CN107163686A - A kind of preparation method and applications of graphene composite conductive ink - Google Patents
A kind of preparation method and applications of graphene composite conductive ink Download PDFInfo
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- CN107163686A CN107163686A CN201710319167.8A CN201710319167A CN107163686A CN 107163686 A CN107163686 A CN 107163686A CN 201710319167 A CN201710319167 A CN 201710319167A CN 107163686 A CN107163686 A CN 107163686A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
Abstract
The invention discloses a kind of preparation method and applications of graphene composite conductive ink, comprise the following steps：(1) graphite oxide is prepared with Hummers methods；(2) dust technology immersion treatment original graphite alkene microplate and multi-walled carbon nanotube are used, so as to be grafted a small amount of oxygen-containing functional group on original graphite alkene microplate and multi-walled carbon nanotube；(3) material obtained by step (2), the graphite oxide obtained by step (1) and thickener are scattered in the mixed solvent together, and carry out being fully ground mixing, obtain the graphene composite conductive ink.Graphene composite conductive printing ink concentration prepared by the present invention is higher, and excellent stability can apply to the fields such as the preparation of inkjet printing, conducting wire and conductive film.
Description
Technical field
The invention belongs to graphene applied technical field, and in particular to a kind of preparation method of graphene composite conductive ink
And its application.
Background technology
2004, the physics professor An Deliegaimu (Geim) of Univ Manchester UK and Constantine's promise were fertile
Xiao Luofu (Novoselov) is successfully peeled off by a kind of simple micromechanics stripping method, i.e. adhesive tape method and has been observed individual layer
Graphene crystal.Graphene be one kind by carbon atom with sp2Hybridized orbit composition hexangle type is in the crystal film of honeycomb lattice
Material, its carbon atom arrangement as graphite monoatomic layer, the carbon atom bonding of each carbon atom and surrounding and constitute positive six
Side shape, each carbon atom that the regular hexagon is actually similar in a phenyl ring, its structure can contribute a non-bonding
Carbon-carbon bond length in electronics, graphene is about 0.142nm.The graphene crystal of individual layer is to build other dimension carbonaceous materials
Elementary cell, it, which is decomposed, can form zero dimension fullerene, and curling can form one-dimensional CNT, and stacking can then form
Three-dimensional graphite.
Its unique property of the special structures shape of graphene.For from molecular level, carbon atom in graphene
Carbon atom in most of property and phenyl ring is similar.However, because graphene is made up of countless hexatomic rings, and its
Contribution of the edge hydrogen atom to molecule is far smaller than phenyl ring, therefore graphene is but also with the different property of many uniquenesses.And from grand
From the point of view of sight aspect, graphene is exactly the graphite of individual layer, therefore its edge character and graphite are similar to a certain extent.Also
It is to say, graphene has the chemical property of condensed-nuclei aromatics and graphite simultaneously.The electron cloud of graphene carbon skeleton rich surrounding causes
It is easy to carry out pi-pi accumulation, so as to form Multi-layer graphite structure, numerous advantageous properties of graphene are exactly from this special knot
What structure was obtained.First, graphene has the specific surface area of super large, up to 2630m2/g；Secondly, graphene also possesses excellent light
Electrical property, the light transmittance of single-layer graphene is up to 97.7%, and its carrier mobility is then up to 2 × 105cm2/V·S；It is also
With calorifics and mechanical property free from worldly cares, its thermal conductivity factor is up to 5000W/mK, and Young's modulus then reaches 1TPa；In addition,
Graphene also possesses a series of uniquenesses such as perfect quantum tunneling effect, the quantum hall effect of half-integer and room-temperature ferromagnetic
Property.Exactly these unique properties cause graphene to be led in composite, energy storage material, sorbing material, photoelectric material etc.
Domain possesses huge potential using value.Wherein, the light transmittance of the excellent electric conductivity of graphene and superelevation makes it in electrically conductive ink
There is huge application potential with film applications.
Electrically conductive ink is a kind of conducing composite material being made up of conductive filler, link stuff, solvent and auxiliary agent.In conductive oil
There are countless conducting particles to be dispersed in link stuff and solvent in ink, in state of insulation, after drying, solvent volatilization, print
Brush product possesses electric conductivity.With nanometer technology develop rapidly and printed electronics technology increasingly mature, nano-level conducting
Ink scientific research at home and abroad and industrial circle are also received more and more attention, and it is in printed circuit board, conductive coating, wireless
Application in the fields such as radio frequency identification, which is also cured day, to be increased.Therefore, research and preparation to nano conductive printing ink has great reality
Border meaning and industrial value.The current relatively broad nano conductive printing ink used has metal nano electrically conductive ink, inorganic semiconductor
Electrically conductive ink, conducting polymer electrically conductive ink and graphite, electric conduction of carbon fiber ink etc..However, made by these nano materials
Standby electrically conductive ink respectively has advantage and disadvantage.Metal nano electrically conductive ink is typically filled out using gold, silver, copper nanoparticle as conduction
Material, although golden nanometer particle and Nano silver grain are with excellent electric conductivity, cost is higher, and Nano silver grain holds
Yi Fashengyin migration phenomenon and cause the precipitation of Argent grain.Although the cost of copper nano-particle ink decreases, but leads
It is electrically not good, and stability is bad, is difficult to disperse, and is easily oxidized after ingress of air.Inorganic semiconducting inks are commonly used to
The fields such as thin film transistor (TFT), solar cell, but electric conductivity is poor.Although conducting polymer can be with solution, stability
It is not good enough with electric conductivity.Graphite, electric conduction of carbon fiber ink cost are relatively low, but electric conductivity and solvent resistance are bad, are simply possible to use in conduction
Property require low product printing.Therefore, the more excellent electrically conductive ink of research and development combination property is then particularly important.
