CN103803534B - A kind of preparation method of Graphene silicon nano power powder composite material - Google Patents
A kind of preparation method of Graphene silicon nano power powder composite material Download PDFInfo
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- CN103803534B CN103803534B CN201210475326.0A CN201210475326A CN103803534B CN 103803534 B CN103803534 B CN 103803534B CN 201210475326 A CN201210475326 A CN 201210475326A CN 103803534 B CN103803534 B CN 103803534B
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Abstract
The present invention is applied to organic semiconducting materials technical field, there is provided a kind of preparation method of Graphene silicon nano power powder composite material, the described method comprises the following steps：Prepare graphene microchip；Graphene microchip is carried out into surface to be modified；The graphene microchip that surface is modified mixes nano silicon particles and is made Graphene silica hybrid material；And Graphene silica hybrid material is made Graphene silicon nano power powder composite material.Large-scale production Graphene silicon nano power powder composite material is industrialized by technical solution of the present invention, with advantages below：Small, the low cost with acid amount and oxidant content；Acid and noxious emission are few, environmentally friendly；Process of Surface Modification is small to graphite lattice damage, easily reduction, product good conductivity.
Description
Technical field
The invention belongs to organic semiconducting materials technical field, more particularly to a kind of Graphene-silicon nanopowder composite wood
The preparation method of material.
Background technology
Graphene is a kind of new carbon widely studied in recent years, is the two dimension that carbon atom is arranged according to hexagonal
Lattice structure.Used as single layer of carbon atom planar materials, Graphene can be obtained by peeling off graphite material.The thickness of Graphene
Only 0.335 nanometer, most thin one kind in known materials is not only, also unusual rigid；Used as simple substance, it is passed at room temperature
The speed for passing electronics is all faster than known all of conductor and semiconductor, and the migration velocity of electronics has reached the 1/ of the light velocity in Graphene
300.Meanwhile, used as single layer of carbon atom structure, the theoretical specific surface area of Graphene is up to 2630m2/g, specific surface area so high
So that the material based on Graphene turns into extremely promising energy storage active material.
Oxidizing process (Hummers methods) being based primarily upon at present and preparing graphene powder material and its composite, graphite exists
In the presence of the strong oxidizers such as H2SO4, HNO3, HClO4, or under electrochemistry peroxidation, graphite oxide is formed after hydrolysis.
Different with graphite, due to the presence of polar group, oxidized graphite flake layer has stronger hydrophilic or polar solvent characteristic.Cause
This, graphite oxide can form individual layer in water or in other polar solvents such as in the presence of ultrasonic wave in external force with peeling-off
Graphene oxide (Graphene Oxide).But, Hummers methods use substantial amounts of soda acid during preparing graphene oxide,
High cost, while produce substantial amounts of soda acid to dump thing, it is unfriendly to environment.
The content of the invention
The embodiment of the present invention aims to overcome that problems of the prior art, there is provided one kind is adapted to low cost industry
The preparation method for change large-scale production, high-quality, reducing the poisonous Graphene-silicon nano composite material for dumping thing.
The embodiment of the present invention is achieved in that a kind of preparation method of Graphene-silicon nano power powder composite material, described
Method is comprised the following steps：Prepare graphene microchip；Graphene microchip is carried out into surface to be modified；The Graphene that surface is modified is micro-
Piece mixing nano silicon particles are made Graphene-silica hybrid material；And Graphene-silica hybrid material is made Graphene-silicon nanometer
Particulate composite；It is described by graphene microchip carry out surface be modified as by gained graphene microchip add the concentrated sulfuric acid in, keep
The temperature of solution is less than 4 DEG C, is slowly added potassium permanganate, and the temperature of solution does not exceed 10 DEG C in adding procedure；Permanganic acid
After potassium addition is finished, the temperature of solution is kept to be less than 10 DEG C of magnetic agitation 90min；Then, in the case of magnetic agitation, slowly
Addition deionized water, while ensureing that the temperature of solution is less than 40 DEG C；Addition hydrogen peroxide, continues to stir 15min；Last filtering drying
Obtain surface modified graphite alkene microplate；It is lazy that Graphene-silica hybrid material is made into Graphene-silicon nano power powder composite material
Property atmosphere protection under 300-1000 DEG C annealing 0.1-2h, obtain Graphene-silicon nano power powder composite material.
