CN109273702A - The all solid state preparation method of irregular micro-nano particle coated with uniform graphene - Google Patents
The all solid state preparation method of irregular micro-nano particle coated with uniform graphene Download PDFInfo
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Abstract
The present invention discloses a kind of all solid state material preparation method in irregular micro-nano particle coated with uniform solid graphite alkene, belongs to new energy materials and its preparation technical field.So that graphite powder interlayer is separated from each other and is adhered in friction process using the shearing force that mechanical milling process generates and is wrapped by microsphere surface, the graphite number of plies is thinned persistently under the effect of continuously physical friction, thin graphene cladding microballoon shell-core structure is ultimately formed, the screening of the size difference of cladding product and graphite powder is recycled to obtain cladding product.Transfer graphene may further be reached by the mixing and ball milling of micro-spheres product and other irregular micro-nano particle solid powder samples, form graphene-solid powder compound to be used for every field.Whole process is not related to any chemical reaction, and simple process, low in cost, environmentally protective, product purity is high and it is simple to post-process, and raw material can repeatedly use, and be suitble to industrialized production.
Description
Technical field
The invention belongs to technical field of new energy material preparation, in particular to irregular micro-nano particle coated with uniform stone
The all solid state preparation method of black alkene.
Background technique
It is used from Univ Manchester UK physicist An Deliegaimu in 2004 and Constantine's Nuo Woxiao love
Since micromechanics stripping method success isolates graphene from graphite, due to its high intensity, low-density, highly conductive, high thermal conductivity, height
The excellent properties such as stable, anticorrosive, wear-resistant and the favor by all trades and professions.Graphene is as conductive, thermally conductive skeleton, anti-corrosion
Erosion medium etc. is used to a variety of materials and carries out the compound performance to improve material, expands the use scope of material.
The structure of graphene composite material has following four: (a) graphene-supported composite material；(b) graphene coated
Composite material；(c) the embedded composite material of graphene；(d) it is based on graphene laminar composite.Existing graphene composite wood
The preparation of material mainly have gaseous recombination, liquid phase are compound, compound three kinds of solid phase.Often required temperature is higher for vapor phase method, causes to produce
With high costs, industrialization extension is difficult, be easy to cause material point in the hot environment of gas phase treatment particularly with inert material
The phenomenon that solving, aoxidizing or restore.The prior art is composite mixed using fluororesin (CYTOP) and the progress of CVD growth graphene,
Though product is stable in the air, when temperature is increased to 500 DEG C, fluoropolymer is decomposed, and doping phenomenon disappears therewith.Also
People grows one layer of graphene on nickel foam surface using chemical vapour deposition technique, then coats one layer of PMMA and form three-dimensional shape structure,
Metallic nickel and PMMA are washed away by acetone and hydrochloric acid to form the graphene of three-dimensional network shape, then by dimethyl silicone polymer
(PDMS) it is added to formation graphene/PDMS composite material in the graphene of three-dimensional shape.This method can introduce other foreign ions and
Technique requires height, and preparation can not be mass produced.
Liquid phase is compound, and it is usually necessary to use two-step methods, pass through the derivative of distinct methods synthesizing graphite alkene or graphene first
Object, then by its in a liquid be doped material uniformly mix merga pass reduction, filtering, evaporation etc. methods removal solution to
Graphene composite material is obtained, however this method not can avoid the agglomeration traits of graphene, and the graphite that this method uses
Ene derivative usually contains different functional groups to reach easily dispersible effect, and post processor is complicated, simultaneously for active
Material is easy to react to keep material rotten with the impurity in liquid or liquid used in liquid phase is compound.The prior art
LiFePO4/graphene composite material is prepared, certain density ferrous sulfate solution is mixed with graphene oxide solution, and
After be added dropwise ammonium dihydrogen phosphate, control solution acid alkalinity and the compound of ferric phosphate and graphene oxide be obtained by filtration, by this
Compound mixes hydro-thermal reaction with lithium hydroxide, reducing agent and LiFePO4/graphene doped and compounded material is obtained by filtration.Also
PVP, PVAc, PVP/PVAc are added in water/DMF dispersion liquid of graphene oxide by people, by heat reduction prepare graphene/
Macromolecule dopant material, but macromolecule matrix material causes the loss in performance by that can degrade after high-temperature process.
And the cladding of graphene can not all be evenly distributed in the material of above method preparation, exist simultaneously a large amount of free graphite alkene,
It causes greatly to challenge to subsequent processing.