Recently, application of the graphene nanosheet in electrically conductive ink is received more and more attention, in theory graphene
In electrically conductive ink can as a kind of conductive filler of efficient and cost-effective, prepared electrically conductive ink can be applied to touch-screen,
Electronic Paper, sensor, wireless radio frequency identification mark, photovoltaic cell, solar cell, conducting wire etc..Because with nanogold
Category particle is compared, and the existing excellent electric conductivity of graphene also has obvious cost advantage.And with traditional graphite, carbon fiber
Electrically conductive ink is compared, and Graphene conductive ink is not only even better in terms of electric conductivity, moreover it is possible to suitable for 3D printing, inkjet printing
Etc. technology.On the other hand, application of the graphene in transparent conductive film is also more and more interested to researchers, in view of graphite
The excellent electric conductivity of alkene, light transmittance, thermal conductivity and pliability, it is thin that transparent graphene conductive film is expected to the traditional ITO of replacement
Film is applied to the photoelectric fields such as liquid crystal display, solar cell, Organic Light Emitting Diode, smart window, touch-screen, as the next generation
Conductive film material.Although the unique charming performance of graphene has attracted numerous researchers, no sooner has one fallen than another steps into the breach, and ground is ground to it
Study carefully, graphene also there are many outstanding achievements in research in the application of electrically conductive ink and conductive film, but still suffers from many needs
The problem of overcoming.
In Graphene conductive ink field, due to the specific surface area of the special two-dimensional structure of graphene and super large, Yi Jishi
Strong Van der Waals force, causes graphene to be difficult to the fine dispersion in solvent and polymeric matrix between black alkene microplate.And oxygen
Although graphite alkene can be scattered in most of solvents, electric conductivity is very low, is led even if its part of recovery is also only capable of after reduction
Electrically, it is impossible to meet requirement of the printed electronics to electric conductivity.At present, the preparation research of Graphene conductive ink is also generally concentrated
Synthesis and scattered, most of preparation method complex steps in conductive filler, cause a large amount of wastes of raw material, cost compared with
Height, and during using a large amount of toxic solvents such as DMF, NMP, acetone, tetrahydrofuran, isophorone etc..Prepared graphene
The electrically conductive ink resin and auxiliary agent more due to the addition of, and organic solvent boiling point is higher, be difficult to volatilize, therefore ink is in print
Solidification can not be realized in relatively low temperature and in the short period during system, limit its application in printed electronics field.
In graphene conductive film field, although had been achieved in terms of its properity and preparation rather rich
Rich achievement, but be intended to prepare the large area high grade of transparency and the film of high conductivity also has certain challenge.At present, graphite
The preparation method of alkene conductive film mainly has chemical vapour deposition technique (CVD), vacuum filtration method, spin-coating method, drop-coating, spraying
Method, self-assembly method, volume to volume method, inkjet printing etc., these preparation methods can be divided into two major classes substantially：CVD and liquid phase point
Scattered post treatment method.CVD prepares transparent graphene conductive film cost height, and its uniformity etc. also has much room for improvement, and is turning
Graphene film is easily broken during shifting.And it is typically all to be based on redox side that solwution method, which prepares graphene film,
Method, the defect introduced in oxidizing process is difficult to complete recovery, therefore prepared graphene conductive film electric conductivity is also difficult to
Compared with traditional material, the electric conductivity to improve film need to then introduce the noble metal nanos such as Au, Ag grain in preparation process
Son, complex process and cost is higher, it is impossible to large-scale application.
As can be seen here, it is necessary to develop a kind of green high-efficient, low cost, the formula without insulating polymer auxiliary agent, lead to
Cross easy-to-use technique to prepare graphene composite conductive ink and film on a large scale, the preparation of electrically conductive ink and film is joined
System gets up, and promotes graphene in the practical application process of photoelectric field.
The content of the invention
It is an object of the invention to overcome prior art defect, there is provided a kind of preparation side of graphene composite conductive ink
Method.
Another object of the present invention is to provide a kind of preparation method of graphene composite conductive film.
