CN103803534A - Preparation method of graphene-silicon nanopowder composite material - Google Patents
Preparation method of graphene-silicon nanopowder composite material Download PDFInfo
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Abstract
The invention is suitable for the technical field of organic semiconductor materials, and provides a preparation method of a graphene-silicon nanopowder composite material. The method comprises the following steps: preparing a graphene microchip; carrying out surface modification on the graphene microchip; mixing the graphene microchip subjected to surface modification with silicon nano particles to prepare a graphene-silicon mixed material; and preparing the graphene-silicon mixed material into the graphene-silicon nanopowder composite material. According to the technical scheme provided by the invention, the method of industrially producing the graphene-silicon nanopowder composite material on a large scale has the advantages of small use level of acids and oxidizing agents, low cost, fewer acids and harmful effluents and environmental friendliness; the lattice of graphite is damaged to a little extent in the surface modification process, and the material is easy to reduce and good in electrical conductivity.
Description
Technical field
The invention belongs to organic semiconductor material technical field, relate in particular to a kind of preparation method of Graphene-silicon nano power powder composite material.
Background technology
Graphene is a kind of new carbon of broad research in recent years, is that carbon atom is arranged the Colloidal particles forming according to hexagonal.As monolayer carbon atomic plane material, Graphene can obtain by peeling off graphite material.The thickness of Graphene only has 0.335 nanometer, is not only one the thinnest in known materials, also very firmly hard; As simple substance, it is all faster than known all conductors and semi-conductor that it at room temperature transmits the speed of electronics, and in Graphene, the travelling speed of electronics has reached 1/300 of the light velocity.Meanwhile, as monolayer carbon atomic structure, the theoretical specific surface area of Graphene is up to 2630m2/g, and so high specific surface area makes to become extremely promising energy storage active material based on the material of Graphene.
Mainly prepare graphene powder material and matrix material thereof based on oxidation style (Hummers method) at present, graphite, under the effect of the strong oxidizers such as H2SO4, HNO3, HClO4, or under electrochemistry peroxidation, forms graphite oxide after hydrolysis.Different with graphite, due to the existence of polar group, oxidized graphite flake layer has the characteristic of stronger hydrophilic or polar solvent.Therefore, graphite oxide, in external force, as peeled off in water or in other polar solvent under hyperacoustic effect, forms mono-layer graphite oxide alkene (GrapheneOxide).But Hummers legal system is for being used a large amount of soda acids in graphene oxide process, cost is high, produces a large amount of soda acids simultaneously and dumps thing, unfriendly to environment.
Summary of the invention
The object of the embodiment of the present invention is to overcome problems of the prior art, and the preparation method of a kind of applicable low-cost industrial scale operation, high quality, the poisonous Graphene-silicon nano composite material that dumps thing of minimizing is provided.
The embodiment of the present invention is achieved in that a kind of preparation method of Graphene-silicon nano power powder composite material, said method comprising the steps of: prepare Graphene microplate; Graphene microplate is carried out to surface modification; The Graphene microplate mixing nano silicon particles of surface modification is made to Graphene-silica hybrid material; And Graphene-silica hybrid material is made to Graphene-silicon nano power powder composite material.
In a preferred embodiment, the described Graphene microplate of preparing comprises the following steps: prepare expanded graphite; The expanded graphite obtaining is mixed with organic solvent; Expanded graphite organic solvent mixed solution is carried out to ultrasonic dissociating and obtain Graphene microplate suspension; And extract Graphene microplate from Graphene microplate suspension.
In a preferred embodiment, the described expanded graphite of preparing, for expansible black lead is placed in to metal or ceramic crucible, under protection of inert gas, is heated to 300-900 degree, keeps temperature 10-60 to divide, and realizes fully and expanding, and is then cooled to room temperature.
In a preferred embodiment, the described expanded graphite of preparing is for to be placed in ceramic crucible or glassware by expansible black lead, with 600-1200W microwave heating 10-60 second, realizes fully and expanding, and is then cooled to room temperature.
In a preferred embodiment, described the expanded graphite obtaining and organic solvent are mixed into gained expanded graphite is placed in to container, pour 100-1000ml organic solvent into, stir.
In a preferred embodiment, describedly expanded graphite organic solvent mixed solution is carried out to ultrasonic dissociating obtain Graphene microplate suspension for being the 1-24 hour that vibrates under 300-1200W condition at sonic oscillation power, Heating temperature is 20-150 degree simultaneously, obtains Graphene microplate suspension.
In a preferred embodiment, the described Graphene microplate that extracts from Graphene microplate suspension, for ultrasonic gained Graphene microplate suspension is left standstill to 0.2-5 hour, removes upper strata suspension, removes throw out, after filtration, in 80 degree baking ovens, dries.
