CN107331439B - Carbon nanotube/nitrogen doped carbon nanotube-nano graphite flakes electrocondution slurry and preparation method - Google Patents
Carbon nanotube/nitrogen doped carbon nanotube-nano graphite flakes electrocondution slurry and preparation method Download PDFInfo
- Publication number
- CN107331439B CN107331439B CN201710457271.3A CN201710457271A CN107331439B CN 107331439 B CN107331439 B CN 107331439B CN 201710457271 A CN201710457271 A CN 201710457271A CN 107331439 B CN107331439 B CN 107331439B
- Authority
- CN
- China
- Prior art keywords
- carbon nanotube
- slurry
- nano graphite
- graphite flakes
- dispersate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
Abstract
The invention discloses a kind of carbon nanotube/nitrogen doped carbon nanotube-nano graphite flakes composite conducting slurries, belong to electrocondution slurry technical field.It is in terms of 100% by the total weight of the carbon nanotube-nano graphite flake composite conducting slurry, which includes 3%~12% dispersate and 88%~97% dispersing agent；Dispersate includes carbon nanotube/nitrogen doped carbon nanotube and nano graphite flakes；Dispersing agent includes additive and solvent.In addition, the preparation method of above-mentioned electrocondution slurry is also provided herein.Can include the following benefits using technical solution provided by the invention: conductive carbon paste has high conductivity, is suitable for the high-end fields such as Radio Frequency Identification Technology；Conductive carbon paste is free of binder, but has splendid film forming；Conductive carbon paste performance is stablized, easily stored；Conductive carbon paste material is simple, preparation process is simple, is suitable for industrialization large scale preparation.
Description
Technical field
The present invention relates to electrocondution slurry technical field, in particular to a kind of carbon nanotube/nitrogen doped carbon nanotube-nano-graphite
Piece composite conducting slurry.
Background technique
Electrocondution slurry be distributed evenly in the particle of conductive material formed in thermoplasticity or thermosetting resin it is viscous
Thick liquid.There is reality in the fields such as solar battery, supercapacitor, energy catalysis to electrode with electrocondution slurry production
Application.Electrocondution slurry is a kind of composite material for having binder, conductive filler, solvent and auxiliary agent to constitute.Wherein, binder is
The film forming matter of electrocondution slurry, dispersing conductive fine particles in a binder, form the suitable silk with certain viscosity and rheological behavior
Wire mark brush or the suspended substance of coating.Electrocondution slurry needs after silk-screen printing or thin film cladding as a kind of intermediate products
Through completion of cure at a certain temperature after a period of time, conductive film layer is finally obtained.
Electrocondution slurry can be divided into carbon slurry, metal paste and the ceramic slurry of modification according to the difference of filler.It closes at present
It is more in the research of conductive carbon paste, but the electrocondution slurry of pure carbon system has that conductivity is low, to find out its cause, being primarily due to
For conventional conductive carbon slurry using carbon black, electrographite as conductive agent, film forming is poor, needs to be added when preparing conductive carbon paste a large amount of
Binder.
Summary of the invention
The embodiment of the invention provides a kind of carbon nanotube-nano graphite flake composite conducting slurry and preparation method thereof, with
Solve the problems, such as that the conductivity of conductive carbon paste in the prior art is low.In order to some aspects of the embodiment to disclosure have one it is basic
Understanding, simple summary is shown below.The summarized section is not extensive overview, nor to determine that key/critical forms
Element or the protection scope for describing these embodiments.Its sole purpose is that some concepts are presented with simple form, in this, as
The preamble of following detailed description.
According to a first aspect of the embodiments of the present invention, a kind of carbon nanotube/nitrogen doped carbon nanotube-nano graphite flakes are provided
Composite conducting slurry.
In some exemplary embodiments, carbon nanotube/nitrogen doped carbon nanotube-nano graphite flakes composite conducting slurry,
It is in terms of 100% by carbon nanotube/nitrogen doped carbon nanotube-nano graphite flakes composite conducting slurry total weight, which includes 3%
~12% dispersate and 88%~97% dispersing agent；
Dispersate includes: carbon nanotube or nitrogen doped carbon nanotube, and, nano graphite flakes；
Dispersing agent includes: additive and solvent.
In some illustrative embodiments, in terms of the total weight of dispersate 100%, the content of nano graphite flakes is 50%
~87.5%, the content of carbon nanotube or nitrogen doped carbon nanotube is 12.5%~50%.
In some illustrative embodiments, solvent is water or N-Methyl pyrrolidone NMP.
In some illustrative embodiments, the average diameter of dispersate is less than 10 microns.
In some illustrative embodiments, additive includes surfactant；
Surfactant is polyvinylpyrrolidone PVP, dodecyl sodium sulfate SDS, methylcellulose CMC and tween-
80, one of siloxanes or a variety of compositions.
In some illustrative embodiments, surfactant PVP, by the total weight of electrocondution slurry be 100% in terms of,
The content of PVP is 0.5%~2%.