The present invention theoretical foundation be：
Graphene and CNT are typical two peacekeepings one-dimensional carbon nano materials, with excellent electric conductivity, mechanicalness,
Thermal conductivity and translucency etc..Therefore, just by the extensive concern of researcher since being come out from them.If using the two simultaneously as leading
Electric filler is used to prepare graphene composite conductive ink, and two-dimentional graphene microchip and one-dimensional CNT are in structure and property
On will form complementation, a kind of cooperative effect can be produced between them, and then give full play to respective advantage so that conductive oil
The various physical and chemical performances of ink are strengthened, with more excellent processing performance and performance.By this composite guide
Electric ink is coated, printing product, also by with more perfect conductive network structure and more excellent electric conductivity.Will be such a
After composite conducting ink is coated in substrate, in the conductive film formed, CNT can make up graphene microchip
Discontinuity, and graphene microchip can then repair the space of carbon nanotube network.However, due to graphene and carbon nanometer
Pipe has high specific surface area and radius-thickness ratio, and there is strong Van der Waals'attractive force, and they are more likely to flock together simultaneously
Settle, therefore, it is the key factor for preparing graphene composite conductive ink how they to be stably scattered in solvent.
The solvent for being capable of the carbon nanomaterial such as fine dispersion graphene at present only has the toxicity such as NMP, DMF, acetone, isophorone larger
Organic solvent, these solvent boiling points are higher, be difficult to volatilize, and prepared ink can not be in lower temperature in printing coating procedure
Solidify with being realized in the short period.Therefore the present invention prepares graphene conductive oil using more green safety and effective solvent
Ink and film.According to the similar principle mixed, when the surface tension of solvent can be with the surface free energy of graphene (at room temperature
46mJ/m2) when being mutually matched balance, graphene microchip just can preferably be disperseed in a solvent.At room temperature, the table of water
Face tension force is 72.86mN/m, and the surface tension of ethanol is 21.97mN/m, thus can be speculated when water and ethanol are mixed by a certain percentage
After conjunction, the surface tension of gained mixed solvent can mutually be balanced with the surface free energy of the material such as graphene, reach phase patibhaga-nimitta
Molten purpose, and the mixed solvent low boiling point, environmental protection.Certainly, only this is also not enough to prepare high concentration, high stability
Graphene composite conductive ink, suitable dispersing aid need to be added again to aid in the progress of the carbon materials such as graphene is good to disperse,
The dispersing aid generally used at present is insulating polymer surfactant, and these pluronic polymers are difficult to remove from finished product,
The electric conductivity of Graphene conductive ink and film can largely be influenceed.In view of GO contains more oxygen-containing functional group,
And with excellent hydrophily, then it should can also be taken as a kind of dispersant to substitute complete nonconducting high molecular form
Face activating agent.First in the minimal amount of oxygen-containing functional group of surface grafting of graphene and multi-walled carbon nanotube, and together with micro GO
It is scattered in the mixed solvent and is ground mixing.The oxy radical of micro GO institutes band partially grafted can be received in graphene and many wall carbon
The surface of mitron, remaining oxy radical is then scattered in solvent phase, plays a part of aid dispersion, prevents graphene and many walls
The reunion sedimentation of CNT, so prepared graphene composite conductive ink is by with more excellent electric conductivity.And
Because GO is as dispersing aid, the amount of addition is few, even can also obtain conduction without reduction treatment after ink solidification
The coating and film of excellent performance, if after reduction, the electric conductivity of film then will further improve, so can be according to application
Need to choose whether to be reduced.
Technical scheme is as follows：
A kind of preparation method of graphene composite conductive ink, comprises the following steps：
(1) graphite oxide (GO) is prepared with Hummers methods；
(2) with dust technology immersion treatment original graphite alkene microplate (GNP) and multi-walled carbon nanotube (MWCNTs), so that original
A small amount of oxygen-containing functional group is grafted on graphene microchip (GNP) and multi-walled carbon nanotube (MWCNTs)；Above-mentioned original graphite alkene is micro-
The number of plies of piece is 1~10 layer, and piece footpath is 0.1~5um, and initial conductivity is 10000~20000S/m；Above-mentioned multi-walled carbon nanotube
Length is 10~30um, and internal diameter is 10~20nm, and initial conductivity is 300~600S/m；
(3) material obtained by step (2), the graphite oxide obtained by step (1) and thickener are scattered in together and mix molten
In agent, and carry out being fully ground mixing, obtain the graphene composite conductive ink；
Wherein, thickener is hydroxypropyl methyl cellulose, acrylic resin, ethyl cellulose, polyvinyl alcohol and terpinol
At least one of, mixed solvent is made up of second alcohol and water with 1~10: 1~10 volume ratio, with the original of dust technology immersion treatment
Beginning graphene microchip, the mass ratio with the multi-walled carbon nanotube of dust technology immersion treatment, graphite oxide, thickener and mixed solvent
For 1~4: 0.1~2: 0.1~1: 0~1: 310~380.
In a preferred embodiment of the invention, the graphite oxide of the step (1) is with 8000 mesh crystalline flake graphites
For raw material, with KMnO4Oxidation intercalation is carried out to original crystalline flake graphite as strong oxidizer with the concentrated sulfuric acid and is made.
In a preferred embodiment of the invention, the original graphite alkene microplate is that the method that is by mechanically pulling off is made.
In a preferred embodiment of the invention, the step (2) is：With dust technology immersion treatment original graphite alkene
1~6h of microplate and multi-walled carbon nanotube, so as to be grafted a small amount of oxygen-containing function on original graphite alkene microplate and multi-walled carbon nanotube
Group, then carries out suction filtration, washing, and dry for standby to the material of gained.