In a preferred embodiment, described Graphene microplate is carried out to surface modification for gained Graphene microplate is added in the vitriol oil, keep the temperature of solution lower than 4 ℃, slowly add potassium permanganate, in adding procedure, the temperature of solution does not exceed 10 ℃; After potassium permanganate adds, keep the temperature of solution lower than 10 ℃ of magnetic agitation 90min; Then, the in the situation that of magnetic agitation, slowly add deionized water, guarantee that the temperature of solution is lower than 40 ℃ simultaneously; Add hydrogen peroxide, continue to stir 15min; Last filtering drying obtains surface modified graphite alkene microplate.
In a preferred embodiment, it is that the surface modified graphite alkene microplate of gained is added in deionized water that the described Graphene microplate mixing nano silicon particles by surface modification obtains Graphene-silica hybrid material, keep the temperature of solution lower than 35 ℃, ultrasonic dispersion 10-60min; Nano silicon particles is joined in deionized water to ultrasonic dispersion 30-60min; Nano silicon particles is easily mixed with surface modified graphite alkene solution, keep solution temperature lower than 35 ℃, ultrasonic dispersion 30-60min; Finally, filter out solution, obtain surface modified graphite alkene-silica hybrid material.
In a preferred embodiment, Graphene-silica hybrid material is made to Graphene-silicon nano power powder composite material for 300-1000 ℃ of annealing 0.1-2h under inert atmosphere protection, obtain Graphene-silicon nano power powder composite material.
In an embodiment of the present invention, produce Graphene-silicon nano power powder composite material by technical solution of the present invention large-scale industrialization, have the following advantages: 1, little by acid amount and oxidant content, cost is low; 2. acid and noxious emission are few, environmentally friendly; 3. Process of Surface Modification is little to graphite lattice damage, easily reduction, product good conductivity.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
In an embodiment of the present invention, by Graphene microplate is carried out to surface modification, then adsorb silicon nanopowder and obtain Graphene-silicon nano power powder composite material.
The implementing procedure of Graphene-silicon nanopowder composite material and preparation method thereof that the embodiment of the present invention provides, details are as follows:
One, prepare Graphene microplate;
1. prepare expanded graphite: expansible black lead is placed in to metal or ceramic crucible, under protection of inert gas, is heated to 300-900 degree, keep temperature 10-60 minute, realize fully and expanding, be then cooled to room temperature.
Or expansible black lead is placed in to ceramic crucible or glassware, with 600-1200W microwave heating 10-60 second, realizes fully and expanding, be then cooled to room temperature.
In specific embodiment, raw material is desirable crystalline flake graphite also.
2. the expanded graphite obtaining is mixed with organic solvent: gained expanded graphite is placed in to container, pours 100-1000ml organic solvent into, described organic solvent is NMP, DMP, toluene, chlorobenzene or trieline, stirs.
3. expanded graphite organic solvent mixed solution is carried out to ultrasonic dissociating and obtain Graphene microplate suspension: be the 1-24 hour that vibrates under 300-1200W condition at sonic oscillation power, heating simultaneously, temperature is 20-150 degree, obtains Graphene microplate suspension.Ultrasonic jitter time is too short in 60 minutes, to such an extent as to the effect that dispersion is dissociated is bad, and the present invention adopts concussion 1-24 hour, can effectively improve dispersion effect.The heating of taking in addition is also conducive to improve dispersion effect.
4. from Graphene microplate suspension, extract Graphene microplate: ultrasonic gained Graphene microplate suspension is left standstill to 0.2-5 hour, get upper strata suspension, remove throw out, after filtration, in 80 degree baking ovens, dry.The present invention, without centrifugal treating, saves fabrication steps, enhances productivity.
Two. Graphene microplate is carried out to surface modification:
Gained Graphene microplate is added in the vitriol oil of 20-100ml, keep the temperature of solution lower than 4 ℃, slowly add the potassium permanganate of 0.5-20g, in adding procedure, the temperature of solution does not exceed 10 ℃.After potassium permanganate adds, keep the temperature of solution lower than 10 ℃ of magnetic agitation 90min.Then, the in the situation that of magnetic agitation, slowly add the deionized water of 150ml, guarantee that the temperature of solution is lower than 40 ℃ simultaneously.Add the hydrogen peroxide of 3ml, continue to stir 15min.Last filtering drying obtains surface modified graphite alkene microplate.
Three. the Graphene microplate mixing nano silicon particles of surface modification is obtained to Graphene-silica hybrid material:
The surface modified graphite alkene microplate of gained is added in 50-500ml deionized water, keep the temperature of solution lower than 35 ℃, ultrasonic dispersion 10-60min.0.5-5g nano silicon particles (30-200nm particle diameter) is joined in 500ml deionized water to ultrasonic dispersion 30-60min.Nano silicon particles solution is mixed with surface modified graphite alkene solution, keep solution temperature lower than 35 ℃, ultrasonic dispersion 30-60min.Finally, filter out solution, obtain surface modified graphite alkene-silica hybrid material.