In some illustrative embodiments, additive further includes one of levelling agent, defoaming agent and binder or more
Kind.
According to a second aspect of the embodiments of the present invention, it is multiple that a kind of carbon nanotube/nitrogen doped carbon nanotube-nano graphite flakes are provided
Close electrocondution slurry preparation method；
In some exemplary embodiments, a kind of carbon nanotube/nitrogen doped carbon nanotube-nano graphite flakes composite guide plasma-based
Preparation method for material is used to prepare electrocondution slurry in above-described embodiment, comprising the following steps:
Dispersate is added in dispersing agent, mechanical stirring is uniform, obtains mixture；Wherein, dispersate includes: carbon nanometer
Pipe or nitrogen doped carbon nanotube, and, nano graphite flakes；Dispersing agent includes: additive and solvent；
Mixture is sanded, electrocondution slurry is obtained.
In some illustrative embodiments, with carbon nanotube/nitrogen doped carbon nanotube-nano graphite flakes composite conducting slurry
Total weight be 100% meter, the content of dispersate is 3%~12%, and the content of dispersing agent is 88%~97%.
In some illustrative embodiments, in terms of the total weight of dispersate 100%, the content of nano graphite flakes is 50%
~87.5%, the content of carbon nanotube or nitrogen doped carbon nanotube is 12.5%~50%.
Technical solution provided in an embodiment of the present invention can include the following benefits:
Conductive carbon paste has high conductivity, is suitable for the high-end fields such as Radio Frequency Identification Technology；
Conductive carbon paste is free of binder, but has splendid film forming；
Conductive carbon paste performance is stablized, easily stored；
Conductive carbon paste material is simple, preparation process is simple, is suitable for industrialization large scale preparation.
It should be understood that above general description and following detailed description be only it is exemplary and explanatory, not
It can the limitation present invention.
Detailed description of the invention
The drawings herein are incorporated into the specification and forms part of this specification, and shows and meets implementation of the invention
Example, and be used to explain the principle of the present invention together with specification.
Fig. 1 be the scanning electron microscope diagrams of nano graphite flakes shown according to an exemplary embodiment, thermogravimetric curve and
Raman map；Wherein: it be hot weight curve, Fig. 1 d is Raman map that Fig. 1 a-1b, which is scanning electron microscope diagram, Fig. 1 c,；
Fig. 2 is the change curve according to its viscosity under different shear rate of the electrocondution slurry shown in embodiment A；
Fig. 3 is the half-wave dipole structural schematic diagram according to the electrocondution slurry preparation of embodiment A preparation；
Fig. 4 is the test data figure to half-wave dipole in Fig. 3 when being applied to Radio Frequency Identification Technology；
Wherein: Fig. 4 a is input reflection coefficient S11Experiment curv, Fig. 4 b be the experiment curv of real gain, Fig. 4 c be
Half-wave dipole in the direction H when antenna pattern, Fig. 4 d in the direction E of half-wave dipole are in 910MHz when 910MHz
Antenna pattern.
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now to skill of the invention
Art scheme carries out described further below, but should not be understood as that limiting the scope of the invention.
A kind of preparation side of carbon nanotube/nitrogen doped carbon nanotube-nano graphite flakes composite conducting slurry provided by the invention
Method is as follows:
Dispersate is added in dispersing agent, mechanical stirring is uniform, obtains mixture；Wherein, dispersate includes carbon nanometer
Pipe or nitrogen doped carbon nanotube, and, nano graphite flakes；Dispersing agent includes additive and solvent；
Mixture is sanded, electrocondution slurry is obtained.
In the present embodiment, it is not added with binder during preparing electrocondution slurry, furthermore uses a kind of new group
It closes, i.e. carbon nanotube/nitrogen doped carbon nanotube-nano graphite flakes, prepares conductive carbon paste.It is prepared using the preparation method of the present embodiment
The completely new conductive carbon paste of one kind of obtained conductive carbon paste, has excellent conductivity and film forming, furthermore conductive carbon paste performance
Stablize, convenient for long-term storage.