In a preferred embodiment, the preparation graphene microchip is comprised the following steps：Prepare expanded graphite；By what is obtained
Expanded graphite mixes with organic solvent；Expanded graphite organic solvent mixed liquor is carried out into ultrasound dissociation and obtains graphene microchip suspension
Liquid；And extract graphene microchip from graphene microchip suspension；
In a preferred embodiment, the expanded graphite for preparing is that expansible graphite is placed in into metal or ceramic crucible
In, under inert gas shielding, 300-900 degree is heated to, keeping temperature 10-60 points, fully expansion is realized, then it is cooled to room
Temperature.
In a preferred embodiment, the expanded graphite for preparing is that expansible graphite is placed in into ceramic crucible or vierics
In ware, with 600-1200W heating using microwaves 10-60 seconds, fully expansion is realized, be then cooled to room temperature.
In a preferred embodiment, the expanded graphite that will be obtained is mixed into organic solvent and puts gained expanded graphite
In container, 100-1000ml organic solvents are poured into, stirred.
In a preferred embodiment, it is described expanded graphite organic solvent mixed liquor to be carried out into ultrasound dissociation to obtain Graphene micro-
Piece suspension is to be vibrated 1-24 hours under the conditions of sonic oscillation power is 300-1200W, while heating-up temperature is 20-150 degree,
Obtain graphene microchip suspension.
In a preferred embodiment, it is by ultrasound gained stone that graphene microchip is extracted in the suspension from graphene microchip
Black alkene microplate suspension stands 0.2-5 hours, takes upper strata suspension, removes sediment, is dried in 80 degree of baking ovens after filtering.
In a preferred embodiment, it is described by surface be modified graphene microchip mix nano silicon particles obtain Graphene-
Silica hybrid material is during the surface modified graphite alkene microplate of gained added into deionized water, to keep the temperature of solution to be less than 35 DEG C,
Ultrasonic disperse 10-60min；Nano silicon particles are added in deionized water, ultrasonic disperse 30-60min；Nano silicon particles are molten
Liquid mixes with surface modified graphite alkene solution, keeps solution temperature to be less than 35 DEG C, ultrasonic disperse 30-60min；Finally, filter out
Solution, obtains surface modified graphite alkene-silica hybrid material.
In an embodiment of the present invention, large-scale production Graphene-silicon nano power is industrialized by technical solution of the present invention
Powder composite material, with advantages below：1st, it is small with acid amount and oxidant content, low cost；2. acid and noxious emission are few, to ring
Border is friendly；3. Process of Surface Modification is small to graphite lattice damage, easily reduction, product good conductivity.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
In an embodiment of the present invention, it is modified by carrying out surface to graphene microchip, then adsorbs silicon nanopowder and is obtained
Graphene-silicon nano power powder composite material.
The implementing procedure of Graphene provided in an embodiment of the present invention-silicon nanopowder composite material and preparation method thereof, describes in detail such as
Under：
First, graphene microchip is prepared；
1. expanded graphite is prepared：During expansible graphite is placed in into metal or ceramic crucible, under inert gas shielding, plus
Heat keeping temperature 10-60 minutes, realizes fully expansion to 300-900 degree, is then cooled to room temperature.
Or during expansible graphite is placed in into ceramic crucible or glassware, with 600-1200W heating using microwaves 10-60
Second, fully expansion is realized, then it is cooled to room temperature.
In a particular embodiment, raw material also can use crystalline flake graphite.
2. the expanded graphite that will be obtained mixes with organic solvent：Gained expanded graphite is placed in container, 100- is poured into
1000ml organic solvents, the organic solvent is NMP, DMP, toluene, chlorobenzene or trichloro ethylene, is stirred.