Solid phase is compound can to occur rotten problem to avoid the above material, but traditional solid phase is compound often only by stone
Black alkene or graphite powder and be doped material and carry out simple ball milling, due between graphene monolithic there are stronger Van der Waals force,
It is easy to attract each other and reunite, simple ball milling not can avoid the agglomeration traits between graphene, and what is obtained is to be incorporated
The mixture of miscellaneous material and graphene.The prior art carries out ball milling cladding using high-pressure graphite ball and aluminum oxide micro-sphere, it is desirable that quilt
Cladding object is necessary for spherical and its size is subject to certain restrictions, and the later use of graphite ene product needs first in chemical solution
Split-up in agent.
Summary of the invention
The purpose of the present invention is to provide all solid state preparation method of irregular micro-nano particle coated with uniform graphene,
To solve the above problems.
To achieve the above object, the invention adopts the following technical scheme:
The all solid state preparation method of irregular micro-nano particle coated with uniform graphene, comprising the following steps:
Step 1, graphene coated microballoon shell-core structure is prepared；
Step 2, graphene coated microballoon shell-core structure is to the transfer on irregular micro-nano particle surface to form graphene
The irregular micro-nano particle of cladding.
Further, step 1 specifically includes the following steps:
1) it by crystalline graphite powder and is wrapped by hard microballoon and mixes to obtain mixture A；
2) mixture A is placed in agate jar, crystalline flake graphite and microballoon generate friction, different-thickness in mechanical milling process
Graphene shifts and is coated to hard microsphere surface, obtains mixture B；
3) graphite powder in mixture B is sifted out, obtains the microballoon shell-core structure C of different-thickness graphene coated；
4) C is wrapped by hard microballoon with new a batch and mixes to obtain mixture D；
5) mixture D is placed in agate jar, further ball milling shifts graphene further between different spheres
Achieve the purpose that removing to obtain the microballoon shell-core structure E of thin graphene cladding.
Further, step 2 specifically includes the following steps:
A) thin uniform layer graphene coated microsphere compound C or E obtained is mixed with irregular micro-nano particle to be covered
Obtain mixture F；
B) mixture F is placed in ball grinder, obtains mixture G after ball milling；
C) mixture G is sieved, removal microballoon obtains thin graphene cladding solid matter compound H.
Further, in step 1), crystalline graphite powder be wrapped by the mass ratio of hard microballoon 1:20 to 1:1 it
Between；In step 4), C and new a batch are wrapped by the mass ratio of hard microballoon between 1:1 to 1:3.
Further, in step 2), the total volume of mixture A is no more than the one third of ball grinder total measurement (volume)；In air
Ball mill ball milling mixing is used under atmosphere, revolving speed is between 200rpm to 300rpm；Ball-milling Time is between 6h to 16h；Step 5)
In, mixture D total volume is no more than the one third of ball grinder total measurement (volume)；Revolving speed is between 200rpm to 300rpm；When ball milling
Between in 8h between for 24 hours.
Further, in step a), C or E and irregular micro-nano particle mass ratio to be covered are between 100:1 to 1:1；Step
It is rapid c) in, ball milling in air atmosphere, revolving speed is between 200rpm to 500rpm；Ball-milling Time is between 6h to 12h.
Further, in step 2 with to be wrapped by the material that hard microballoon mixes further include amorphous graphite and graphite particle；Quilt
Cladding hard microballoon includes metallic microspheres, oxidate microspheres, nitride or carbide microballoon, and the size of microballoon arrives 5mm at 20 μm
Between.
Further, irregular micro-nano particle includes spherical powder, flakelike powder, particle powder or crystallite etc., irregularly
Micro-nano particle size range is between 100nm to 500 μm.
Further, ball grinder is that agate jar, teflon seal ball grinder, stainless steel seal ball grinder, hard
Matter alloy seal ball grinder, aluminium oxide/corundum sealing ball grinder, zirconium oxide sealing ball grinder, polyurethane seal ball grinder, carbonization
Silicon seals one of ball grinder or sealed nylon ball grinder.