In a preferred embodiment of the invention, the equipment used in the ground and mixed of the step (3) is sand mill
Or basket-type grinder, grinding speed setting is 2000~3000rpm, and the time of ground and mixed is 3~24h, and abrasive media is 0.2
~2mm zirconium oxide bead.
Another technical scheme of the present invention is as follows：
A kind of preparation method of graphene composite conductive film, is entered using above-mentioned graphene composite conductive ink as presoma
Row coating and reduction treatment.
In a preferred embodiment of the invention, the coating uses drop-coating or spin-coating method.
In a preferred embodiment of the invention, the reduction treatment is that HI is reduced or high annealing reduction.
Beneficial effects of the present invention：
1st, formulation green safety of the invention, cost are relatively low, and the high molecular surfactant of insulation is substituted with micro GO, with
Second alcohol and water is as mixed solvent, and prepared graphene composite conductive ink environment is friendly, strong applicability, and application is more
Extensively；
2nd, preparation technology of the invention is simple and easy to do, efficiency is higher, directly makes respectively to lead by simple step ground and mixed
Good interaction is carried out between electric filler, stable dispersion, high performance graphene composite conductive ink is made, the technique has
The industrialization applied to Graphene conductive ink is hoped to mass produce.
3rd, the graphene composite conductive printing ink concentration prepared by the present invention is higher, and excellent stability can apply to ink-jet and beat
The fields such as the preparation of print, conducting wire and conductive film.
4th, using the graphene composite conductive ink of the invention prepared as presoma, simple drop-coating and spin-coating method are passed through
The graphene conductive film of excellent performance is can be prepared by, the preparation of graphene conductive film and Graphene conductive ink is closely joined
System gets up, and further promotes the application process of graphene.
5th, the graphene conductive film prepared by the present invention has very excellent electric conductivity, can not only be attached directly to
It in substrate, also intactly can peel off, different application field requirements can be met.
Brief description of the drawings
Fig. 1 prepares the process chart of graphene composite conductive ink and film for the present invention；
Fig. 2 is the specific schematic diagram of the graphene composite conductive ink used in the embodiment of the present invention 1, wherein, a is the present invention
The apparent figure of graphene composite conductive ink product prepared by embodiment 1, b is each original in graphene composite conductive ink of the present invention
Microcosmic effect mechanism figure between material；
Fig. 3 is the photo of the graphene conductive film prepared by the embodiment of the present invention, wherein, a is the institute of the embodiment of the present invention 1
The apparent figure of graphene conductive film of preparation, b is the apparent figure of graphene conductive film prepared by the embodiment of the present invention 2, and c is this
The gained graphene conductive film of inventive embodiments 1 is suspended in HI solution, and d is that the graphene prepared by the embodiment of the present invention 3 is led
Conductive film；E is the graphene conductive film prepared by the embodiment of the present invention 4, and f is that the gained of the embodiment of the present invention 1 is independent without support
Graphene conductive film；
Fig. 4 is the SEM phenograms of graphene conductive film prepared by the embodiment of the present invention 1, wherein, a is implemented for the present invention
The plane of disruption SEM phenograms of the gained graphene conductive film of example 1, b is the flat of the gained graphene conductive film of the embodiment of the present invention 1
Face SEM phenograms；
Fig. 5 is the TEM phenograms of the graphene composite conductive ink prepared by the embodiment of the present invention 1；
Fig. 6 is EDS comparison diagram of the graphene conductive film of the preparation of the embodiment of the present invention 2 before and after reduction, wherein, a is
EDS test result figure of the graphene conductive film before reduction prepared by the embodiment of the present invention 2, b is the institute of the embodiment of the present invention 2
EDS test result figure of the graphene conductive film of preparation after being reduced by HI；
Fig. 7 is the comparison diagram before and after the processing of each raw material components in the embodiment of the present invention, wherein, a is all realities of the invention
Infrared spectrum contrast of the original graphene microchip in dust technology before and after the processing in example is applied, b is original in all embodiments of the invention
Multi-walled carbon nanotube dust technology before and after the processing infrared spectrum contrast, c for the present invention as traditional Hummers methods obtained by GO and
The infrared spectrum contrast of mechanical stripping graphene microchip, d is the gained graphene conductive film of the embodiment of the present invention 2 before and after reduction
Infrared spectrum contrast；
Fig. 8 is Raman comparison diagram of the graphene conductive film of the embodiment of the present invention 2 before and after reduction；
Fig. 9 is XRD comparison diagram of the graphene conductive film of the preparation of the embodiment of the present invention 2 before and after reduction, wherein, a is
XRD phenogram of the graphene conductive film of the embodiment of the present invention 2 before reduction, b is the graphene conductive of the embodiment of the present invention 2
XRD phenogram of the film after reduction.
Embodiment
Technical scheme is further detailed and described below by way of embodiment combination accompanying drawing.
