, the invention provides a kind of graphene coated silicon composite cathode material, it includes the cavity structure being made up of Graphene and the silicon nanoparticle being coated in described cavity structure, the particle diameter of described silicon nanoparticle is 1～100nm, and the percetage by weight shared by silicon nanoparticle is 5～95%.The cavity structure that this Graphene is constituted is similar to pea pods, is tightly coated on wherein by described silicon grain.
Second aspect, the preparation method that the invention provides a kind of graphene coated silicon composite cathode material as the aforementioned, it comprises the steps:
Graphite oxide powder and silica flour are scattered in deionized water, carry out lyophilization after mixing under ultrasound condition, under ultrasound condition, both can silica flour be carried out fully dispersed, and graphite oxide powder can be peeled off again, obtain graphene oxide；
Product after described lyophilization is carried out post processing, obtains graphene coated silicon composite cathode material.
Preferably, described cryodesiccated temperature is-80～10 DEG C, and pressure is 0～101000Pa.If higher than this scope, will be significantly high to the requirement of instrument and freeze drying equipment, thus greatly improving production cost；If lower than this scope, it will be difficult to ensure refrigerating effect.
Preferably, the mass ratio of described graphite oxide powder and silica flour is 1:(0.2～5), the mass ratio of described graphite oxide powder and deionized water is 1:(0.2～5).Graphite oxide powder can make graphite oxide powder fully dispersed in deionized water with the ratio of silica flour and the ratio of graphite oxide powder and deionized water, makes silica flour fully dispersed in graphite oxide simultaneously.
Preferably, the method for described post processing is the one in following process:
A, the product after lyophilization is scattered in solvent, at 100～240 DEG C, carries out solvent thermal reaction, obtain graphene coated silicon composite cathode material；This temperature range can make graphene oxide be reduced to Graphene, can not reach reduction effect lower than 100 DEG C, can be significantly high higher than 240 DEG C of requirements to pressure vessel, greatly improves production cost.
B, the product after lyophilization is carried out at 200～1200 DEG C high-temperature calcination, obtain graphene coated silicon composite cathode material.This calcination temperature range can make graphene oxide be reduced to Graphene, can not reach reduction effect lower than 200 DEG C, can be significantly high higher than 1200 DEG C of requirements to calciner, causes that production cost improves.
Preferably, described solvent is selected from one or more in water, methanol, ethanol, ethylene glycol, ether, acetone, oxolane, benzene,toluene,xylene, DMF, N-Methyl pyrrolidone.
Preferably, the heating rate of described high-temperature calcination is 0.5～40 DEG C/min.This heating rate can ensure that graphene oxide is effectively reduced to Graphene, will not produce obvious bulking effect.
Preferably, the temperature of described high-temperature calcination is 700～1000 DEG C.
Preferably, described high-temperature calcination carries out in any one atmosphere following:
Air, nitrogen, argon or hydrogen volume mark be 1～20% hydrogen-argon-mixed.
The third aspect, present invention also offers the application in preparing lithium ion battery of a kind of graphene coated silicon composite cathode material as the aforementioned.
Compared with prior art, the present invention has following beneficial effect:
1, the present invention creatively adopts the method that lyophilization is combined with heat treatment phase, and synthetic method is simple, it is not necessary to adjust pH value, it is not required that any reducing agent or surfactant, it is not necessary to use expensive instrument, also without loaded down with trivial details experimental procedure.The abundant raw material used, and cheap and easy to get, product yield is high, and solvent for use also can be recycled, and whole experimentation efficiency is high, and controllability is strong, with low cost, simple and environmentally-friendly, is suitable for industrialized production；
2, in the building-up process of the present invention, first lyophilization is being passed through in the situation of graphite oxide powder and silica flour mix homogeneously, silica flour is fixed on and shrinks in the graphene oxide reunited, then by further heat treatment, graphene oxide is further shrinkage crimping while being reduced, being wrapped up more closely wherein by silicon powder particle, it is stable that this allows for the material structure prepared by the present invention, and pattern is homogeneous；
3, in the composite synthesized by the present invention, the Graphene being closely coated on silicon face can be greatly improved the electric conductivity of material, and the cavity that the closing that Graphene is formed or class are closed can effectively cushion the negative effect that silicon grain volumetric expansion causes, thus maintaining the stability of material structure；
4, being used in lithium ion battery by synthesized a kind of Semen Pisi sativi shape graphene coated silicon composite cathode material, discharge capacity is up to 3215mAh/g first, and coulombic efficiency is 74% first, and shows circulation and the high rate performance of excellence.