Compared with prior art, the present invention has following technical effect:
Whole process of the invention is physical process, and the formation of first step graphene coated microballoon shell-core structure is by ball milling mistake
The shearing force that journey generates makes crystalline graphite powder cut thin by metallic microspheres high-speed cutting and is adhered to microsphere surface, constant
Shear action under in metallic microspheres surface formed thickness uniformly, the graphene layer of structural integrity, and can be by further
The metallic microspheres of ball milling single cladding and uncoated new a collection of metallic microspheres achieve the purpose that graphene is further thinned.Second
It is using graphene-microballoon shell-core structure compound and to be wrapped by not that step transfer graphene uniform, which coats irregular micro-nano particle,
Force of rolling friction between regular material grains reaches higher peeling rate under slow-speed of revolution ball milling condition, so that microsphere surface
Graphene layer be transferred in continuous friction process and be wrapped by material surface, it is multiple to form the irregular nano particle of graphene-
Object is closed, achievees the purpose that graphene directly coats.
This method simple process, environmentally protective, material therefor crystalline graphite powder, microballoon, cheap, post-processing it is simple and
It can repeatedly use, required equipment is only general milling machine, invests smaller, and cost is relatively low, for different microballoons or subsequent
Cladding sample only needs adjustment ball milling parameter, and product qualities are high, without adhesion and cladding microballoon is easily separated with graphite powder, can be multiple
Reuse does not influence performance, and high production efficiency is suitble to industrialized production.
Detailed description of the invention
Fig. 1 is the principle of the present invention schematic diagram；
Fig. 2 is crystalline flake graphite-copper ball state diagram after first step ball milling of the present invention；
Fig. 3 is graphene-copper ball core-shell structure compound after present invention cladding；
Fig. 4 is that ball milling starts lithium aluminium hydride reduction and graphene-copper ball compound mixing shape in preceding tank in the embodiment of the present invention 2
State figure；
Fig. 5 a and b are that the lithium aluminium hydride reduction before coating in the embodiment of the present invention 2 and graphene-lithium aluminium hydride reduction after cladding are compound
Object comparison diagram；
Fig. 6 a and b are that graphene-lithium aluminium hydride reduction compound suppresses balling-up product figure in application examples 1 of the present invention；
Specific embodiment
Just specific implementation step and application case of the invention are done to illustrate below, it shall be highlighted that following real
It applies example to be not intended to limit the invention, any modification for being made all within the spirits and principles of the present invention, equivalent replacement and change
Into etc., it should all be included in the protection scope of the present invention.
The all solid state preparation method of irregular micro-nano particle coated with uniform graphene, comprising the following steps:
Step 1, graphene coated microballoon shell-core structure is prepared；
Step 2, graphene coated microballoon shell-core structure is to the transfer on irregular micro-nano particle surface to form graphene
The irregular micro-nano particle of cladding.
Step 1 specifically includes the following steps:
1) it by crystalline graphite powder and is wrapped by hard microballoon and mixes to obtain mixture A；
2) mixture A is placed in agate jar, crystalline flake graphite and microballoon generate friction, different-thickness in mechanical milling process
Graphene shifts and is coated to hard microsphere surface, obtains mixture B；
3) graphite powder in mixture B is sifted out, obtains the microballoon shell-core structure C of different-thickness graphene coated；
4) C is wrapped by hard microballoon with new a batch and mixes to obtain mixture D；
5) mixture D is placed in agate jar, further ball milling shifts graphene further between different spheres
Achieve the purpose that removing to obtain the microballoon shell-core structure E of thin graphene cladding.
Step 2 specifically includes the following steps:
A) thin uniform layer graphene coated microsphere compound C or E obtained is mixed with irregular micro-nano particle to be covered
Obtain mixture F；
B) mixture F is placed in ball grinder, obtains mixture G after ball milling；
C) mixture G is sieved, removal microballoon obtains thin graphene cladding solid matter compound H.
In step 1), crystalline graphite powder and the mass ratio of hard microballoon is wrapped by between 1:20 to 1:1；Step 4)
In, C and new a batch are wrapped by the mass ratio of hard microballoon between 1:1 to 1:3.
In step 2), the total volume of mixture A is no more than the one third of ball grinder total measurement (volume)；Ball is used in air atmosphere
Grinding machine ball milling mixing, revolving speed is between 200rpm to 300rpm；Ball-milling Time is between 6h to 16h；In step 5), mixture D
Total volume is no more than the one third of ball grinder total measurement (volume)；Revolving speed is between 200rpm to 300rpm；Ball-milling Time is in 8h to for 24 hours
Between.