As shown in figure 1, a kind of preparation method of graphene composite conductive ink, comprises the following steps：
(1) graphite oxide is prepared with Hummers methods；
(2) use dust technology immersion treatment original graphite alkene microplate and multi-walled carbon nanotube so that original graphite alkene microplate and
A small amount of oxygen-containing functional group is grafted on multi-walled carbon nanotube；The number of plies of above-mentioned original graphite alkene microplate is 1~10 layer, and piece footpath is
0.1~5um, initial conductivity is 10000~20000S/m；Above-mentioned multi-wall carbon nano-tube length of tube is 10~30um, and internal diameter is 10
~20nm, initial conductivity is 300~600S/m；
(3) material obtained by step (2), the graphite oxide obtained by step (1) and thickener are scattered in together and mix molten
In agent, and carry out being fully ground mixing, obtain the graphene composite conductive ink；
Wherein, thickener is hydroxypropyl methyl cellulose, acrylic resin, ethyl cellulose, polyvinyl alcohol and terpinol
At least one of, mixed solvent is made up of second alcohol and water with 1~10: 1~10 volume ratio, with the original of dust technology immersion treatment
Beginning graphene microchip, the mass ratio with the multi-walled carbon nanotube of dust technology immersion treatment, graphite oxide, thickener and mixed solvent
For 1~4: 0.1~2: 0.1~1: 0~1: 310~380.
In step (1), it is with 8000 mesh crystalline flake graphites that the traditional Hummers methods of the utilization, which prepare graphite oxide (GO),
For raw material, with KMnO4Oxidation intercalation is carried out to original crystalline flake graphite as strong oxidizer with the concentrated sulfuric acid.The concrete technology of the step
Flow is：1. 2g crystalline graphite powders are accurately weighed, the dense H of 100ml are measured2SO4It is mixed in beaker, is placed in carrying out in ice-water bath
Stirring, mixing；2. 11-12g potassium permanganate powders are weighed, are slowly added into equipped with original crystalline flake graphite and dense H2SO4Beaker
In, and keep ice-water bath 30min；3. after ice-water bath 30min, 2h is stirred under normal temperature water-bath, afterwards toward being slowly added in beaker
150ml distilled water, during release amount of heat；4. it is down to after room temperature, appropriate 30% mass fraction is added into beaker
H2O2, occur redox reaction with strong oxidizer, strong oxidizer neutralized, golden yellow is become to solution；5. gained is produced
Thing stands 24h, removes supernatant, washing and centrifugation using distilled water to the progress of bottom precipitum repeatedly, until the PH of product
It is worth partial neutral (PH >=6)；6. solid product is collected, is freeze-dried, it is standby；7. 1.-technique 6. is repeated；Flow, is prepared
The GO of sufficient amount, applied to graphene composite conductive ink and the preparation research of film.
Graphene microchip to GO and mechanical stripping carries out infrared spectrum characterization contrast, as a result as shown in Figure 7 c.It can be seen that GO
Infrared spectrum in the obvious characteristic peak of the oxy radical such as hydroxyl, carbonyl more, and the graphene microchip of mechanical stripping then without
These oxygen-containing functional groups.
In step (2), the original graphite alkene microplate is by mechanically pulling off method and is prepared, and its number of plies is 1-10
Layer, piece footpath is 0.1-5um, and initial conductivity is 10000-20000S/m.The multi-wall carbon nano-tube length of tube is 10-30um, interior
Footpath is 10-20nm, and initial conductivity is 300-600S/m.The dust technology processing refers to original graphite alkene and multi-wall carbon nano-tube
Pipe is soaked in dilute nitric acid solution respectively to be reacted, and soak time is 1-6h, then carries out suction filtration, washing, and be baked to
It is standby.The concrete technology flow process of the step is：1. 10g original graphite alkene and multi-wall carbon nano-tube pipe powder is weighed respectively, and is divided
Do not pour into two wide-mouth brown reagent bottles；2. toward adding equivalent in two wide-mouth brown reagent bottles and enough dust technologies are molten
Liquid, can fully flood solid powder；3. after immersion reaction 1-6h, suction filtration removes dilute nitric acid solution, and utilizes distilled water pair
Solid powder carries out repeatedly washing, suction filtration, and the pH value to filtrate is neutrality, collects solid product, dry for standby；4. repeat 1.-
3. technological process, is made the graphene and multi-walled carbon nanotube with micro oxygen containing functional group of sufficient amount, applied to graphite
The preparation research of alkene composite conducting ink and film.
Compared with prior art, the present invention can be prevented effectively from the addition of insulating polymer auxiliary agent using GO as dispersing aid,
While fine dispersion effect is obtained, additionally it is possible to improve the conduction of graphene composite conductive ink and film to a certain extent
Performance.In addition, step (1) and step (2) can be carried out simultaneously, technique is easy, it is easy to operation and industrialization.
Infrared spectrum characterization analysis is carried out to dust technology graphene microchip before and after the processing and multi-walled carbon nanotube, as a result such as
Shown in Fig. 7 (a-b).As can be seen that original GNP is without any oxygen-containing functional group, and after dilute HNO3 immersion treatment, into
Work(has been grafted above-OH groups (3735cm-1), C=O groups (1794cm-1), the partial double bond structure in its phenyl ring is broken,
Form C-H singly-bounds (2923cm-1) and C-C groups (1384cm-1).And original MWCNTs surfaces are i.e. already provided with a small amount of
Hydroxyl (3416cm-1), after dilute HNO3 immersion treatment, successfully C=O groups (1654cm has been gone up in grafting again on its surface-1).As can be seen here, by simple dust technology immersion treatment, a little oxygen-containing functional group can be connected on GNP and MWCNTs surfaces,
These oxy radicals can react during ground and mixed with the part oxygen-containing functional group on GO, so that hydrophobicity
GNP and MWCNTs can in aqueous solvent stable dispersion, graphene composite conductive ink is made.