Accompanying drawing explanation
By reading detailed description non-limiting example made with reference to the following drawings, the other features, objects and advantages of the present invention will become more apparent upon:
Fig. 1 is the SEM figure of the Semen Pisi sativi shape graphene coated silicon composite cathode material that the embodiment of the present invention 1 prepares；
Fig. 2 is that the Novel anode material hydroxy chloride cobalt that the present invention adopts embodiment 1 to obtain is assembled into the lithium ion battery electric current density with 100mA/g, twice charging and discharging curve figure before the voltage range of 1.2～0.01V；
Fig. 3 is that the Novel anode material hydroxy chloride cobalt that the present invention adopts embodiment 7 to obtain is assembled into the lithium ion battery electric current density with 100mA/g, twice charging and discharging curve figure before the voltage range of 1.2～0.01V.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.Following example will assist in those skilled in the art and are further appreciated by the present invention, but do not limit the present invention in any form.It should be pointed out that, to those skilled in the art, without departing from the inventive concept of the premise, it is also possible to make some deformation and improvement.These broadly fall into protection scope of the present invention.
In the present invention, the preparation method of graphite oxide is as follows:
Under 0～20 DEG C of water-bath, 3～5g graphite powder is added in 100～150mL concentrated sulphuric acid, the lower addition 10～20g potassium permanganate of stirring, stir 3～4h, temperature rises to 30～35 DEG C, adding 300～500mL deionized water, stir 1～3h, adding 15～25mL mass concentration is the hydrogenperoxide steam generator of 30%, stir 5～20 minutes, through centrifugation, also dried with the hydrochloric acid solution of mass concentration 5%, deionized water cyclic washing, obtain graphite oxide.
The assembling of lithium ion battery is as follows with method of testing:
The binding agent of the Semen Pisi sativi shape graphene coated silicon composite cathode material of the present invention and the 20wt.% N-Methyl pyrrolidone solution of the butadiene-styrene rubber-sodium carboxymethyl cellulose emulsion of 2wt.% or Kynoar that concentration is 0.02g/mL (solid content be) and the conductive agent (SuperP conductive carbon black) of 20wt.% are mixed, it is coated in after stirring on Copper Foil, puts in baking oven 60～80 DEG C of drying.It is washed into pole piece with the drift of diameter 12～16mm again, puts in vacuum drying oven and dry 8～12 hours at 60～120 DEG C, be then transferred into being full of in the glove box of argon.With metal lithium sheet for electrode, ENTEKPE perforated membrane is barrier film, the ethylene carbonate of 1mol/L lithium hexafluoro phosphate and dimethyl carbonate (volume ratio 1:1) mixed solution are electrolyte, and in this electrolyte, add the fluorinated ethylene carbonate of 10% (volume fraction), it is assembled into CR2016 button cell, carrying out constant current charge-discharge performance test on LAND battery test system (offer of Wuhan Jin Nuo Electronics Co., Ltd.), discharge and recharge blanking voltage is relative to Li/Li+It is 1.2～0.01V.
The electrolyte of lithium ion battery is not limited to the ethylene carbonate of above-mentioned lithium hexafluoro phosphate and the mixed solution of dimethyl carbonate, and it can be the electrolyte of lithium salts, solvent and electrolysis additive composition, and described lithium salts includes lithium hexafluoro phosphate (LiPF6), LiBF4 (LiBF4) or lithium perchlorate (LiClO4) etc. mineral-type salt and the organic salt such as biethyl diacid lithium borate (LiBOB), two (trifluoromethane sulfonic acid) imine lithium (LiTFSI), described solvent includes at least one in ethylene carbonate (EC), Allyl carbonate (PC), dimethyl carbonate (DMC) and diethyl carbonate (DEC), and in electrolyte, lithium salt is less than 2mol/L.Described electrolysis additive includes fluorinated ethylene carbonate (FEC), vinylene carbonate (VC) etc..