3. expanded graphite organic solvent mixed liquor is carried out into ultrasound dissociation and obtain graphene microchip suspension：In sonic oscillation
Power under the conditions of 300-1200W to vibrate 1-24 hours, while heating, temperature is 20-150 degree, obtains graphene microchip suspension
Liquid.The ultrasonic disperse time is too short within 60 minutes, so that the effect of dispersion dissociation is bad, the present invention is small using concussion 1-24
When, can effectively improve dispersion effect.The heating taken in addition is also beneficial to improve dispersion effect.
4. graphene microchip is extracted from graphene microchip suspension：Ultrasound gained graphene microchip suspension is stood
0.2-5 hours, upper strata suspension is taken, remove sediment, dried in 80 degree of baking ovens after filtering.The present invention without centrifugal treating,
Save fabrication steps, improve production efficiency.
Graphene microchip is carried out surface and is modified by two,：
The temperature of solution in the concentrated sulfuric acid of gained graphene microchip addition 20-100ml, will be kept to be less than 4 DEG C, be slowly added
The potassium permanganate of 0.5-20g, the temperature of solution does not exceed 10 DEG C in adding procedure.After potassium permanganate addition is finished, keep
The temperature of solution is less than 10 DEG C of magnetic agitation 90min.Then, in the case of magnetic agitation, it is slowly added the deionization of 150ml
Water, while ensureing that the temperature of solution is less than 40 DEG C.The hydrogen peroxide of 3ml is added, continues to stir 15min.Last filtering drying is obtained
Surface modified graphite alkene microplate.
The graphene microchip that be modified on surface by three, mixes nano silicon particles and obtains Graphene-silica hybrid material：
By in the surface modified graphite alkene microplate addition 50-500ml deionized waters of gained, the temperature of solution is kept to be less than 35
DEG C, ultrasonic disperse 10-60min.0.5-5g nano silicon particles (30-200nm particle diameters) are added in 500ml deionized waters, are surpassed
Sound disperses 30-60min.Nano silicon particles solution is mixed with surface modified graphite alkene solution, keeps solution temperature to be less than 35 DEG C,
Ultrasonic disperse 30-60min.Finally, solution is filtered out, surface modified graphite alkene-silica hybrid material is obtained.
Graphene-silica hybrid material is made Graphene-silicon nano power powder composite material by four,：Under inert atmosphere protection
By surface modified graphite alkene-silica hybrid material in 300-1000 DEG C of annealing 0.1-2h, Graphene-silicon nanopowder composite wood is obtained
Material.
Presently preferred embodiments of the present invention is described in further detail below：
Embodiment one
The implementing procedure of Graphene-silicon nano composite material preparation method is as follows in the present embodiment：
During the mesh expansible graphites of 1g 50 are placed in into metal or ceramic crucible, under inert gas shielding, 900 are heated to
Degree.Gained expanded graphite is placed in container, 250mlNMP is poured into, stirred, be then 1000W bars in sonic oscillation power
Vibrated 8 hours under part, while heating, heating-up temperature is 80 degree.Filtering drying, obtains graphene microchip.Gained Graphene is micro-
Piece is added in the concentrated sulfuric acid of 100ml, keeps the temperature of solution to be less than 4 DEG C, the potassium permanganate of 0.5g is slowly added, in adding procedure
The temperature of middle solution does not exceed 10 DEG C.The temperature of solution is kept to be less than 10 DEG C of magnetic agitation 90min.Then, in magnetic agitation
In the case of, the deionized water of 150ml is slowly added, while ensureing that the temperature of solution is less than 40 DEG C.The hydrogen peroxide of 3ml is added,
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 waters, the temperature of solution is kept to be less than 35 DEG C, ultrasonic disperse 10-60min.By 0.5g nano silicon particles (50nm
Particle diameter) it is added in 200ml deionized waters, ultrasonic disperse 30min.By nano silicon particles solution and surface modified graphite alkene solution
Mixing, keeps solution temperature to be less than 35 DEG C, ultrasonic disperse 30-60min.Filter out solution, drying obtain surface modified graphite alkene-
Silica hybrid material.800 DEG C of annealing 1h, obtain Graphene-silicon nano power powder composite material under inert atmosphere protection.