It is made by above-mentioned steps (1) and step (2) after the conductive filler of sufficient amount, the different formula of trial and preparation work
Skill carries out the preparation of graphene composite conductive ink and film.
Embodiment 1
According to technical scheme disclosed by the invention, carry out following proportioning and operate：
(1) material of following mass parts is taken：The treated graphene microchip of 3 parts of dust technologies, 0.75 part of dust technology are treated
Multi-walled carbon nanotube, 0.75 part of GO, 100 parts of ethanol, 260 parts of water mixed, ultrasound it is pre-dispersed after, put into basket grinding
Ground and mixed 4h in machine, speed setting is 2000rpm, and the graphene composite conductive oil for being not added with any pluronic polymer is made
Ink；
(2) prepared graphene composite conductive ink is coated on slide by drop-coating, made by heating molten
After agent evaporation, in the graphene conductive film that uniformly continuous is obtained in slide substrate；
(3) take a piece of above-mentioned gained graphene conductive film to be divided into three equal parts and carry out contrast test：A copy of it is not made
Any processing, portion carry out reduction treatment, portion in HI and high annealing reduction treatment are carried out at 300 DEG C；
(4) resistivity of three graphene films after above-mentioned divide equally by different disposal is tested with four-point probe,
The microscopic appearance of graphene composite conductive ink and film is characterized using field-emission scanning Electronic Speculum and transmission electron microscope.
As shown in Fig. 2 being capable of stable dispersion, and concentration as the graphene composite conductive ink prepared by the embodiment of the present invention
It is higher.Microcosmic effect mechanism in the graphene composite conductive ink of the present invention between each conductive material is as shown in Figure 2 b, original
GNP and MWCNTs are after the immersion treatment by dust technology, and its surface can connect minimal amount of oxygen-containing functional group.In ground and mixed
During these oxygen-containing functional groups can be reacted with the part oxygen-containing functional group on GO so that GNP and MWCNTs
Surface be connected to extremely hydrophilic GO microplates, effectively prevent hydrophobic GNP and MWCNTs itself from occurring to reunite and settling, most
The graphene composite conductive ink of stable dispersion is made eventually.As shown in Figure 3 a, the graphene conductive prepared by the embodiment of the present invention
Film is uniform and smooth, and the graphene composite conductive printing ink concentration obtained by the present invention is higher, therefore the conductive film formed
It is thicker and light tight.When carrying out reduction treatment to graphene conductive film using HI, deposition is carried on the graphene on slide
Conductive film intactly can peel off, and be suspended in the surface of HI solution, as shown in Figure 3 c, will can peel off afterwards
Graphene conductive film be transferred to other target substrates and applied, or directly drying obtains independent unsupported graphene and led
Conductive film, as illustrated in figure 3f.Graphene conductive film prepared by the embodiment of the present invention after different reduction treatments, its
Sheet resistivity can be reduced significantly, be shown in Table 1.These results indicate made by such a graphene composite conductive ink
Film can meet form and conduction needs of the different field to conductive film, with very wide application prospect.Fig. 4 and
SEM the and TEM characterization result figures of graphene composite conductive ink and film of the Fig. 5 prepared by the embodiment of the present invention, can see
Go out, good compound overlap joint can be carried out between each conductive filler, form continuous conductive network structure (Fig. 4 a), MWCNTs institutes shape
Into structure be mixed in graphene microchip stacking interlayer, support (Fig. 4 b) can be played a part of.MWCNTs can not only be
Non-touching graphene microchip plays a part of bridge overlap joint (Fig. 5 a), also can mutually wind overlap joint and form network structure,
Basic unit's support of overlap joint is stacked with as graphene microchip, meanwhile, also there is part MWCNTs to be carried in graphene microchip (figure
5b-d).These overlapping modes each contribute to improve the bulk properties of graphene film, increase answering for graphene composite conductive ink
Use scope.
Embodiment 2
According to technical scheme disclosed by the invention, carry out following proportioning and operate：
(1) raw material of following mass parts is taken：The treated graphene microchip of 1 part of dust technology, 0.2 part of dust technology are treated
Multi-walled carbon nanotube, 0.25 part of GO, 100 parts of ethanol, 260 parts of water are mixed, and after ultrasound is pre-dispersed, put into basket-type grinder
Middle grinding 4h, speed setting is 2000rpm, the graphene composite conductive ink for being not added with any pluronic polymer is made；
(2) prepared graphene composite conductive ink is coated on slide by drop-coating, made by heating molten
After agent evaporation, in the graphene conductive film that uniformly continuous is obtained in slide substrate；
(3) take a piece of above-mentioned gained graphene conductive film to be divided into three equal parts and carry out contrast test：A copy of it is not made
Any processing, portion carry out reduction treatment, portion in HI and high annealing reduction treatment are carried out at 300 DEG C；
(4) resistivity of three graphene films after above-mentioned divide equally by different disposal is tested with four-point probe,
And EDS, infrared spectrum, Raman and XRD test signs are carried out to the graphene conductive film before and after reduction treatment.