Embodiment 1
The preparation method that the present embodiment relates to a kind of Semen Pisi sativi shape graphene coated silicon composite cathode material, described method comprises the steps:
Nano silica fume and 40mg graphite oxide powder that 80mg particle diameter is about 20nm are scattered in 20ml deionized water, after ultrasonic disperse, in-50 DEG C, when pressure is 5Pa after lyophilization 36 hours, by dried sample dispersion in 40ml dehydrated alcohol, it is placed in the reactor of inner liner polytetrafluoroethylene and carries out solvent thermal reaction, reaction temperature is 170 DEG C, react 12 hours, reacted product deionized water wash, in-50 DEG C, lyophilization 24 hours when pressure is 5Pa, obtain Semen Pisi sativi shape graphene coated silicon composite cathode material.In this composite, shared by nano silicon particles, mass ratio is about 83%.
The SEM of the Semen Pisi sativi shape graphene coated silicon composite cathode material that the present embodiment prepares schemes as it is shown in figure 1, composite presents Semen Pisi sativi shape microscopic appearance, and namely what be wrapped in outer layer is Graphene, and silicon grain is wrapped by wherein.
The Semen Pisi sativi shape graphene coated silicon composite cathode material that the present embodiment prepares is assembled into battery and carries out charge-discharge test, as shown in Figure 2, battery is under the electric current density of 100mA/g, in the voltage range of 1.2～0.01V during discharge and recharge, embedding lithium capacity is 3215mAh/g first, reversible capacity is 2379mAh/g first, and first circle coulombic efficiency is 74%.The reversible capacity of second time circulation is 2374mAh/g, and almost without loss compared with first time, it is 95% that coulombic efficiency also increases rapidly.
Comparative example 1
Being dispersed in 20ml deionized water by 80mg silica flour (mean diameter 20nm) and 40mg graphite oxide powder, ultrasonic 60min makes it be uniformly dispersed, and then carries out spray drying, inlet temperature is at 220 DEG C, outlet temperature, at 140 DEG C, removes moisture, obtains the composite of graphene oxide and silicon；Then it is placed in high temperature furnace, pass into hydrogen-argon-mixed (containing 5v/v% hydrogen), it is warming up to 600 DEG C and carries out the high temperature anneal, it is incubated 5 hours, graphene oxide is made to reduce, then naturally cooling to room temperature, obtain silicon graphene composite negative pole material, this material forms diameter and is about the class spherical composite pellets of 400nm.In above-mentioned preparation process, the graphene oxide of addition generates Graphene to last reduction, and its proportion of goods damageds are 40%.
Prepared silicon graphene composite is assembled into battery and carries out charge-discharge test, under the electric current density of 100mA/g, in the voltage range of 1.2～0.01V during discharge and recharge, its initial coulomb efficiency is 64%, reversible capacity is only 1748mAh/g first, the reversible capacity of the 2nd circulation is 1602mAh/g, and decay is substantially.
Embodiment 2
The preparation method that the present embodiment relates to a kind of Semen Pisi sativi shape graphene coated silicon composite cathode material, described method comprises the steps:
Nano silica fume and 10mg graphite oxide powder that 80mg particle diameter is about 1nm are scattered in 50ml deionized water, after ultrasonic disperse, in 10 DEG C, when pressure is 101000Pa after lyophilization 72 hours, by dried sample dispersion in 10mlN, in dinethylformamide, it is placed in the reactor of inner liner polytetrafluoroethylene and carries out solvent thermal reaction, reaction temperature is 240 DEG C, react 2 hours, reacted product deionized water wash, in 10 DEG C, lyophilization 72 hours when pressure is 101000Pa, obtain Semen Pisi sativi shape graphene coated silicon composite.In this composite, shared by nano silicon particles, mass ratio is about 95%.
The Semen Pisi sativi shape graphene coated silicon composite cathode material that the present embodiment prepares is assembled into battery and carries out charge-discharge test, be 50mA/g in electric current density, when voltage range is 1.2～0.01V, carry out charge-discharge test.Embedding lithium capacity is up to 3810mAh/g first, and reversible capacity is 2023mAh/g first, and first circle efficiency is 53%.
Embodiment 3
The preparation method that the present embodiment relates to a kind of Semen Pisi sativi shape graphene coated silicon composite, described method comprises the steps:
Nano silica fume and 200mg graphite oxide powder that 5mg particle diameter is about 100nm are scattered in 40ml deionized water, after ultrasonic disperse, in-80 DEG C, when pressure is 0Pa after lyophilization 2 hours, by dried sample dispersion in 200ml ethylene glycol, it is placed in the reactor of inner liner polytetrafluoroethylene and carries out solvent thermal reaction, reaction temperature is 100 DEG C, react 72 hours, reacted product deionized water wash, in-80 DEG C, lyophilization 12 hours when pressure is 0Pa, obtain Semen Pisi sativi shape graphene coated silicon composite.In this composite, shared by nano silicon particles, mass ratio is about 5%.