In step a), C or E and irregular micro-nano particle mass ratio to be covered are between 100:1 to 1:1；In step c),
Ball milling under air atmosphere, revolving speed is between 200rpm to 500rpm；Ball-milling Time is between 6h to 12h.
In step 2 with to be wrapped by the material that hard microballoon mixes further include amorphous graphite and graphite particle；It is wrapped by hard
Microballoon includes metallic microspheres, oxidate microspheres, nitride or carbide microballoon, and the size of microballoon is at 20 μm between 5mm.
Irregular micro-nano particle includes spherical powder, flakelike powder, particle powder or crystallite etc., irregular micro-nano particle ruler
Very little range is between 100nm to 500 μm.
Ball grinder is agate jar, teflon seal ball grinder, stainless steel seals ball grinder, hard alloy seals
Ball grinder, aluminium oxide/corundum sealing ball grinder, zirconium oxide sealing ball grinder, polyurethane seal ball grinder, silicon carbide seal ball milling
One of tank or sealed nylon ball grinder.
Embodiment:
Prepare graphene coated microballoon shell-core structure；
A) crystalline flake graphite (16 mesh, carbon content >=99%) and copper ball (400 μm of diameter) are mixed in proportion, crystalline flake graphite with
For the mass ratio of copper ball between 1:10 to 1:1, preferred mass ratio is 1:3；The size of copper ball between 20 μm to 500 μm,
It is preferred that obtaining mixture A between 200 μm to 500 μm；
B) mixture A is placed in agate jar, total volume is no more than the one third of ball grinder total measurement (volume), preferably general assembly
Doses total measurement (volume) a quarter between one third；Ball mill ball milling mixing is used in air atmosphere, and revolving speed exists
Between 200rpm to 300rpm, preferably revolving speed is between 230rpm to 280rpm；Time, preferably the time existed between 6h to 16h
Between 8h to 12h, mixture B is obtained；
C) crystalline flake graphite in mixture B is sifted out, the copper ball of remainder cladding different-thickness graphene, referred to as mixture
C；
D) mixture C and copper ball are mixed in proportion, the mass ratio of mixture C and copper ball is excellent between 1:1 to 1:3
Selecting mass ratio is 1:2, obtains mixture D；
E) mixture D is placed in agate jar, total volume is no more than the one third of ball grinder total measurement (volume), preferably general assembly
Doses total measurement (volume) a quarter between one third；Ball mill ball milling mixing is used in air atmosphere, and revolving speed exists
Between 200rpm to 300rpm, preferably revolving speed is between 230rpm to 280rpm；Time, the preferably time existed in 8h between for 24 hours
Between 10h to 18h, the copper ball E for uniformly coating thin graphene is obtained；
Graphene provided by the invention shifts to form graphene packet from shell-core structure to irregular micro-nano particle surface
The preparation method of the irregular micro-nano particle covered, comprising the following steps:
A) the copper microballoon for uniformly coating different-thickness graphene is obtained with above-mentioned method for coating；
B) the copper microballoon of certain mass coated graphite alkene is placed in ball grinder, other solid powder samples, powder is added
Sample size is between 10nm to 500 μm, and preferred size range is 100nm to 200 μm, the copper microballoon and powder of coated graphite alkene
Sample quality ratio is between 100:1 to 1:1, and preferred mass ratio is between 30:1 to 10:1, and in air atmosphere, (oxidizable sample is set
In argon atmosphere or vacuum) under ball milling, revolving speed between 200rpm to 500rpm, preferably revolving speed 350rpm to 450rpm it
Between, Ball-milling Time is between 6h to 12h, and the preferably time is between 8h to 12h.
C) b) gained mixture is sieved, removes copper ball, gained is that thin graphene uniformly coats solid powder sample.
Embodiment 1:
A) crystalline flake graphite (16 mesh, carbon content >=99%) 30g is weighed, copper ball (400 μm of diameter) 60g is uniformly mixed；
B) said mixture is placed in agate jar, uses ball mill ball milling mixing in air atmosphere, setting revolving speed is
250rpm, Ball-milling Time 10h；
C) remaining crystalline flake graphite in b) gained mixture is sifted out (sieve aperture is 0.03mm), remainder cladding different-thickness
The copper ball of graphene；
D) copper ball after c) middle gained cladding is placed in clean agate jar, the same specification of 120g (diameter 400 is added
μm) clean copper ball is uniformly mixed；
E) setting ball milling parameter is revolving speed 250rpm, time 12h, obtains thin uniform layer graphene coated copper ball product.
