CN104916826B - A kind of graphene coated silicium cathode material and preparation method thereof - Google Patents
A kind of graphene coated silicium cathode material and preparation method thereof Download PDFInfo
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- CN104916826B CN104916826B CN201510385666.8A CN201510385666A CN104916826B CN 104916826 B CN104916826 B CN 104916826B CN 201510385666 A CN201510385666 A CN 201510385666A CN 104916826 B CN104916826 B CN 104916826B
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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Abstract
The present invention relates to ion cathode material lithium technical field, and in particular to a kind of graphene coated silicium cathode material and preparation method thereof, the preparation method comprises the following steps：A, preparation graphene oxide suspension；B, prepare silicon nanoparticle suspension；C, prepare graphene coated silicium cathode material.The preparation method of the present invention uses electrostatic self-assembled synthetic technology, and raw material sources are extensively, cheap, and synthetic method is simple, and process conditions are easy to control, workable, reproducible.The graphene coated silicium cathode material specific capacity of the present invention is high, and cycle performance and high rate performance are excellent, and first discharge specific capacity reaches 2746mAh/g under 0.01 1.2V, 200mA/g current densities, and 803.8mAh/g is maintained at by 100 circulation specific discharge capacities.
Description
Technical field
The present invention relates to ion cathode material lithium technical field, and in particular to a kind of graphene coated silicium cathode material and its
Preparation method.
Background technology
The advantages of lithium ion battery is because of its high-energy-density, high power density, long life, is most promising storage
Can chemical cell.Although lithium ion nineteen ninety begins to commercialization, the need for its energy-storage property still can not meet people, especially
It is that these are needed on the electrokinetic cell of bigger energy density and power density in electrical vehicular power power supply.Meanwhile, as portable
The widely used battery of formula electronic equipment, the performance that lithium ion battery is also required to improve constantly its performance to meet continuous improvement will
The summation market demand.Therefore, high performance lithium ion battery is developed, becomes study hotspot in recent years.One of crucial grinds
It is exactly that research and development have more height ratio capacity, more high charge-discharge speed, the negative material of longer service life cycle to study carefully direction.
Silicon is its higher theoretical specific capacity as the sharpest edges of lithium ion battery negative material（Theoretical capacity is
4200mAh/g）, but its in charge and discharge process due to volumetric expansion easily cause structure destruction, capacity sharp-decay.At present for
The modification of high power capacity silicium cathode material is mainly using the body of the method formation cladding such as surface modification, doping, compound or high degree of dispersion
System, by improving the mechanical property of material, to alleviate volumetric expansion is produced during removal lithium embedded internal stress to material structure
Destruction, so as to improve its electrochemical cycle stability.
The extra large nurses of the strong K of peace moral of Univ Manchester UK in 2004（AndreK.Geim）It is made Deng with mechanical split the law
Independent graphene.Physics, chemistry, the scientist of Material Field have started systematic research to graphene since then.Graphene is
The carbon six-membered cyclic two-dimensional structure of sp2 hydridization formation, is most of carbons material, particularly graphite type material（Such as zero dimension fowler
Alkene, one-dimensional nano carbon pipe, three-dimensional graphite）Basic building block.Each C atoms of graphene pass through very strong δ keys covalent bond and its
Its three C atom is connected, therefore graphene is had fabulous mechanical strength.Each remaining p track electricity of C atoms
Son, the big pi bond of delocalization for foring conjugation in the direction vertical with graphene planes, electronics can be moved freely in crystal so that
Graphene has good electric conductivity.Graphene be although proved can with monoatomic two-dimensional structure individualism, but because
The calorifics undulation of diverging, can cause graphene to produce the out-of-flatness of feature, even gauffer and curling.On the one hand, science
Family study and can control the substrate of graphene gauffer, and study the relation between charge mobility and gauffer.On the other hand, it is sharp
With the intrinsic fold of graphene and the microstructure of curling, composite graphite alkene and other materials prepare graphene composite material, have
There are the excellent properties that unit material is different.
Therefore, it is necessary to research and develop a kind of specific capacity high and good cycling stability graphene coated silicium cathode material and its system
Preparation Method, has solved the deficiencies in the prior art.
The content of the invention
In order to overcome shortcoming and defect present in prior art, it is an object of the invention to provide a kind of graphene coated
The preparation method of silicium cathode material, the preparation method uses electrostatic self-assembled synthetic technology, and raw material sources are extensively, cheap,
Synthetic method is simple, and process conditions are easy to control, workable, reproducible.
It is an object of the invention to provide a kind of graphene coated silicium cathode material, the graphene coated silicium cathode material ratio
Capacity is high, and cycle performance and high rate performance are excellent, and first discharge specific capacity reaches under 0.01-1.2V, 200mA/g current densities
2746mAh/g, 803.8mAh/g is maintained at by 100 circulation specific discharge capacities.
The purpose of the present invention is achieved through the following technical solutions：A kind of preparation method of graphene coated silicium cathode material,
Comprise the following steps：
A, preparation graphene oxide suspension：
A1, under conditions of ice-water bath, concentrated phosphoric acid is added into the concentrated sulfuric acid, is stirred, graphite is then added, stirring is equal
It is even, potassium permanganate powder is slow added into, 30-60min is stirred, 45-55 DEG C is then heated to, 20-28h is stirred, is reacted
Thing；
A2, the obtained reactants of step A1 are cooled to room temperature and are poured slowly into the mixed liquor of frozen water and hydrogen peroxide, so
After centrifuge, and washed with watery hydrochloric acid, it is 6.8-7.2 to be then washed with deionized water to pH value, and obtained product is at 45-55 DEG C
Vacuum drying, is made graphite oxide；
A3, by graphite oxide ultrasonic disperse made from step A2 in deionized water, formed graphene oxide suspension；
B, prepare silicon nanoparticle suspension：
B1, under conditions of ice-water bath, the concentrated sulfuric acid is added into hydrogen peroxide, is stirred, then add simple substance nano-silicon
Particle, continues to stir, and centrifuge washing obtains treated silicon nanoparticle after drying；
B2, the silicon nanoparticle ultrasonic disperse for treating step B1 are in absolute ethyl alcohol, and idol is slowly added dropwise in heating water bath
Join agent, the silicon nanoparticle of coupling agent surface modification is made in constant temperature stirring 8-16h, cooling, suction filtration after drying；
B3, by the silicon nanoparticle ultrasonic disperse of coupling agent surface modification made from step B2 in deionized water, formed
The silicon nanoparticle suspension of silane coupler surface modification；
C, prepare graphene coated silicium cathode material：
C1, receiving silane coupler surface modification made from graphene oxide suspension made from step A3 and step B3
The suspension mixing of rice silicon grain, stirs, centrifuge washing obtains mixture；
C2, the mixture for obtaining step C1 carry out high-temperature process under protective atmosphere, prepare graphene coated silicium cathode
Material.