The Semen Pisi sativi shape graphene coated silicon composite cathode material that the present embodiment prepares is assembled into battery and carries out charge-discharge test, be 50mA/g in electric current density, when voltage range is 1.2～0.01V, carry out charge-discharge test.Embedding lithium capacity is 1203mAh/g first, and reversible capacity is 554mAh/g first, and first circle efficiency is 53%.
Embodiment 4
The preparation method that the present embodiment relates to a kind of Semen Pisi sativi shape graphene coated silicon composite, described method comprises the steps:
Nano silica fume and 40mg graphite oxide powder that 80mg particle diameter is about 40nm are scattered in 40ml deionized water; after ultrasonic disperse; in-80 DEG C; when pressure is 0Pa after lyophilization 12 hours; dried sample is placed in tube furnace, under nitrogen protection, is warming up to 1000 DEG C with the speed of 0.5 DEG C/min; it is naturally cooling to room temperature after keeping 2h, namely obtains Semen Pisi sativi shape graphene coated silicon composite.In this composite, shared by nano silicon particles, mass ratio is about 90%.
The Semen Pisi sativi shape graphene coated silicon composite cathode material that the present embodiment prepares is assembled into battery and carries out charge-discharge test, be 50mA/g in electric current density, when voltage range is 1.2～0.01V, carry out charge-discharge test.Embedding lithium capacity is 3741mAh/g first, and reversible capacity is 2821mAh/g first, and first circle efficiency is 75%.Second time reversible capacity is 1957mAh/g, and coulombic efficiency is 87%.
Embodiment 5
The preparation method that the present embodiment relates to a kind of Semen Pisi sativi shape graphene coated silicon composite, described method comprises the steps:
Nano silica fume and 80mg graphite oxide powder that 80mg particle diameter is about 40nm are scattered in 80ml deionized water, after ultrasonic disperse, in-80 DEG C, lyophilization 12 hours when pressure is 0Pa, dried sample is placed in tube furnace, under 5v/v% hydrogen-argon-mixed atmosphere, is warming up to 700 DEG C with the speed of 10 DEG C/min, it is naturally cooling to room temperature after keeping 6h, namely obtains Semen Pisi sativi shape graphene coated silicon composite.In this composite, shared by nano silicon particles, mass ratio is about 70%.
The Semen Pisi sativi shape graphene coated silicon composite cathode material that the present embodiment prepares is assembled into battery and carries out charge-discharge test, be 50mA/g in electric current density, when voltage range is 1.2～0.01V, carry out charge-discharge test.Embedding lithium capacity is 2905mAh/g first, and reversible capacity is 2021mAh/g first, and first circle efficiency is 70%.
Embodiment 6
The preparation method that the present embodiment relates to a kind of Semen Pisi sativi shape graphene coated silicon composite, described method comprises the steps:
Nano silica fume and 80mg graphite oxide powder that 80mg particle diameter is about 40nm are scattered in 80ml deionized water, after ultrasonic disperse, in-80 DEG C, when pressure is 0Pa after lyophilization 12 hours, dried sample is placed in tube furnace, in air atmosphere, is warming up to 100 DEG C with the speed of 50 DEG C/min, it is naturally cooling to room temperature after keeping 72h, namely obtains Semen Pisi sativi shape graphene coated silicon composite.In this composite, shared by nano silicon particles, mass ratio is about 60%.
The Semen Pisi sativi shape graphene coated silicon composite cathode material that the present embodiment prepares is assembled into battery and carries out charge-discharge test, be 100mA/g in electric current density, when voltage range is 1.2～0.01V, carry out charge-discharge test.Embedding lithium capacity is 1815mAh/g first, and reversible capacity is 1001mAh/g first, and first circle efficiency is 55%.