Embodiment two
The implementing procedure of Graphene-silicon composite preparation method is as follows in the present embodiment：
During 1g expansible graphites are placed in into ceramic crucible or glassware, with 800W heating using microwaves 30 seconds.Then cool down
To room temperature.Gained expanded graphite is placed in container, 250mlNMP is poured into, stirred, be then in sonic oscillation power
Vibrated 8 hours under the conditions of 1000W, while heating, heating-up temperature is 80 degree.Filtering drying, obtains graphene microchip.By gained stone
Black alkene microplate is added in the concentrated sulfuric acid of 100ml, keeps the temperature of solution to be less than 4 DEG C, is slowly added the potassium permanganate of 0.5g, is being added
Plus during the temperature of solution do not exceed 10 DEG C.The temperature of solution is kept to be less than 10 DEG C of magnetic agitation 90min.Then, in magnetic
In the case that power is stirred, the deionized water of 150ml is slowly added, while ensureing that the temperature of solution is less than 40 DEG C.Addition 3ml's is double
Oxygen water, continues to stir 15min.Filtering drying obtains surface modified graphite alkene microplate.By the surface modified graphite alkene microplate of gained
Add in 200ml deionized waters, keep the temperature of solution to be less than 35 DEG C, ultrasonic disperse 10-60min.By 0.5g nano silicon particles
(50nm particle diameters) is added in 200ml deionized waters, ultrasonic disperse 30min.By nano silicon particles solution and surface modified graphite
Alkene solution mixes, and keeps solution temperature to be less than 35 DEG C, ultrasonic disperse 30-60min.Solution is filtered out, drying obtains surface and is modified
Graphene-silica hybrid material.800 DEG C of annealing 1h, obtain Graphene-silicon nano power powder composite material under inert atmosphere protection.
Embodiment three
The implementing procedure of Graphene-silicon composite preparation method is as follows in the present embodiment：
1g crystalline flake graphites are placed in container, 100ml NMP are poured into, stirred, be then in sonic oscillation power
Vibrated 8 hours under the conditions of 1000W, while heating, heating-up temperature is 80 degree.Filtering drying, obtains graphene microchip.By gained stone
Black alkene microplate is added in the concentrated sulfuric acid of 50ml, keeps the temperature of solution to be less than 4 DEG C, is slowly added the potassium permanganate of 0.5g, is being added
Plus during the temperature of solution do not exceed 10 DEG C.The temperature of solution is kept to be less than 10 DEG C of magnetic agitation 90min.Then, in magnetic
In the case that power is stirred, the deionized water of 100ml is slowly added, while ensureing that the temperature of solution is less than 40 DEG C.Addition 3ml's is double
Oxygen water, continues to stir 15min.Filtering drying obtains surface modified graphite alkene microplate.By the surface modified graphite alkene microplate of gained
Add in 200ml deionized waters, keep the temperature of solution to be less than 35 DEG C, ultrasonic disperse 10-60min.By 0.5g nano silicon particles
(50nm particle diameters) is added in 200ml deionized waters, ultrasonic disperse 30min.By nano silicon particles solution and surface modified graphite
Alkene solution mixes, and keeps solution temperature to be less than 35 DEG C, ultrasonic disperse 30-60min.Solution is filtered out, drying obtains surface and is modified
Graphene-silica hybrid material.800 DEG C of annealing 1h, obtain Graphene-silicon nano power powder composite material under inert atmosphere protection.
Presently preferred embodiments of the present invention is the foregoing is only, is not intended to limit the invention, it is all in essence of the invention
Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.