It is preferred that, in the step A1, the mass ratio of graphite and potassium permanganate is 1-3：2-6, the addition of the concentrated sulfuric acid is
The volume ratio of 60-360mL/1-3g graphite, concentrated phosphoric acid and the concentrated sulfuric acid is 1-4:6-36.
The present invention is by the way that the mass ratio of graphite and potassium permanganate is controlled in 1-3：2-6, the addition control of the concentrated sulfuric acid exists
The volume ratio of 60-360mL/1-3g graphite, concentrated phosphoric acid and the concentrated sulfuric acid is 1-4:6-36, can preferably form graphite oxide, carry
Hyperoxia graphite yield and purity.It is more highly preferred to, the mass ratio of graphite and potassium permanganate is 2：4, the addition of the concentrated sulfuric acid is
210mL/2g graphite.
It is preferred that, in the step A2, the mass fraction of hydrogen peroxide is 10%-30%, and the volume ratio of frozen water and hydrogen peroxide is
120-400：10-30, the mass fraction of watery hydrochloric acid is 3%-6%.
The present invention is by the way that by the mass fraction control of hydrogen peroxide, in 10%-30%, the volume ratio control of frozen water and hydrogen peroxide exists
120-400：10-30, can improve the reactivity and purification effect of graphite oxide, obtained graphite oxide yield and purity
It is high.It is more highly preferred to, the mass fraction of hydrogen peroxide is 20%, the volume ratio of frozen water and hydrogen peroxide is 260：20.
The present invention is by the way that the mass fraction of watery hydrochloric acid is controlled in 3%-6%, and clean result is good, can improve graphite oxide receipts
Rate and purity.It is more highly preferred to, the mass fraction of watery hydrochloric acid is 4.5%.
It is preferred that, in the step A3, the time of ultrasonic disperse is oxidation in 30-120min, graphene oxide suspension
The concentration of graphene is 0.1-1mg/mL.
The present invention is by the way that by the time control of ultrasonic disperse, in 30-120min, dispersion effect is good, obtained graphene coated
Silicium cathode material specific capacity is high, and cycle performance and high rate performance are excellent.It is more highly preferred to, the time of ultrasonic disperse is 75min.
The present invention is by the way that by the concentration control of graphene oxide in graphene oxide suspension, in 0.1-1mg/mL, it can be with
Silicon nanoparticle in the silicon nanoparticle suspension of silane coupler surface modification is preferably combined, and makes electronegative oxidation stone
Black alkene is just coated on the surface of the silicon nanoparticle of positively charged, and obtained graphene coated silicium cathode material specific capacity is high, circulation
Performance and high rate performance are excellent.It is more highly preferred to, the concentration of graphene oxide is 0.5mg/mL in graphene oxide suspension.
It is preferred that, in the step B1, the mass fraction of hydrogen peroxide is 25%-35%, the concentrated sulfuric acid and hydrogen peroxide volume ratio
For 120-300：20-60, the addition of simple substance silicon nanoparticle is the 0.3-0.5g/30-50mL concentrated sulfuric acids.The quality of the concentrated sulfuric acid point
Number is 98%.
The present invention is by the way that the mass fraction of hydrogen peroxide is controlled in 25%-35%, and the volume ratio of the concentrated sulfuric acid and hydrogen peroxide is controlled
In 120-300：20-60, the addition of simple substance silicon nanoparticle is the 0.3-0.5g/30-50mL concentrated sulfuric acids, with strong oxidizing property
The concentrated sulfuric acid/dioxygen water mixed liquid processing simple substance silicon nanoparticle, the concentrated sulfuric acid/dioxygen water mixed liquid being capable of oxidizing simple substance silicon grain
Surface, simple substance silicon face is oxidized and generates a large amount of silicone hydroxyls, and obtained graphene coated silicium cathode material specific capacity is high, follows
Ring performance and high rate performance are excellent.It is more highly preferred to, the mass fraction of hydrogen peroxide is 30%, the volume ratio of the concentrated sulfuric acid and hydrogen peroxide
For 210：40.
It is preferred that, in the step B2, the addition of absolute ethyl alcohol is the nanometer that 100-300mL/0.1-0.3g is treated
The volume ratio of silicon grain, coupling agent and absolute ethyl alcohol is 2-6：100-300, silane coupler is Silane coupling agent KH550, water-bath
The temperature of heating is 65-75 DEG C.
The present invention is by the way that the addition of absolute ethyl alcohol is controlled in nano-silicon treated 100-300mL/0.1-0.3g
The volume ratio of grain, coupling agent and absolute ethyl alcohol is controlled in 2-6：100-300, is treated by the concentrated sulfuric acid/dioxygen water mixed liquid
Simple substance silicon nanoparticle is dispersed in absolute ethyl alcohol, heating water bath, adds Silane coupling agent KH550（Gamma-aminopropyl-triethoxy
Silane）, now, the silicone hydroxyl after the silicone hydroxyl on silicon nanoparticle surface is hydrolyzed with Silane coupling agent KH550 crosslinks condensation
Reaction, is connected to the surface of simple substance silicon nanoparticle, and the aobvious alkalescence of amino of its end makes simple substance silicon nanoparticle surface band just
Electricity, obtained graphene coated silicium cathode material specific capacity is high, and cycle performance and high rate performance are excellent.It is more highly preferred to, it is anhydrous
The volume ratio of the silicon nanoparticle that the addition of ethanol treats for 200mL/0.2g, coupling agent and absolute ethyl alcohol is 3：200.
The silane coupler that the present invention is used can also be other types of silane coupler, not depart from present inventive concept
On the premise of it is any it is obvious replacement within protection scope of the present invention.