Embodiment 7
The preparation method that the present embodiment relates to a kind of Semen Pisi sativi shape graphene coated silicon composite cathode material, described method comprises the steps:
Nano silica fume and 50mg graphite oxide powder that 80mg particle diameter is about 20nm are scattered in 20ml deionized water, after ultrasonic disperse, in-50 DEG C, when pressure is 1Pa after lyophilization 36 hours, by dried sample dispersion in 40ml deionized water, it is placed in the reactor of inner liner polytetrafluoroethylene and carries out solvent thermal reaction, reaction temperature is 170 DEG C, react 12 hours, reacted product deionized water wash, in-50 DEG C, lyophilization 24 hours when pressure is 1Pa, obtain Semen Pisi sativi shape graphene coated silicon composite cathode material.In this composite, shared by nano silicon particles, mass ratio is about 80%.
The Semen Pisi sativi shape graphene coated silicon composite cathode material that the present embodiment prepares is assembled into battery and carries out charge-discharge test, as shown in Figure 3, battery is under the electric current density of 100mA/g, in the voltage range of 1.2～0.01V during discharge and recharge, embedding lithium capacity is 2756mAh/g first, reversible capacity is 1973mAh/g first, and first circle coulombic efficiency is 71.6%.The reversible capacity of second time circulation is 1972mAh/g, and it is 94% that coulombic efficiency also increases rapidly.
In summary it can be seen, the present invention creatively adopts the method that lyophilization is combined with heat treatment phase, and synthetic method is simple, pH value need not be adjusted, also without any reducing agent or surfactant, it is not necessary to use expensive instrument, also without loaded down with trivial details experimental procedure.The abundant raw material used, and cheap and easy to get, product yield is high, and solvent for use also can be recycled, and whole experimentation efficiency is high, and controllability is strong, with low cost, simple and environmentally-friendly, is suitable for industrialized production；
In the building-up process of the present invention, first lyophilization is being passed through in the situation of graphite oxide powder and silica flour mix homogeneously, silica flour is fixed on and shrinks in the graphene oxide reunited, then by further heat treatment, graphene oxide is further shrinkage crimping while being reduced, being wrapped up more closely wherein by silicon powder particle, it is stable that this allows for the material structure prepared by the present invention, and pattern is homogeneous；
By inventing in synthesized composite, the Graphene being closely coated on silicon face can be greatly improved the electric conductivity of material, and the cavity that the closing that Graphene is formed or class are closed can effectively cushion the negative effect that silicon grain volumetric expansion causes, thus maintaining the stability of material structure；
Being used in lithium ion battery by synthesized a kind of Semen Pisi sativi shape graphene coated silicon composite cathode material, discharge capacity is up to 3215mAh/g first, and coulombic efficiency is 74% first, and shows circulation and the high rate performance of excellence.
Above specific embodiments of the invention are described.It is to be appreciated that the invention is not limited in above-mentioned particular implementation, those skilled in the art can make various deformation or amendment within the scope of the claims, and this has no effect on the flesh and blood of the present invention.
Claims (10)
1. a graphene coated silicon composite cathode material, it is characterized in that, including the cavity structure being made up of Graphene and the silicon nanoparticle being coated in described cavity structure, the particle diameter of described silicon nanoparticle is 1～100nm, and the percetage by weight shared by silicon nanoparticle is 5～95%.
2. the preparation method of a graphene coated silicon composite cathode material as claimed in claim 1, it is characterised in that comprise the steps:
Graphite oxide powder and silica flour are scattered in deionized water, under ultrasound condition, after mixing, carry out lyophilization；
Product after described lyophilization is carried out post processing, obtains graphene coated silicon composite cathode material.
3. the preparation method of graphene coated silicon composite cathode material as claimed in claim 2, it is characterised in that: described cryodesiccated temperature is-80～10 DEG C, and pressure is 0～101000Pa.
4. the preparation method of graphene coated silicon composite cathode material as claimed in claim 2, it is characterized in that: the mass ratio of described graphite oxide powder and silica flour is 1:(0.2～5), the mass ratio of described graphite oxide powder and deionized water is 1:(0.2～5).
5. the preparation method of graphene coated silicon composite cathode material as claimed in claim 2, it is characterised in that the method for described post processing is the one in following process:
A, the product after lyophilization is scattered in solvent, at 100～240 DEG C, carries out solvent thermal reaction, obtain graphene coated silicon composite cathode material；
B, the product after lyophilization is carried out at 100～1000 DEG C high-temperature calcination, obtain graphene coated silicon composite cathode material.