Four. Graphene-silica hybrid material is made to Graphene-silicon nano power powder composite material: under inert atmosphere protection by surface modified graphite alkene-silica hybrid material 300-1000 ℃ annealing 0.1-2h, obtain Graphene-silicon nano power powder composite material.
Below preferred embodiment of the present invention is described in further detail:
Embodiment mono-
In the present embodiment, the implementing procedure of Graphene-silicon Nano-composite materials method is as follows:
1g50 order expansible black lead is placed in to metal or ceramic crucible, under protection of inert gas, is heated to 900 degree.Gained expanded graphite being placed in to container, pouring 250ml NMP into, stir, is then under 1000W condition, to vibrate 8 hours at sonic oscillation power, heating simultaneously, and Heating temperature is 80 degree.Filtering drying, obtains Graphene microplate.Gained Graphene microplate is added in the vitriol oil of 100ml, keep the temperature of solution lower than 4 ℃, slowly add the potassium permanganate of 0.5g, in adding procedure, the temperature of solution does not exceed 10 ℃.Keep the temperature of solution lower than 10 ℃ of magnetic agitation 90min.Then, the in the situation that of magnetic agitation, slowly add the deionized water of 150ml, guarantee that the temperature of solution is lower than 40 ℃ simultaneously.Add the hydrogen peroxide of 3ml, continue to stir 15min.Filtering drying obtains surface modified graphite alkene microplate.The surface modified graphite alkene microplate of gained is added in 200ml deionized water, keep the temperature of solution lower than 35 ℃, ultrasonic dispersion 10-60min.0.5g nano silicon particles (50nm particle diameter) is joined in 200ml deionized water to ultrasonic dispersion 30min.Nano silicon particles solution is mixed with surface modified graphite alkene solution, keep solution temperature lower than 35 ℃, ultrasonic dispersion 30-60min.Filter out solution, dry and obtain surface modified graphite alkene-silica hybrid material.Under inert atmosphere protection, 800 ℃ of annealing 1h, obtain Graphene-silicon nano power powder composite material.
Embodiment bis-
In the present embodiment, Graphene-silicon composite preparation method's implementing procedure is as follows:
1g expansible black lead is placed in to ceramic crucible or glassware, with 800W microwave heating 30 seconds.Then be cooled to room temperature.Gained expanded graphite being placed in to container, pouring 250ml NMP into, stir, is then under 1000W condition, to vibrate 8 hours at sonic oscillation power, heating simultaneously, and Heating temperature is 80 degree.Filtering drying, obtains Graphene microplate.Gained Graphene microplate is added in the vitriol oil of 100ml, keep the temperature of solution lower than 4 ℃, slowly add the potassium permanganate of 0.5g, in adding procedure, the temperature of solution does not exceed 10 ℃.Keep the temperature of solution lower than 10 ℃ of magnetic agitation 90min.Then, the in the situation that of magnetic agitation, slowly add the deionized water of 150ml, guarantee that the temperature of solution is lower than 40 ℃ simultaneously.Add the hydrogen peroxide of 3ml, continue to stir 15min.Filtering drying obtains surface modified graphite alkene microplate.The surface modified graphite alkene microplate of gained is added in 200ml deionized water, keep the temperature of solution lower than 35 ℃, ultrasonic dispersion 10-60min.0.5g nano silicon particles (50nm particle diameter) is joined in 200ml deionized water to ultrasonic dispersion 30min.Nano silicon particles solution is mixed with surface modified graphite alkene solution, keep solution temperature lower than 35 ℃, ultrasonic dispersion 30-60min.Filter out solution, dry and obtain surface modified graphite alkene-silica hybrid material.Under inert atmosphere protection, 800 ℃ of annealing 1h, obtain Graphene-silicon nano power powder composite material.