The present invention by the way that the temperature control of heating water bath, at 65-75 DEG C, is heated by hydro-thermal, silicon nanoparticle surface
Silicone hydroxyl after silicone hydroxyl is hydrolyzed with Silane coupling agent KH550 crosslinks condensation reaction, is connected to simple substance silicon nanoparticle
Surface, the aobvious alkalescence of amino of its end, makes simple substance silicon nanoparticle surface positively charged, obtained graphene coated silicium cathode material
Specific capacity is high, and cycle performance and high rate performance are excellent.It is more highly preferred to, the temperature of heating water bath is 70 DEG C.
It is preferred that, in the step B3, silane coupler in the silicon nanoparticle suspension of silane coupler surface modification
The concentration of the silicon nanoparticle of surface modification is 2-6mg/mL.
The present invention passes through silane coupler surface modification in the silicon nanoparticle suspension by silane coupler surface modification
Silicon nanoparticle concentration control in 2-6mg/mL, it can preferably be tied with the graphene oxide in graphene oxide suspension
Close, electronegative graphene oxide is just coated on the surface of the silicon nanoparticle of positively charged, obtained graphene coated silicon is born
Pole material specific capacity is high, and cycle performance and high rate performance are excellent.It is more highly preferred to, the nano-silicon of silane coupler surface modification
The concentration of the silicon nanoparticle of silane coupler surface modification is 4mg/mL in grain suspension.
It is preferred that, in the step C1, the silicon nanoparticle of graphene oxide suspension and silane coupler surface modification
The volume ratio of suspension is 100-300：10-50.
The present invention is by by the silicon nanoparticle suspension of graphene oxide suspension and silane coupler surface modification
Volume ratio is controlled in 100-300：10-50, the silicon nanoparticle of electronegative graphene oxide and positively charged by electrostatic interaction,
Attract each other, electronegative graphene oxide is just coated on the surface of the silicon nanoparticle of positively charged, obtained graphene coated
Silicium cathode material specific capacity is high, and cycle performance and high rate performance are excellent.It is more highly preferred to, graphene oxide suspension is even with silane
The volume ratio for joining the silicon nanoparticle suspension of agent surface modification is 200：30.
It is preferred that, in the step C2, the temperature of high-temperature process is 600-800 DEG C, and the time of high-temperature process is 1-6h, is protected
Shield atmosphere is the mixed gas of nitrogen, argon gas or nitrogen and argon gas.
The present invention is by the way that by the temperature control of high-temperature process, at 600-800 DEG C, the time control of high-temperature process, will in 1-6h
The graphene oxide high temperature reduction for being coated on silicon nanoparticle surface prepares graphene coated silicium cathode material, obtained stone
Black alkene coated Si negative material specific capacity is high, and cycle performance and high rate performance are excellent.It is more highly preferred to, the temperature of high-temperature process is
700 DEG C, the time of high-temperature process is 3h.
The protective atmosphere of the present invention can also be other protective gas, any aobvious without departing from the inventive concept of the premise
And the replacement being clear to is within protection scope of the present invention.
The preparation principle of the graphene coated silicon grain negative material of the present invention is prepared using electrostatic self-assembled method：It is first
First, graphite oxide ultrasonic disperse is formed into negatively charged aobvious acidity in deionized water（Surface of graphene oxide contains substantial amounts of hydroxyl
Base, carboxyl etc., H can be provided in water+Ion, so graphene oxide is negatively charged in water, the aobvious acidity of its suspension）Oxidation
Graphene suspension；With the concentrated sulfuric acid with strong oxidizing property/dioxygen water mixed liquid processing simple substance silicon nanoparticle, the concentrated sulfuric acid/bis-
Oxygen water mixed liquid is capable of the surface of oxidizing simple substance silicon grain, and simple substance silicon face is oxidized and generates a large amount of silicone hydroxyls, by mixing
Liquid processing simple substance silicon nanoparticle is dispersed in absolute ethyl alcohol, and heating water bath adds Silane coupling agent KH550（γ-aminopropyl three
Ethoxysilane）, now, the silicone hydroxyl after the silicone hydroxyl on silicon nanoparticle surface is hydrolyzed with Silane coupling agent KH550 is handed over
Join condensation reaction, be connected to the surface of simple substance silicon nanoparticle, the aobvious alkalescence of amino of its end makes simple substance silicon nanoparticle surface
Positively charged, is centrifuged, washing, and the silicon nanoparticle for forming Silane coupling agent KH550 surface modification in deionized water is disperseed again
Suspension；Graphene oxide suspension is mixed with the silicon nanoparticle suspension of Silane coupling agent KH550 surface modification, magnetic force
Stirring, the silicon nanoparticle of electronegative graphene oxide and positively charged is attracted each other by electrostatic interaction, electronegative oxidation
Graphene is just coated on the surface of the silicon nanoparticle of positively charged, centrifuges, and washs, and dries, and high-temperature process will be coated on nano-silicon
The graphene oxide high temperature reduction of particle surface prepares graphene coated silicium cathode material.
The preparation method of the present invention uses electrostatic self-assembled synthetic technology, and raw material sources are extensive, cheap, synthetic method
Simply, process conditions are easy to control, workable, reproducible.
A kind of graphene coated silicium cathode material, the graphene coated silicium cathode material is according to preparation side described above
Method is made.
The graphene coated silicium cathode material specific capacity of the present invention is high, and cycle performance and high rate performance are excellent, in 0.01-
First discharge specific capacity reaches 2746mAh/g under 1.2V, 200mA/g current density, is kept by 100 circulation specific discharge capacities
In 803.8mAh/g.
The beneficial effects of the present invention are：The preparation method of the present invention uses electrostatic self-assembled synthetic technology, raw material sources
Extensively, cheap, synthetic method is simple, and process conditions are easy to control, workable, reproducible.
The graphene coated silicium cathode material specific capacity of the present invention is high, and cycle performance and high rate performance are excellent, in 0.01-
First discharge specific capacity reaches 2746mAh/g under 1.2V, 200mA/g current density, is kept by 100 circulation specific discharge capacities
In 803.8mAh/g.