Embodiment 2:
A) 50g embodiment 1 gained graphene-copper ball shell-core cladding sample is weighed to be placed in stainless steel jar mill；
B) (inert atmosphere) 2g lithium aluminium hydride reduction powder is added into ball grinder in glove box, and closed ball milling tank makes in tank
Full of argon gas.Setting ball milling parameter is revolving speed 450rpm, time 12h；
C) b) gained mixture is sieved (sieve aperture is 0.02mm) in glove box, removes copper ball, obtains graphene packet
Cover lithium aluminium hydride reduction compound.
Embodiment 3:
A) 30g embodiment 1 gained graphene-copper ball shell-core cladding sample is weighed to be placed in stainless steel jar mill；
B) 1g iron phosphate powder is added into ball grinder uniformly to mix, closed ball milling tank, setting ball milling parameter is revolving speed
400rpm, time 12h；
C) by b) gained mixture sieving (sieve aperture is 0.02mm), copper ball is removed, graphene-coated lithium iron phosphate is obtained
Sample.
Application examples 1:
The lithium aluminium hydride reduction powder coated using solid graphite alkene in embodiment 2 releases hydrogen material as hydrolysis.
A) it weighs about 0.84g graphene-lithium aluminium hydride reduction composite powder sample and is put into spherical die, apply about 12MPa pressure
Compacting balling-up in power 2 minutes or so, sample ball；
B) cutting diameter is respectively 26mm, 22mm, and with a thickness of the aluminium foil disk of 0.03mm, aluminium foil is respectively placed in sample ball
Upper and lower hemisphere face, with custom mold pressing and wrapping；
C) ice thaw characteristics of the sample are tested using draining water gathering of gas law: sample being placed in 15ml deionized water, room temperature
Under the conditions of record experimental data；
D) lithium aluminium hydride reduction bead fully reacting in 1h of aluminium foil package graphene uniform cladding, reaction is at the uniform velocity controllable and produces
Object hydrogen free of losses.
Aluminium foil wraps up the lithium aluminium hydride reduction sample hydrogen storage mass ratio of graphene uniform densification cladding up to 18% or more, comprising
In the case where water, hydrogen storage mass ratio also can reach 9% or more.
Application examples 2:
As described in example 3 above, graphene can also coat other metal oxides such as SnO2, Co3O4, Fe2O3, TiO2 etc.
As lithium battery material, good electric conductivity is realized, promote specific surface area and volume energy density.Metal (metal oxide) is such as
Au, ZnO, NiO, MnO2, conducting polymer such as polyaniline, polypyrrole etc. are made with the compound composition conductive network structure of graphene uniform
For the electrode material of supercapacitor, power density, energy density, specific capacitance and the cycle performance of supercapacitor can be improved
Deng.
Application examples 3:
It may be implemented to store lithium aluminium hydride reduction, lithium hydride, sodium hydride under air atmosphere using the uniform cladding process of solid graphite alkene
Realize that ambient air atmosphere is transported safely etc. active substance, and by further coating aluminium foil, polymer shell etc..
Application examples 4:
Using the excellent chemical sensitivities and high sensitivity and stability of graphene, added in detector material uniformly thin
Layer graphene carries out the compound sensitivity for being greatly improved and detecting to gas molecule.Thus can prepare as NO2 molecular detector,
NH3 molecular detector etc..
Claims (9)
1. all solid state preparation method of irregular micro-nano particle coated with uniform graphene, which is characterized in that including following step
It is rapid:
Step 1, graphene coated microballoon shell-core structure is prepared；
Step 2, graphene coated microballoon shell-core structure is to the transfer on irregular micro-nano particle surface to form graphene coated
Irregular micro-nano particle.
2. all solid state preparation method of irregular micro-nano particle coated with uniform graphene according to claim 1,
Be characterized in that, step 1 specifically includes the following steps:
1) it by crystalline graphite powder and is wrapped by hard microballoon and mixes to obtain mixture A；
2) mixture A is placed in agate jar, crystalline flake graphite and microballoon generate friction, different-thickness graphite in mechanical milling process
Alkene shifts and is coated to hard microsphere surface, obtains mixture B；
3) graphite powder in mixture B is sifted out, obtains the microballoon shell-core structure C of different-thickness graphene coated；
4) C is wrapped by hard microballoon with new a batch and mixes to obtain mixture D；
5) mixture D is placed in agate jar, further ball milling makes graphene, and further transfer reaches between different spheres
The purpose of removing is to obtain the microballoon shell-core structure E that thin graphene coats.