Graphene conductive film apparent form prepared by the embodiment of the present invention is passing through reduction treatment as shown in Figure 3 b
Afterwards, its resistivity is greatly lowered.As shown in fig. 6, as the graphene conductive film prepared by the embodiment of the present invention in warp
Cross after HI reduction treatments, its oxygen content is obviously reduced, illustrate that the restoring method of the present invention is practicable, can effectively remove thin
Oxygen-containing functional group in film, exactly because and in film oxygen content reduction, the sheet resistivity of film just further subtracted
It is small.As shown in figure 7d, graphene conductive film is after reduction treatment, and the infrared spectrum absorpting peak of hydroxyl and carbonyl disappears
, this illustrates that reduction treatment can effectively remove the oxygen-containing functional group in film to a certain extent.Pass through Raman and XRD
Microstructure change to graphene conductive film before and after reduction treatment is characterized, and analyzes reduction according to outcome research
Processing is to the influence caused by the microstructure of graphene conductive film.Fig. 8 is that the graphene prepared by the embodiment of the present invention is led
Raman of the conductive film before and after reduction treatment characterizes comparison diagram, it can be seen that graphene conductive film passes through HI reduction treatments
Afterwards, in its Raman spectrogram D peaks and G peaks strength ratio ID/IGSignificantly increase.Illustrate that restoring method used in the present invention can be by
Oxy radical is effectively removed in graphene film, and the GO added is reduced into rGO, in reduction process, in membrane structure
Sp3Hydbridized carbon atoms transform into sp2Hydbridized carbon atoms, reduce the degree of order of film microstructure to a certain extent.And
And due to the disappearance of the oxy radicals such as hydroxyl, carboxyl in reduction process, some regiochemistry keys on lamella may be caused
The I of graphene film after fracture so that the defect in conductive film microstructure increases, therefore reductionD/IGValue has increased.This
XRD characterization result of the graphene conductive film before and after reduction is as shown in figure 9, by micro GO aid dispersions obtained by inventive embodiments
The film that is prepared from of graphene composite conductive ink have a point at 2 θ=26.26 ° and strong characteristic diffraction peak, show
Arrangement in the microstructure of graphene conductive film between layers is fine and close and orderly, and crystallinity is higher.But in warp
Cross after reduction treatment, characteristic diffraction peak intensity of the graphene conductive film in the position substantially weakens, because reducing
The fracture of key is there occurs in Cheng Zhong, film microstructure, causes the defect on conductive filler surface to increase, the plane of graphene microchip
After size has also reduced, and oxy radical in the film is removed, the combination between lamella and lamella is more loose,
The distance between lamella has increased, and film microstructure becomes more unordered.By the illustration in Fig. 9 it can also be seen that by micro-
The film that the graphene composite conductive ink of amount GO aid dispersions is prepared from occurs in that an intensity is weaker at 11.92 ° and spread out
Peak is penetrated, the peak is GO characteristic diffraction peak.But graphene conductive film is after by reduction treatment, GO characteristic diffraction peak
Substantially disappear, the substitute is a weaker diffraction maximums of 23.70 ° of appearance, as shown in Figure 3 b, this is again effectively
Prove that the micro GO in film is successfully reduced into rGO, the peak is compared with the characteristic diffraction peak of graphene, intensity is substantially more
It is weak.
Embodiment 3
According to technical scheme disclosed by the invention, carry out following proportioning and operate：
(1) raw material of following mass parts is taken：It is many that the treated graphene microchip of 4 parts of dust technologies, 2 parts of dust technologies are treated
Wall carbon nano tube, 1 part of GO, 1 part of hydroxypropyl methyl cellulose, 205 parts of ethanol, 130 parts of water are mixed, after ultrasound is pre-dispersed,
Put into and 4h ground in basket-type grinder, speed setting is 2000rpm, the higher graphene composite conductive oil of obtained viscosity
Ink；
(2) prepared graphene composite conductive ink is coated on slide by drop-coating, made by heating molten
After agent evaporation, in the graphene conductive film that uniformly continuous is obtained in slide substrate；
(3) take a piece of above-mentioned gained graphene conductive film to be divided into three equal parts and carry out contrast test：A copy of it is not made
Any processing, portion carry out reduction treatment, portion in HI and high annealing reduction treatment are carried out at 300 DEG C；
(4) resistivity of three graphene films after above-mentioned divide equally by different disposal is tested with four-point probe.
Graphene conductive film apparent form prepared by the present embodiment as shown in Figure 3 d, after reduction treatment, its
Resistivity is greatly lowered.