The present invention has clad structure using graphene coated silicium cathode material made from electrostatic self-assembled method, so as to
The expansion of silicon electrode is buffered, graphene is imitated with more excellent electric conductivity to strengthen transmission of the electronics in graphene coated silicon
Rate, is conducive to improving the storage lithium specific capacity and cycle performance of graphene coated silicon.
The present invention is smaller using graphene coated silicium cathode material granule made from electrostatic self-assembled method, can improve graphite
The specific surface area of alkene coated Si, so as to reduce diffusion length of the lithium ion in graphene coated silicon, is conducive to improving graphene
The storage lithium specific capacity of coated Si, contributes to the infiltration of electrolyte, so as to improve the electronic conductance of graphene coated silicium cathode material
Rate, Research Thinking is provided to seek novel cathode material for lithium ion battery.
Brief description of the drawings
Fig. 1 is the projection electron microscope of graphene coated silicium cathode material made from embodiment 1.
Fig. 2 is the standard powder diffraction pattern of graphene coated silicium cathode material made from embodiment 1.
Fig. 3 is graphene coated silicium cathode material made from embodiment 1 under 0.01-1.2V, 200mA/g current density
First charge-discharge curve map.
Fig. 4 is graphene coated silicium cathode material made from embodiment 1 under 0.01-1.2V, 200mA/g current density
Cycle performance curve map.
Fig. 5 is graphene coated silicium cathode material made from embodiment 2 under 0.01-1.2V, 200mA/g current density
Cycle performance curve map.
Fig. 6 is graphene coated silicium cathode material made from embodiment 3 under 0.01-1.2V, 200mA/g current density
Cycle performance curve map.
Embodiment
For the ease of the understanding of those skilled in the art, further is made to the present invention with reference to embodiment and accompanying drawing 1-6
Explanation, the content that embodiment is referred to not limitation of the invention.
The instrument used in tem analysis that the present invention is used is Rigaku electronics corporation（JEOL）JEOLJEM2010 types
Projection electron microscope（TEM）The microscopic appearance of specimen surface is observed, accelerating potential is 200KV, and sample preparation is using absolute ethyl alcohol point
It is added dropwise after dissipating on conducting resinl surface, air drying.
The instrument used in XRD analysis that the present invention is used spreads out for Beijing Pu Xi all purpose instruments Co., Ltd XD-2 type X-rays
Penetrate instrument（XRD）Characterize the crystal phase structure of prepared final product.Test condition is Cu targets, K α radiation, 36kV, 30mA, step width
0.02o, scanning range 10~80o.Sample is that powder is placed in the pressing of sample stage groove, is directly detected.
The instrument used in charge-discharge test that the present invention is used for new Weir Electronics Co., Ltd. of Shenzhen BTS51800
Battery test system, model CT-3008W carries out electro-chemical test in 0.01-1.2V voltage ranges.
Embodiment 1
A kind of preparation method of graphene coated silicium cathode material, comprises the following steps：
A, preparation graphene oxide suspension：Under conditions of ice-water bath, take 3.0g graphite be added to 360mL sulfuric acid and
In the mixed liquor of 40mL concentrated phosphoric acids, stir, slowly 6.0g potassium permanganate be added in the mixed liquor, stirred,
50 DEG C, and mechanical agitation 24h are then heated to, reactant is obtained；Reactant is cooled to room temperature and 400mL frozen water is poured slowly into
In mixed liquor with 30mL mass fractions for 30% hydrogen peroxide, then the mixed liquor is centrifuged, and use 500mL
Mass fraction washs for 5% HCl, and it is 7 or so to be then washed with deionized water to pH value, and obtained product is true at a temperature of 50 DEG C
Sky is dried to remove water, and graphite oxide is made；Weigh appropriate graphite oxide to be distributed in deionized water, ultrasonic 30min, prepare
Into 1.0mg/mL graphene oxide suspension；
B, prepare silicon nanoparticle suspension：Under conditions of ice-water bath, the 10mL concentrated sulfuric acids are added into 40mL hydrogen peroxide,
Stir, then add 0.4g simple substance silicon nanoparticles, continue to stir 8h, centrifuge washing obtains treated receive after drying
Rice silicon grain；The silicon nanoparticle for taking 0.2g treated is added in 100mL absolute ethyl alcohols, ultrasonic disperse 30min, 70 DEG C of water-bath
Stirring, is slowly added dropwise 1mLKH550, and the nano-silicon of KH550 surface modifications is made in constant temperature stirring 12h, cooling, suction filtration after drying
Grain；Again the silicon nanoparticle suspension for being configured to 1.0mg/mL KH550 surface modifications in deionized water is disperseed；
C, prepare graphene coated silicium cathode material：By 200mL 1.0mg/mL graphene oxide suspension and 800mL
1.0mg/mL KH550 surface modifications silicon nanoparticle suspension mixing, stir 8h, centrifuge washing, argon atmosphere
Lower 700 DEG C of processing 2h, prepares graphene coated silicium cathode material.
A kind of graphene coated silicium cathode material, the graphene coated silicium cathode material is according to preparation side described above
Method is made.
As shown in figure 1, silicon grain is about 50 ~ 300 nanometers, and by graphene coated；Graphene coated silicium cathode material
XRD is as shown in Figure 2.28.5 °, 47.3 °, 56.2 °, 69.1 °, 76.5 ° belong to elemental silicon characteristic peak, the feature at 28.5 °
Peak belongs to graphene.
The electrochemical property test of graphene coated silicium cathode material prepared by embodiment 1：
Graphene coated silicium cathode material prepared by embodiment 1 and conductive carbon black, binding agent Vingon（PVDF）
In mass ratio 8: 1: 1 mixing, add appropriate 1-METHYLPYRROLIDONE（NMP）Stir, be applied on copper foil, dried in vacuum
In being dried at 90 DEG C in case, graphene coated silicium cathode material electrodes piece is obtained in sheet-punching machine top shear blade.The electrode obtained is done into negative pole,
Metal lithium sheet is positive pole, and electrolyte is to contain 1MLiPF6/（EC+DMC）（Volume ratio is 1: 1）Mixed system, barrier film is poly- for micropore
Propylene film（Celgard2400）, full of argon gas（Ar）Glove box in be assembled into 2025 type button cells.With the new prestige in Shenzhen
You carry out charge-discharge performance test by Electronics Co., Ltd.'s BTS51800 battery test systems.