3. all solid state preparation method of irregular micro-nano particle coated with uniform graphene according to claim 1,
Be characterized in that, step 2 specifically includes the following steps:
A) thin uniform layer graphene coated microsphere compound C or E obtained is mixed mixed with irregular micro-nano particle to be covered
Close object F；
B) mixture F is placed in ball grinder, obtains mixture G after ball milling；
C) mixture G is sieved, removal microballoon obtains thin graphene cladding solid matter compound H.
4. all solid state preparation method of irregular micro-nano particle coated with uniform graphene according to claim 2,
It is characterized in that, in step 1), crystalline graphite powder and is wrapped by the mass ratio of hard microballoon between 1:20 to 1:1；Step 4)
In, C and new a batch are wrapped by the mass ratio of hard microballoon between 1:1 to 1:3.
5. all solid state preparation method of irregular micro-nano particle coated with uniform graphene according to claim 2,
It is characterized in that, in step 2), the total volume of mixture A is no more than the one third of ball grinder total measurement (volume)；It uses in air atmosphere
Ball mill ball milling mixing, revolving speed is between 200rpm to 300rpm；Ball-milling Time is between 6h to 16h；In step 5), mixture
D total volume is no more than the one third of ball grinder total measurement (volume)；Revolving speed is between 200rpm to 300rpm；Ball-milling Time is arrived in 8h
Between for 24 hours.
6. all solid state preparation method of irregular micro-nano particle coated with uniform graphene according to claim 3,
It is characterized in that, in step a), C or E and irregular micro-nano particle mass ratio to be covered are between 100:1 to 1:1；In step c),
Ball milling in air atmosphere, revolving speed is between 200rpm to 500rpm；Ball-milling Time is between 6h to 12h.
7. all solid state preparation method of irregular micro-nano particle coated with uniform graphene according to claim 2,
Be characterized in that, in step 2 with to be wrapped by the material that hard microballoon mixes further include amorphous graphite and graphite particle；It is wrapped by hard
Microballoon is one of metallic microspheres, oxidate microspheres, nitride or carbide microballoon, the size of microballoon 20 μm to 5mm it
Between.
8. all solid state preparation method of irregular micro-nano particle coated with uniform graphene according to claim 3,
It is characterized in that, irregular micro-nano particle includes spherical powder, flakelike powder, particle powder or crystallite, irregular micro-nano particle ruler
Very little range is between 100nm to 500 μm.
9. irregular micro-nano particle coated with uniform graphene is all solid state according to Claims 2 or 3 any one
Preparation method, which is characterized in that ball grinder is agate jar, teflon seal ball grinder, stainless steel seal ball grinder,
Hard alloy seals ball grinder, aluminium oxide/corundum sealing ball grinder, zirconium oxide seals ball grinder, polyurethane seal ball grinder, carbon
SiClx seals one of ball grinder or sealed nylon ball grinder.
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| CN110143587A (en) * | 2019-05-27 | 2019-08-20 | 西安交通大学 | A method of so that graphene uniform is loaded micro-and nano-particles |
| CN110255542A (en) * | 2019-06-28 | 2019-09-20 | 沈阳航空航天大学 | A kind of grapheme tube and preparation method thereof |
| CN110428978A (en) * | 2019-07-28 | 2019-11-08 | 五邑大学 | One kind being based on NiMoO4The preparation method of the energy storage electrode of@graphite composite material |
| CN110790236A (en) * | 2019-09-26 | 2020-02-14 | 西安交通大学 | Method for coating nano ammonium perchlorate by graphene wet process |
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| CN110143587A (en) * | 2019-05-27 | 2019-08-20 | 西安交通大学 | A method of so that graphene uniform is loaded micro-and nano-particles |
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| CN111303524A (en) * | 2020-04-15 | 2020-06-19 | 西安交通大学 | Graphene-based permanent antistatic plastic master batch, preparation method thereof and permanent antistatic plastic based on graphene-based permanent antistatic plastic master batch |
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| CN112063433B (en) * | 2020-08-24 | 2022-03-04 | 中国地质科学院郑州矿产综合利用研究所 | Alumina-graphene with core-shell structure and preparation method thereof |
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