Claims (8)
1. the preparation method of a kind of Graphene-silicon nano power powder composite material, it is characterised in that methods described includes following step
Suddenly：
Prepare graphene microchip；
Graphene microchip is carried out into surface to be modified；
The graphene microchip that surface is modified mixes nano silicon particles and is made Graphene-silica hybrid material；And
Graphene-silica hybrid material is made Graphene-silicon nano power powder composite material；
It is described by graphene microchip carry out surface be modified as by gained graphene microchip add the concentrated sulfuric acid in, keep solution temperature
Less than 4 DEG C, potassium permanganate is slowly added, the temperature of solution does not exceed 10 DEG C in adding procedure；Potassium permanganate addition is finished
Afterwards, the temperature of solution is kept to be less than 10 DEG C of magnetic agitation 90min；Then, in the case of magnetic agitation, it is slowly added deionization
Water, while ensureing that the temperature of solution is less than 40 DEG C；Addition hydrogen peroxide, continues to stir 15min；Last filtering drying must change to surface
Property graphene microchip；
It is described that Graphene-silica hybrid material is made into Graphene-silicon nano power powder composite material is under inert atmosphere protection
300-1000 DEG C of annealing 0.1-2h, obtains Graphene-silicon nano power powder composite material.
2. the method for claim 1, it is characterised in that the preparation graphene microchip is comprised the following steps：
Prepare expanded graphite；
The expanded graphite that will be obtained mixes with organic solvent；
Expanded graphite organic solvent mixed liquor is carried out into ultrasound dissociation and obtains graphene microchip suspension；And
Graphene microchip is extracted from graphene microchip suspension.
3. method as claimed in claim 2, it is characterised in that the expanded graphite for preparing is that expansible graphite is placed in into metal
Or in ceramic crucible, under inert gas shielding, 300-900 degree is heated to, keeping temperature 10-60 points, fully expansion is realized,
Then it is cooled to room temperature.
4. method as claimed in claim 2, it is characterised in that the expanded graphite for preparing is that expansible graphite is placed in into ceramics
In crucible or glassware, with 600-1200W heating using microwaves 10-60 seconds, fully expansion is realized, be then cooled to room temperature.
5. method as claimed in claim 2, it is characterised in that the expanded graphite that will be obtained and organic solvent be mixed into by
Gained expanded graphite is placed in container, pours into 100-1000mL organic solvents, is stirred.
6. method as claimed in claim 2, it is characterised in that described that expanded graphite organic solvent mixed liquor is carried out into ultrasonic solution
It is to be vibrated 1-24 hours under the conditions of sonic oscillation power is 300-1200W from graphene microchip suspension is obtained, while heating
Temperature is 20-150 degree, obtains graphene microchip suspension.
7. method as claimed in claim 2, it is characterised in that extract graphene microchip in the suspension from graphene microchip
It is that ultrasound gained graphene microchip suspension is stood 0.2-5 hours, takes upper strata suspension, sediment is removed, 80 after filtering
Dried in degree baking oven.
8. the method for claim 1, it is characterised in that the graphene microchip that surface is modified mixes silicon nanometer
It is during the surface modified graphite alkene microplate of gained added into deionized water, to keep solution that grain obtains Graphene-silica hybrid material
Temperature is less than 35 DEG C, ultrasonic disperse 10-60min；Nano silicon particles are added in deionized water, ultrasonic disperse 30-60min；
Nano silicon particles solution is mixed with surface modified graphite alkene solution, keeps solution temperature to be less than 35 DEG C, ultrasonic disperse 30-
60min；Finally, solution is filtered out, surface modified graphite alkene-silica hybrid material is obtained.
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| CN104923796B (en) * | 2015-06-11 | 2017-03-29 | 中国石油大学(北京) | A kind of method of preparation of industrialization graphene coated nanometer aluminium powder |
| CN106744857B (en) * | 2016-12-30 | 2019-03-08 | 尹宗杰 | 3D printing graphene-metallic composite, preparation method and application |
| CN107323044B (en) * | 2017-06-23 | 2019-07-09 | 过冬 | A kind of preparation method of conductive paper/glass fiber flame retardant composite material |
| CN108183204A (en) * | 2017-12-06 | 2018-06-19 | 华南农业大学 | A kind of silicon nanometer sheet-graphene nanometer sheet composite material and preparation and application |
| 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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