It can be seen that material first discharge specific capacity under 0.01-1.2V, 200mA/g current densities reaches from Fig. 3 and 4
To 2746mAh/g, 803.8mAh/g is maintained by 100 circulation specific discharge capacities, with preferable electrochemistry cycle performance.
Embodiment 2
A kind of preparation method of graphene coated silicium cathode material, comprises the following steps：
A, preparation graphene oxide suspension：Under conditions of ice-water bath, take 3.0g graphite be added to 360mL sulfuric acid and
In the mixed liquor of 40mL concentrated phosphoric acids, stir, slowly 6.0g potassium permanganate be added in the mixed liquor, stirred,
50 DEG C, and mechanical agitation 24h are then heated to, reactant is obtained；Reactant is cooled to room temperature and 400mL frozen water is poured slowly into
In mixed liquor with 30mL mass fractions for 30% hydrogen peroxide, then the mixed liquor is centrifuged, and use 500mL
Mass fraction washs for 5% HCl, and it is 7 or so to be then washed with deionized water to pH value, and obtained product is true at a temperature of 50 DEG C
Sky is dried to remove water, and graphite oxide is made；Weigh appropriate graphite oxide to be distributed in deionized water, ultrasonic 30min, prepare
Into 1.0mg/mL graphene oxide suspension.
B, prepare silicon nanoparticle suspension：Under conditions of ice-water bath, the 10mL concentrated sulfuric acids are added into 40mL hydrogen peroxide,
Stir, then add 0.4g simple substance silicon nanoparticles, continue to stir 8h, centrifuge washing obtains treated receive after drying
Rice silicon grain；The silicon nanoparticle for taking 0.2g treated is added in 100mL absolute ethyl alcohols, ultrasonic disperse 30min, 70 DEG C of water-bath
Stirring, is slowly added dropwise 1mLKH550, and the nano-silicon of KH550 surface modifications is made in constant temperature stirring 12h, cooling, suction filtration after drying
Grain；Again the silicon nanoparticle suspension for being configured to 1.0mg/mL KH550 surface modifications in deionized water is disperseed.
C, prepare graphene coated silicium cathode material：By 150mL 1.0mg/mL graphene oxide suspension and 800mL
1.0mg/mL KH550 surface modifications silicon nanoparticle suspension mixing, stir 8h, centrifuge washing, argon atmosphere
Lower 700 DEG C of processing 2h, prepares graphene coated silicium cathode material.
A kind of graphene coated silicium cathode material, the graphene coated silicium cathode material is according to preparation side described above
Method is made.
The electrochemical property test of graphene coated silicium cathode material prepared by embodiment 2：
Graphene coated silicium cathode material prepared by embodiment 2 and conductive carbon black, binding agent Vingon（PVDF）
In mass ratio 8: 1: 1 mixing, add appropriate 1-METHYLPYRROLIDONE（NMP）Stir, be applied on copper foil, dried in vacuum
In being dried at 90 DEG C in case, graphene coated silicium cathode material electrodes piece is obtained in sheet-punching machine top shear blade.The electrode obtained is done into negative pole,
Metal lithium sheet is positive pole, and electrolyte is to contain 1MLiPF6/（EC+DMC）（Volume ratio is 1: 1）Mixed system, barrier film is poly- for micropore
Propylene film（Celgard2400）, full of argon gas（Ar）Glove box in be assembled into 2025 type button cells.With the new prestige in Shenzhen
You carry out charge-discharge performance test by Electronics Co., Ltd.'s BTS51800 battery test systems.
As can be seen from Figure 5 first discharge specific capacity of the material under 0.01-1.2V, 200mA/g current densities reaches
To 3507.3mAh/g, 630.5mAh/g is maintained by 100 circulation specific discharge capacities, shows that the material has preferable electricity
Chemical property.
Embodiment 3
A kind of preparation method of graphene coated silicium cathode material, comprises the following steps：
A, preparation graphene oxide suspension：Under conditions of ice-water bath, take 3.0g graphite be added to 360mL sulfuric acid and
In the mixed liquor of 40mL concentrated phosphoric acids, stir, slowly 6.0g potassium permanganate be added in the mixed liquor, stirred,
50 DEG C, and mechanical agitation 24h are then heated to, reactant is obtained；Reactant is cooled to room temperature and 400mL frozen water is poured slowly into
In mixed liquor with 30mL mass fractions for 30% hydrogen peroxide, then the mixed liquor is centrifuged, and use 500mL
Mass fraction washs for 5% HCl, and it is 7 or so to be then washed with deionized water to pH value, and obtained product is true at a temperature of 50 DEG C
Sky is dried to remove water, and graphite oxide is made；Weigh appropriate graphite oxide to be distributed in deionized water, ultrasonic 30min, prepare
Into 1.0mg/mL graphene oxide suspension.
B, prepare silicon nanoparticle suspension：Under conditions of ice-water bath, the 10mL concentrated sulfuric acids are added into 40mL hydrogen peroxide,
Stir, then add 0.4g simple substance silicon nanoparticles, continue to stir 8h, centrifuge washing obtains treated receive after drying
Rice silicon grain；The silicon nanoparticle for taking 0.2g treated is added in 100mL absolute ethyl alcohols, ultrasonic disperse 30min, 70 DEG C of water-bath
Stirring, is slowly added dropwise 1mLKH550, and the nano-silicon of KH550 surface modifications is made in constant temperature stirring 12h, cooling, suction filtration after drying
Grain；Again the silicon nanoparticle suspension for being configured to 1.0mg/mL KH550 surface modifications in deionized water is disperseed.
C, prepare graphene coated silicium cathode material：By 100mL 1.0mg/mL graphene oxide suspension and 800mL
1.0mg/mL KH550 surface modifications silicon nanoparticle suspension mixing, stir 8h, centrifuge washing, argon atmosphere
Lower 700 DEG C of processing 2h, prepares graphene coated silicium cathode material.
A kind of graphene coated silicium cathode material, the graphene coated silicium cathode material is according to preparation side described above
Method is made.