Embodiment 4
According to technical scheme disclosed by the invention, carry out following proportioning and operate：
(1) raw material of following mass parts is taken：It is many that the treated graphene microchip of 2 parts of dust technologies, 1 part of dust technology are treated
Wall carbon nano tube, 0.2 part of GO, 60 parts of ethanol, 310 parts of water are mixed, and after ultrasound is pre-dispersed, is put into basket-type grinder and are ground
4h is ground, speed setting is 2000rpm, the graphene composite conductive ink for being not added with any pluronic polymer is made；
(2) prepared graphene composite conductive ink is coated on slide by drop-coating, made by heating molten
After agent evaporation, in the graphene conductive film that uniformly continuous is obtained in slide substrate；
(3) take a piece of above-mentioned gained graphene conductive film to be divided into three equal parts and carry out contrast test：A copy of it is not made
Any processing, portion carry out reduction treatment, portion in HI and high annealing reduction treatment are carried out at 300 DEG C；
(4) resistivity of three graphene films after above-mentioned divide equally by different disposal is tested with four-point probe.
Graphene conductive film apparent form prepared by the present embodiment as shown in Figure 3 e, after reduction treatment, its
Resistivity is greatly lowered.
In summary, in conjunction with the test result of graphene conductive film sheet resistivity in table 1, one kind of the present invention is illustrated
It is feasible by the graphene composite conductive ink and method for manufacturing thin film of micro-oxidation graphite aid dispersion.First pass through traditional
Hummers methods carry out GO preparation, pass through simple dilute HNO3Handle successfully to be grafted on original GNP and MWCNTs and contain on a small quantity
Oxygen groups, it are mixed with micro GO the mixed solvent for being scattered in second alcohol and water, during ground and mixed, the part on GO contains
Oxygen groups can be interacted with GNP, MWCNTs, and scattered effect is well helped so as to play, and stable and uniform is finally made
And the higher graphene composite conductive ink of concentration.Prepared graphene composite conductive ink, no matter there is no added thickener,
The good graphene conductive film of uniformly continuous, electric conductivity, and gained graphene conductive film can be made by drop-coating
When being reduced in HI solution, intactly it can be split away off from slide, it is follow-up that this point facilitates film to carry out
Using.MWCNTs can either play bridge snap action for non-touching graphene sheet layer in graphene conductive film, also can be
The conductive network structure of support type is formed between the graphene layer of stacking.The major part that reduction treatment can be removed effectively in film contains
Oxygen groups and impurity, the process can produce certain influence to the microstructure of graphene conductive film, and improve film
Electric conductivity.
Table 1
The foregoing is only a preferred embodiment of the present invention, therefore can not limit the scope that the present invention is implemented according to this, i.e.,
The equivalent changes and modifications made according to the scope of the claims of the present invention and description, all should still belong in the range of the present invention covers.
Claims (8)
1. a kind of preparation method of graphene composite conductive ink, it is characterised in that：Comprise the following steps：
(1) graphite oxide is prepared with Hummers methods；
(2) dust technology immersion treatment original graphite alkene microplate and multi-walled carbon nanotube are used, so that original graphite alkene microplate and many walls
A small amount of oxygen-containing functional group is grafted on CNT；The number of plies of above-mentioned original graphite alkene microplate be 1~10 layer, piece footpath be 0.1~
5um, initial conductivity is 10000~20000S/m；Above-mentioned multi-wall carbon nano-tube length of tube be 10~30um, internal diameter be 10~
20nm, initial conductivity is 300~600S/m；
(3) material obtained by step (2), the graphite oxide obtained by step (1) and thickener are scattered in the mixed solvent together,
And carry out being fully ground mixing, obtain the graphene composite conductive ink；
Wherein, thickener is in hydroxypropyl methyl cellulose, acrylic resin, ethyl cellulose, polyvinyl alcohol and terpinol
At least one, mixed solvent is made up of second alcohol and water with 1~10: 1~10 volume ratio, with the original stone of dust technology immersion treatment
Black alkene microplate, with the mass ratio of the multi-walled carbon nanotube of dust technology immersion treatment, graphite oxide, thickener and mixed solvent it is 1
~4: 0.1~2: 0.1~1: 0~1: 310~380.
2. preparation method as claimed in claim 1, it is characterised in that：The graphite oxide of the step (1) is with 8000 mesh squamas
Piece graphite is raw material, with KMnO4Oxidation intercalation is carried out to original crystalline flake graphite as strong oxidizer with the concentrated sulfuric acid and is made.
3. preparation method as claimed in claim 1, it is characterised in that：The original graphite alkene microplate is to be by mechanically pulling off method
It is made.
4. preparation method as claimed in claim 1, it is characterised in that：The step (2) is：It is original with dust technology immersion treatment
1~6h of graphene microchip and multi-walled carbon nanotube, so as to be grafted a small amount of contain on original graphite alkene microplate and multi-walled carbon nanotube
Oxygen functional group, then carries out suction filtration, washing, and dry for standby to the material of gained.
5. preparation method as claimed in claim 1, it is characterised in that：Equipment used in the ground and mixed of the step (3) is
Sand mill or basket-type grinder, grinding speed setting are 2000~3000rpm, and the time of ground and mixed is 3~24h, grinding medium
Matter is 0.2~2mm zirconium oxide bead.
6. a kind of preparation method of graphene composite conductive film, it is characterised in that：Will with any right in claim 1 to 5
Described graphene composite conductive ink is asked to be coated as presoma and reduction treatment.
7. preparation method as claimed in claim 6, it is characterised in that：The coating uses drop-coating or spin-coating method.
8. preparation method as claimed in claim 6, it is characterised in that：The reduction treatment be HI reduce or high annealing also
It is former.
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