Embodiment tri-
In the present embodiment, Graphene-silicon composite preparation method's implementing procedure is as follows:
1g crystalline flake graphite being placed in to container, pouring 100ml NMP into, stir, is then under 1000W condition, to vibrate 8 hours at sonic oscillation power, heating simultaneously, and Heating temperature is 80 degree.Filtering drying, obtains Graphene microplate.Gained Graphene microplate is added in the vitriol oil of 50ml, keep the temperature of solution lower than 4 ℃, slowly add the potassium permanganate of 0.5g, in adding procedure, the temperature of solution does not exceed 10 ℃.Keep the temperature of solution lower than 10 ℃ of magnetic agitation 90min.Then, the in the situation that of magnetic agitation, slowly add the deionized water of 100ml, guarantee that the temperature of solution is lower than 40 ℃ simultaneously.Add the hydrogen peroxide of 3ml, continue to stir 15min.Filtering drying obtains surface modified graphite alkene microplate.The surface modified graphite alkene microplate of gained is added in 200ml deionized water, keep the temperature of solution lower than 35 ℃, ultrasonic dispersion 10-60min.0.5g nano silicon particles (50nm particle diameter) is joined in 200ml deionized water to ultrasonic dispersion 30min.Nano silicon particles solution is mixed with surface modified graphite alkene solution, keep solution temperature lower than 35 ℃, ultrasonic dispersion 30-60min.Filter out solution, dry and obtain surface modified graphite alkene-silica hybrid material.Under inert atmosphere protection, 800 ℃ of annealing 1h, obtain Graphene-silicon nano power powder composite material.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. a preparation method for Graphene-silicon nano power powder composite material, is characterized in that, said method comprising the steps of:
Prepare Graphene microplate;
Graphene microplate is carried out to surface modification;
The Graphene microplate mixing nano silicon particles of surface modification is made to Graphene-silica hybrid material; And
Graphene-silica hybrid material is made to Graphene-silicon nano power powder composite material.
2. the method for claim 1, is characterized in that, the described Graphene microplate of preparing comprises the following steps:
Prepare expanded graphite;
The expanded graphite obtaining is mixed with organic solvent;
Expanded graphite organic solvent mixed solution is carried out to ultrasonic dissociating and obtain Graphene microplate suspension; And
From Graphene microplate suspension, extract Graphene microplate.
3. method as claimed in claim 2, is characterized in that, the described expanded graphite of preparing is for to be placed in metal or ceramic crucible by expansible black lead; under protection of inert gas, be heated to 300-900 degree, keep temperature 10-60 to divide; realize fully and expanding, be then cooled to room temperature.
4. method as claimed in claim 2, is characterized in that, the described expanded graphite of preparing is for to be placed in ceramic crucible or glassware by expansible black lead, with 600-1200W microwave heating 10-60 second, realizes fully and expanding, and is then cooled to room temperature.
5. method as claimed in claim 2, is characterized in that, described the expanded graphite obtaining and organic solvent are mixed into gained expanded graphite is placed in to container, pours 100-1000ml organic solvent into, stirs.
6. method as claimed in claim 2, it is characterized in that, describedly expanded graphite organic solvent mixed solution is carried out to ultrasonic dissociating obtain Graphene microplate suspension for being the 1-24 hour that vibrates under 300-1200W condition at sonic oscillation power, Heating temperature is 20-150 degree simultaneously, obtains Graphene microplate suspension.
7. method as claimed in claim 2, it is characterized in that, the described Graphene microplate that extracts from Graphene microplate suspension, for ultrasonic gained Graphene microplate suspension is left standstill to 0.2-5 hour, removes upper strata suspension, remove throw out, after filtration, in 80 degree baking ovens, dry.
8. the method for claim 1, it is characterized in that, described Graphene microplate is carried out to surface modification for gained Graphene microplate is added in the vitriol oil, keep the temperature of solution lower than 4 ℃, slowly add potassium permanganate, in adding procedure, the temperature of solution does not exceed 10 ℃; After potassium permanganate adds, keep the temperature of solution lower than 10 ℃ of magnetic agitation 90min; Then, the in the situation that of magnetic agitation, slowly add deionized water, guarantee that the temperature of solution is lower than 40 ℃ simultaneously; Add hydrogen peroxide, continue to stir 15min; Last filtering drying obtains surface modified graphite alkene microplate.
9. the method for claim 1, it is characterized in that, it is that the surface modified graphite alkene microplate of gained is added in deionized water that the described Graphene microplate mixing nano silicon particles by surface modification obtains Graphene-silica hybrid material, keep the temperature of solution lower than 35 ℃, ultrasonic dispersion 10-60min; Nano silicon particles is joined in deionized water to ultrasonic dispersion 30-60min; Nano silicon particles is easily mixed with surface modified graphite alkene solution, keep solution temperature lower than 35 ℃, ultrasonic dispersion 30-60min; Finally, filter out solution, obtain surface modified graphite alkene-silica hybrid material.
10. the method for claim 1, is characterized in that, described by Graphene-silica hybrid material make Graphene-silicon nano power powder composite material under inert atmosphere protection 300-1000 ℃ annealing 0.1-2h, obtain Graphene-silicon nano power powder composite material.
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| CN111500005A (en) * | 2019-01-30 | 2020-08-07 | 家登精密工业股份有限公司 | Cycloolefin composition and semiconductor container using the same |
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