The electrochemical property test of graphene coated silicium cathode material prepared by embodiment 3：
Graphene coated silicium cathode material prepared by embodiment 3 and conductive carbon black, binding agent Vingon（PVDF）
In mass ratio 8: 1: 1 mixing, add appropriate 1-METHYLPYRROLIDONE（NMP）Stir, be applied on copper foil, dried in vacuum
In being dried at 90 DEG C in case, graphene coated silicium cathode material electrodes piece is obtained in sheet-punching machine top shear blade.The electrode obtained is done into negative pole,
Metal lithium sheet is positive pole, and electrolyte is to contain 1MLiPF6/（EC+DMC）（Volume ratio is 1: 1）Mixed system, barrier film is poly- for micropore
Propylene film（Celgard2400）, full of argon gas（Ar）Glove box in be assembled into 2025 type button cells.With the new prestige in Shenzhen
You carry out charge-discharge performance test by Electronics Co., Ltd.'s BTS51800 battery test systems.
As can be seen from Figure 6 first discharge specific capacity of the material under 0.01-1.2V, 200mA/g current densities reaches
To 3378.7mAh/g, 530.8mAh/g is maintained by 100 circulation specific discharge capacities, shows that the material has preferable electricity
Chemical property.
Embodiment 4
A kind of preparation method of graphene coated silicium cathode material, comprises the following steps：
A, preparation graphene oxide suspension：
A1, under conditions of ice-water bath, concentrated phosphoric acid is added into the concentrated sulfuric acid, is stirred, graphite is then added, stirring is equal
It is even, potassium permanganate powder is slow added into, 30min is stirred, 45 DEG C are then heated to, 20h is stirred, obtains reactant；
A2, the obtained reactants of step A1 are cooled to room temperature and are poured slowly into the mixed liquor of frozen water and hydrogen peroxide, so
After centrifuge, and washed with watery hydrochloric acid, it is 6.8 to be then washed with deionized water to pH value, and obtained product is dry in 45 DEG C of vacuum
It is dry, graphite oxide is made；
A3, by graphite oxide ultrasonic disperse made from step A2 in deionized water, formed graphene oxide suspension；
B, prepare silicon nanoparticle suspension：
B1, under conditions of ice-water bath, the concentrated sulfuric acid is added into hydrogen peroxide, is stirred, then add simple substance nano-silicon
Particle, continues to stir, and centrifuge washing obtains treated silicon nanoparticle after drying；
B2, the silicon nanoparticle ultrasonic disperse for treating step B1 are in absolute ethyl alcohol, and idol is slowly added dropwise in heating water bath
Join agent, the silicon nanoparticle of coupling agent surface modification is made in constant temperature stirring 8h, cooling, suction filtration after drying；
B3, by the silicon nanoparticle ultrasonic disperse of coupling agent surface modification made from step B2 in deionized water, formed
The silicon nanoparticle suspension of silane coupler surface modification；
C, prepare graphene coated silicium cathode material：
C1, receiving silane coupler surface modification made from graphene oxide suspension made from step A3 and step B3
The suspension mixing of rice silicon grain, stirs, centrifuge washing obtains mixture；
C2, the mixture for obtaining step C1 carry out high-temperature process under protective atmosphere, prepare graphene coated silicium cathode
Material.
In the step A1, the mass ratio of graphite and potassium permanganate is 1：2, the addition of the concentrated sulfuric acid is 60mL/1g graphite,
Concentrated phosphoric acid and the volume ratio of the concentrated sulfuric acid are 1:6.
In the step A2, the mass fraction of hydrogen peroxide is 10%, and the volume ratio of frozen water and hydrogen peroxide is 120：10, dilute salt
The mass fraction of acid is 3%.
In the step A3, the time of ultrasonic disperse is the concentration of graphene oxide in 30min, graphene oxide suspension
For 0.1mg/mL.
In the step B1, the mass fraction of hydrogen peroxide is 25, and the volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 120：20, simple substance
The addition of silicon nanoparticle is the 0.3g/30mL concentrated sulfuric acids.
In the step B2, the addition of absolute ethyl alcohol is the silicon nanoparticle that 100mL/0.1g is treated, coupling agent with
The volume ratio of absolute ethyl alcohol is 2：100, silane coupler is Silane coupling agent KH550, and the temperature of heating water bath is 65 DEG C.
In the step B3, silane coupler surface modification in the silicon nanoparticle suspension of silane coupler surface modification
Silicon nanoparticle concentration be 2mg/mL.
In the step C1, graphene oxide suspension and the silicon nanoparticle suspension of silane coupler surface modification
Volume ratio is 100：10.
In the step C2, the temperature of high-temperature process is 600 DEG C, and the time of high-temperature process is 6h, and protective atmosphere is nitrogen.
A kind of graphene coated silicium cathode material, the graphene coated silicium cathode material is according to preparation side described above
Method is made.
Embodiment 5
A kind of preparation method of graphene coated silicium cathode material, comprises the following steps：
A, preparation graphene oxide suspension：
A1, under conditions of ice-water bath, concentrated phosphoric acid is added into the concentrated sulfuric acid, is stirred, graphite is then added, stirring is equal
It is even, potassium permanganate powder is slow added into, 45min is stirred, 50 DEG C are then heated to, 24h is stirred, obtains reactant；
A2, the obtained reactants of step A1 are cooled to room temperature and are poured slowly into the mixed liquor of frozen water and hydrogen peroxide, so
After centrifuge, and washed with watery hydrochloric acid, it is 7.0 to be then washed with deionized water to pH value, and obtained product is dry in 50 DEG C of vacuum
It is dry, graphite oxide is made；
A3, by graphite oxide ultrasonic disperse made from step A2 in deionized water, formed graphene oxide suspension；
B, prepare silicon nanoparticle suspension：
B1, under conditions of ice-water bath, the concentrated sulfuric acid is added into hydrogen peroxide, is stirred, then add simple substance nano-silicon
Particle, continues to stir, and centrifuge washing obtains treated silicon nanoparticle after drying；
B2, the silicon nanoparticle ultrasonic disperse for treating step B1 are in absolute ethyl alcohol, and idol is slowly added dropwise in heating water bath
Join agent, the silicon nanoparticle of coupling agent surface modification is made in constant temperature stirring 12h, cooling, suction filtration after drying；
B3, by the silicon nanoparticle ultrasonic disperse of coupling agent surface modification made from step B2 in deionized water, formed
The silicon nanoparticle suspension of silane coupler surface modification；
C, prepare graphene coated silicium cathode material：
C1, receiving silane coupler surface modification made from graphene oxide suspension made from step A3 and step B3
The suspension mixing of rice silicon grain, stirs, centrifuge washing obtains mixture；
C2, the mixture for obtaining step C1 carry out high-temperature process under protective atmosphere, prepare graphene coated silicium cathode
Material.