6. the preparation method of graphene coated silicon composite cathode material as claimed in claim 5, it is characterized in that, described solvent is selected from one or more in water, methanol, ethanol, ethylene glycol, ether, acetone, oxolane, benzene,toluene,xylene, DMF, N-Methyl pyrrolidone.
7. the preparation method of graphene coated silicon composite cathode material as claimed in claim 5, it is characterised in that the heating rate of described high-temperature calcination is 0.5～50 DEG C/min.
8. the preparation method of graphene coated silicon composite cathode material as claimed in claim 5, it is characterised in that the temperature of described high-temperature calcination is 700～1000 DEG C.
9. the preparation method of graphene coated silicon composite cathode material as claimed in claim 5, it is characterised in that described high-temperature process carries out in any one atmosphere following:
Air, nitrogen, argon or hydrogen volume mark be 1～20% hydrogen-argon-mixed.
10. the graphene coated silicon composite cathode material as described in any one in claim 2～9 application in preparing lithium ion battery.
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| CN201610205702.2A CN105762360B (en) | 2016-04-01 | 2016-04-01 | Graphene coated silicon composite cathode material and its preparation method and application |
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| CN106159227A (en) * | 2016-07-27 | 2016-11-23 | 电子科技大学 | silicon-carbon composite lithium ion battery cathode material and preparation method thereof |
| CN106953088A (en) * | 2017-04-24 | 2017-07-14 | 广东烛光新能源科技有限公司 | A kind of silicon-carbon cathode material and preparation method thereof |
| CN107026262A (en) * | 2017-04-21 | 2017-08-08 | 上海杉杉科技有限公司 | The spherical hard charcoal negative material of high power capacity of surface graphene coated |
| CN107342411A (en) * | 2017-07-05 | 2017-11-10 | 安徽科达洁能新材料有限公司 | A kind of preparation method of graphene silicon carbon lithium ion battery cathode |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633256A (en) * | 2012-04-16 | 2012-08-15 | 中国科学院上海硅酸盐研究所 | Preparation method of graphene colloid dispersion solution |
| CN103035890A (en) * | 2011-10-09 | 2013-04-10 | 海洋王照明科技股份有限公司 | Silicon and graphene composite electrode material and preparation method thereof |
| CN104409702A (en) * | 2014-11-21 | 2015-03-11 | 黑龙江科技大学 | Preparation method of N-doped coated graphene micron silicon composite material |
| CN104591154A (en) * | 2013-10-31 | 2015-05-06 | 青岛泰浩达碳材料有限公司 | Preparation method for graphene composite material |
| CN105226249A (en) * | 2015-09-11 | 2016-01-06 | 王晓亮 | A kind of 3 SiC 2/graphite alkene core-shell material and Synthesis and applications thereof with gap |
| CN105439128A (en) * | 2015-11-09 | 2016-03-30 | 国网智能电网研究院 | Preparation method for porous graphene lithium ion battery positive electrode material |
-
2016
- 2016-04-01 CN CN201610205702.2A patent/CN105762360B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103035890A (en) * | 2011-10-09 | 2013-04-10 | 海洋王照明科技股份有限公司 | Silicon and graphene composite electrode material and preparation method thereof |
| CN102633256A (en) * | 2012-04-16 | 2012-08-15 | 中国科学院上海硅酸盐研究所 | Preparation method of graphene colloid dispersion solution |
| CN104591154A (en) * | 2013-10-31 | 2015-05-06 | 青岛泰浩达碳材料有限公司 | Preparation method for graphene composite material |
| CN104409702A (en) * | 2014-11-21 | 2015-03-11 | 黑龙江科技大学 | Preparation method of N-doped coated graphene micron silicon composite material |
| CN105226249A (en) * | 2015-09-11 | 2016-01-06 | 王晓亮 | A kind of 3 SiC 2/graphite alkene core-shell material and Synthesis and applications thereof with gap |
| CN105439128A (en) * | 2015-11-09 | 2016-03-30 | 国网智能电网研究院 | Preparation method for porous graphene lithium ion battery positive electrode material |
Non-Patent Citations (1)
| Title |
|---|
| XIAOSI ZHOU ET AL.: ""Facile synthesis of silicon nanoparticles inserted into graphene sheets as improved anode materials for lithium-ion batteries"", 《CHEMICAL COMMUNICATIONS》 * |
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