In the step A1, the mass ratio of graphite and potassium permanganate is 2：4, the addition of the concentrated sulfuric acid is 210mL/2g stones
The volume ratio of ink, concentrated phosphoric acid and the concentrated sulfuric acid is 2.5:21.
In the step A2, the mass fraction of hydrogen peroxide is 20%, and the volume ratio of frozen water and hydrogen peroxide is 260：20, dilute salt
The mass fraction of acid is 4.5%.
In the step A3, the time of ultrasonic disperse is the concentration of graphene oxide in 75min, graphene oxide suspension
For 0.5mg/mL.
In the step B1, the mass fraction of hydrogen peroxide is 30%, and the volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 210：40, it is single
The addition of matter silicon nanoparticle is the 0.4g/40mL concentrated sulfuric acids.
In the step B2, the addition of absolute ethyl alcohol is the silicon nanoparticle that 200mL/0.2g is treated, coupling agent with
The volume ratio of absolute ethyl alcohol is 4：200, silane coupler is Silane coupling agent KH550, and the temperature of heating water bath is 70 DEG C.
In the step B3, silane coupler surface modification in the silicon nanoparticle suspension of silane coupler surface modification
Silicon nanoparticle concentration be 4mg/mL.
In the step C1, graphene oxide suspension and the silicon nanoparticle suspension of silane coupler surface modification
Volume ratio is 200：30.
In the step C2, the temperature of high-temperature process is 700 DEG C, and the time of high-temperature process is 3h, and protective atmosphere is argon gas.
A kind of graphene coated silicium cathode material, the graphene coated silicium cathode material is according to preparation side described above
Method is made.
Embodiment 6
A kind of preparation method of graphene coated silicium cathode material, comprises the following steps：
A, preparation graphene oxide suspension：
A1, under conditions of ice-water bath, concentrated phosphoric acid is added into the concentrated sulfuric acid, is stirred, graphite is then added, stirring is equal
It is even, potassium permanganate powder is slow added into, 60min is stirred, 55 DEG C are then heated to, 28h is stirred, obtains reactant；
A2, the obtained reactants of step A1 are cooled to room temperature and are poured slowly into the mixed liquor of frozen water and hydrogen peroxide, so
After centrifuge, and washed with watery hydrochloric acid, it is 7.2 to be then washed with deionized water to pH value, and obtained product is dry in 55 DEG C of vacuum
It is dry, graphite oxide is made；
A3, by graphite oxide ultrasonic disperse made from step A2 in deionized water, formed graphene oxide suspension；
B, prepare silicon nanoparticle suspension：
B1, under conditions of ice-water bath, the concentrated sulfuric acid is added into hydrogen peroxide, is stirred, then add simple substance nano-silicon
Particle, continues to stir, and centrifuge washing obtains treated silicon nanoparticle after drying；
B2, the silicon nanoparticle ultrasonic disperse for treating step B1 are in absolute ethyl alcohol, and idol is slowly added dropwise in heating water bath
Join agent, the silicon nanoparticle of coupling agent surface modification is made in constant temperature stirring 16h, cooling, suction filtration after drying；
B3, by the silicon nanoparticle ultrasonic disperse of coupling agent surface modification made from step B2 in deionized water, formed
The silicon nanoparticle suspension of silane coupler surface modification；
C, prepare graphene coated silicium cathode material：
C1, receiving silane coupler surface modification made from graphene oxide suspension made from step A3 and step B3
The suspension mixing of rice silicon grain, stirs, centrifuge washing obtains mixture；
C2, the mixture for obtaining step C1 carry out high-temperature process under protective atmosphere, prepare graphene coated silicium cathode
Material.
In the step A1, the mass ratio of graphite and potassium permanganate is 3：6, the addition of the concentrated sulfuric acid is 360mL/3g stones
The volume ratio of ink, concentrated phosphoric acid and the concentrated sulfuric acid is 4:36.
In the step A2, the mass fraction of hydrogen peroxide is 30%, and the volume ratio of frozen water and hydrogen peroxide is 400：30, dilute salt
The mass fraction of acid is 6%.
In the step A3, time of ultrasonic disperse is the dense of graphene oxide in 120min, graphene oxide suspension
Spend for 1mg/mL.
In the step B1, the mass fraction of hydrogen peroxide is 35%, and the volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 300：60, it is single
The addition of matter silicon nanoparticle is the 0.5g/50mL concentrated sulfuric acids.
In the step B2, the addition of absolute ethyl alcohol is the silicon nanoparticle that 300mL/0.3g is treated, coupling agent with
The volume ratio of absolute ethyl alcohol is 6：300, silane coupler is Silane coupling agent KH550, and the temperature of heating water bath is 75 DEG C.
In the step B3, silane coupler surface modification in the silicon nanoparticle suspension of silane coupler surface modification
Silicon nanoparticle concentration be 6mg/mL.
In the step C1, graphene oxide suspension and the silicon nanoparticle suspension of silane coupler surface modification
Volume ratio is 300：50.
In the step C2, the temperature of high-temperature process is 800 DEG C, and the time of high-temperature process is 1h, and protective atmosphere is nitrogen
With the mixed gas of argon gas.
A kind of graphene coated silicium cathode material, the graphene coated silicium cathode material is according to preparation side described above
Method is made.
Above-described embodiment is the present invention preferably implementation, and in addition, the present invention can be realized with other manner,
Any obvious replacement is within protection scope of the present invention on the premise of not departing from present inventive concept.
Claims (6)
1. a kind of preparation method of graphene coated silicium cathode material, it is characterised in that：Comprise the following steps：
A, preparation graphene oxide suspension：
A1, under conditions of ice-water bath, concentrated phosphoric acid is added into the concentrated sulfuric acid, is stirred, graphite is then added, stirred,
Potassium permanganate powder is slow added into, 30-60min is stirred, 45-55 DEG C is then heated to, 20-28h is stirred, obtains reactant；
A2, the obtained reactants of step A1 are cooled to room temperature and are poured slowly into the mixed liquor of frozen water and hydrogen peroxide, Ran Houli
The heart is separated, and is washed with watery hydrochloric acid, and it is 6.8-7.2 to be then washed with deionized water to pH value, and obtained product is in 45-55 DEG C of vacuum
Dry, graphite oxide is made；
A3, by graphite oxide ultrasonic disperse made from step A2 in deionized water, formed graphene oxide suspension；
B, prepare silicon nanoparticle suspension：
B1, under conditions of ice-water bath, the concentrated sulfuric acid is added into hydrogen peroxide, is stirred, then add simple substance silicon nanoparticle,
Continue to stir, centrifuge washing obtains treated silicon nanoparticle after drying；
B2, the silicon nanoparticle ultrasonic disperse for treating step B1 are in absolute ethyl alcohol, and it is even that silane is slowly added dropwise in heating water bath
Join agent, the silicon nanoparticle of silane coupler surface modification is made in constant temperature stirring 8-16h, cooling, suction filtration after drying；
B3, by the silicon nanoparticle ultrasonic disperse of silane coupler surface modification made from step B2 in deionized water, formed
The silicon nanoparticle suspension of silane coupler surface modification；
C, prepare graphene coated silicium cathode material：
C1, the nano-silicon by silane coupler surface modification made from graphene oxide suspension made from step A3 and step B3
Particle suspension liquid is mixed, and is stirred, centrifuge washing obtains mixture；
C2, the mixture for obtaining step C1 carry out high-temperature process under protective atmosphere, prepare graphene coated silicium cathode material,
The temperature of high-temperature process is 600-800 DEG C；
In the step A1, the mass ratio of graphite and potassium permanganate is 1-3：2-6, the addition of the concentrated sulfuric acid is 60-360mL/1-
The volume ratio of 3g graphite, concentrated phosphoric acid and the concentrated sulfuric acid is 1-4:6-36；
In the step A2, the mass fraction of hydrogen peroxide is 10%-30%, and the volume ratio of frozen water and hydrogen peroxide is 120-400：10-
30, the mass fraction of watery hydrochloric acid is 3%-6%；
In the step A3, the time of ultrasonic disperse is the concentration of graphene oxide in 30-120min, graphene oxide suspension
For 0.1-1mg/mL；
In the step B1, the mass fraction of hydrogen peroxide is 25%-35%, and the volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 120-300：
20-60, the addition of simple substance silicon nanoparticle is the 0.3-0.5g/30-50mL concentrated sulfuric acids.
2. a kind of preparation method of graphene coated silicium cathode material according to claim 1, it is characterised in that：The step
In rapid B2, the addition of absolute ethyl alcohol is the silicon nanoparticle that 100-300mL/0.1-0.3g is treated, silane coupler and nothing
The volume ratio of water-ethanol is 2-6：100-300, silane coupler is Silane coupling agent KH550, and the temperature of heating water bath is 65-75
℃。
3. a kind of preparation method of graphene coated silicium cathode material according to claim 1, it is characterised in that：The step
In rapid B3, the silicon nanoparticle of silane coupler surface modification in the silicon nanoparticle suspension of silane coupler surface modification
Concentration is 2-6mg/mL.
4. a kind of preparation method of graphene coated silicium cathode material according to claim 1, it is characterised in that：The step
In rapid C1, the volume ratio of graphene oxide suspension and the silicon nanoparticle suspension of silane coupler surface modification is 100-
300：10-50.
5. a kind of preparation method of graphene coated silicium cathode material according to claim 1, it is characterised in that：The step
In rapid C2, the temperature of high-temperature process is 600-800 DEG C, and the time of high-temperature process is 1-6h, and protective atmosphere is nitrogen, argon gas or nitrogen
The mixed gas of gas and argon gas.
6. a kind of graphene coated silicium cathode material, it is characterised in that：The graphene coated silicium cathode material will according to right
The preparation method described in any one of 1-5 is asked to be made.
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| CN113193180B (en) * | 2021-04-16 | 2023-05-26 | 西安交通大学 | Preparation method of silicon/functionalized graphene intercalation composite material with surface coupling activity |
| CN113422016A (en) * | 2021-06-16 | 2021-09-21 | 内蒙古碳烯石墨新材料有限公司 | Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof |
| CN115650807A (en) * | 2022-09-26 | 2023-01-31 | 北京理工大学 | Preparation method of composite material of graphene loaded with nitrogen-containing compound |
| CN115536383B (en) * | 2022-11-02 | 2023-04-07 | 株洲火炬安泰新材料有限公司 | High-density ITO green body sintering method with accurate process control |
| CN117069982B (en) * | 2023-10-10 | 2024-02-09 | 山东乐康电器科技有限公司 | Target potential pole piece for releasing reduction ions, preparation method and application thereof in mattress |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491318A (en) * | 2011-12-13 | 2012-06-13 | 河北工业大学 | Method for preparing graphene oxide |
| CN104752696A (en) * | 2015-01-22 | 2015-07-01 | 湖州创亚动力电池材料有限公司 | Preparation method of graphene-based silicon and carbon composite negative electrode material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014148849A1 (en) * | 2013-03-20 | 2014-09-25 | 주식회사 아모그린텍 | Anode active material for secondary battery, anode, secondary battery using anode, and method for manufacturing secondary battery |
-
2015
- 2015-07-03 CN CN201510385666.8A patent/CN104916826B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491318A (en) * | 2011-12-13 | 2012-06-13 | 河北工业大学 | Method for preparing graphene oxide |
| CN104752696A (en) * | 2015-01-22 | 2015-07-01 | 湖州创亚动力电池材料有限公司 | Preparation method of graphene-based silicon and carbon composite negative electrode material |
Non-Patent Citations (1)
| Title |
|---|
| 硅/石墨烯纳米复合材料作为锂离子电池负极材料的研究;李国瑞;《中国优秀硕士学位论文全文数据库·工程科技Ⅱ辑》;20140515(第5期);第C042-602页 * |
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