In the prior art, for conventional conductive carbon slurry using carbon black, artificial graphite as conductive agent, film forming is poor, is preparing
When electrocondution slurry or electrocondution slurry needs to be added when in use a large amount of binders, low so as to cause conductivity.Although open at present
Electrocondution slurry is prepared by carbon nanotube and graphene be compound, but for carbon nanotube and the compound preparation conductive paste of nano graphite flakes
Material but has not been reported.In addition, the report about nano graphite flakes as conductive filler, is usually required to addition binder, such as phenol
Urea formaldehyde, epoxy resin and polyurethane resin etc., and the preparation for electrocondution slurry or electrically conductive ink, although nano graphite flakes
It is a kind of conductive carbon material, but rarely has document to use nano graphite flakes as conductive agent through retrieval discovery.Return its reason, Ke Nengyu
To carbon nanotube, the excellent benefit energy relevant report on conductive agent is related with graphene in recent years, especially for graphene, due to
The characteristics such as its electron mobility with superelevation, thermal conductivity, high carrier mobility, and its structure determines that electronics can be two
Conduction, is counted as conductive agent ideal so far in dimension space.In addition, no matter nano graphite flakes or carbon nanotube, mix
Nitrogen carbon nanotube, separately as conductive agent in use, conductive effect is lower, therefore nano graphite flakes with respect to for graphene not
Studied personnel are good or even ignored.Although but graphene superior performance, it is at high cost.In comparison, economically come
Say nano graphite flakes cost be far below than graphene, and according to it is subsequent test show using this paper mentioned carbon nanotube/
Nitrogen doped carbon nanotube-nano graphite flakes composite conducting slurry, can obtain excellent electrical properties, even better than most of document report
The scheme using graphene in road.Return its reason, mainly since the graphene defect of presently commercially available industrialized production is high, leads
Electric effect is poor.
Preferably, with carbon nanotube/nitrogen doped carbon nanotube-nano graphite flakes composite conducting slurry total weight for 100%
Meter, the content of dispersate are 3%~12%, and the content of dispersing agent is 88%~97%.
This gives when preparation carbon nanotube/nitrogen doped carbon nanotube-nano graphite flakes composite conducting slurry, disperse
The optimum ratio range of agent and dispersate.When preparing electrocondution slurry, need to meet simultaneously excellent conductivity and film forming.Point
After the content of scattered matter is higher than 12%, electrocondution slurry viscosity is excessively high；When dispersate content is lower than 3%, the viscosity mistake of electrocondution slurry
Low, no matter electrocondution slurry viscosity is too low or excessively high, all causes to be difficult to grind uniformly, and be unfavorable for subsequent film.
Preferably, in terms of the total weight of dispersate 100%, the content of nano graphite flakes is 50%~87.5%, carbon nanometer
The content of pipe or nitrogen doped carbon nanotube is 12.5%~50%.
From the aspect of electricity and mechanics two, in order to enable electrocondution slurry has excellent electric property, and make simultaneously
The carbon film of preparation has preferable mechanical characteristic, and this gives optimal nano graphite flakes and carbon nanotube or nitrating carbon
The filler weight ratio of nanotube.Through further research, it has been found that with carbon nanotube/nitrogen doped carbon nanotube-nano graphite flakes composite guide
The total weight of plasma-based material is 100% meter, when the content of dispersate is 6%, for the carbon film electricity of dispersate pure nano-carbon tube slurry
For conductance in 70S/cm, its conductivity can be improved by being added after nano graphite flakes, when 16.7% nano-graphite is added in dispersate
Carbon film conductivity is improved to 140S/cm piece (referring to the test result of following embodiment B) afterwards, and when 50% nano graphite flakes of addition
When carbon film conductivity significant increase to 873S/cm (referring to the test result of following embodiment E).Thus, it can be known that with nanometer stone
The conductivity of the increase of ink sheet ratio, carbon film rises.But it is found through analysing and comparing, when carbon nanotube/nitrogen doped carbon nanotube content
When lower than 12.5%, the carbon film of electrocondution slurry coating is excessively crisp, poor mechanical property, therefore carbon nanotube/nitrogen doped carbon nanotube
Content must not drop below 12.5%.In addition, carbon nanotube/nitrogen doped carbon nanotube content cannot be greater than 50%, this is because working as
When content is greater than 50%, the conductivity of carbon film is lower.It is right when finding carbon nanotube replacing with nitrogen doped carbon nanotube after study
The Effect on Mechanical Properties of carbon film after electrocondution slurry and coating is little, but the conductivity of carbon film can be improved；Although nitrating carbon
The conductivity of carbon film, but the thermal conductivity of meeting large effect carbon film can be improved in nanotube, makes a concrete analysis of as described below related real
Apply example and test data.
According to carbon nanotube/nitrogen doped carbon nanotube-nano graphite flakes composite conducting of the method preparation in above-described embodiment
Slurry are as follows: by the total weight of carbon nanotube-nano graphite flake composite conducting slurry be 100% in terms of, the slurry include 3%~12%
Dispersate and 88%~97% dispersing agent；Wherein,
Dispersate includes: carbon nanotube or nitrogen doped carbon nanotube, and, nano graphite flakes；
Dispersing agent includes additive and solvent.
It is a kind of new such as above-mentioned explanation and analysis to preparation method it is found that being free of binder in the proportion of electrocondution slurry
Combination, i.e. carbon nanotube-nano graphite flake.The electrocondution slurry has excellent conductivity and film forming, and performance is stablized,
Convenient for storing for a long time.
Further, in terms of the total weight of dispersate 100%, the content of nano graphite flakes is 50%~87.5%, and carbon is received
The content of mitron is 12.5%~50%.
To nano graphite flakes and carbon nanotube in the dispersate of electrocondution slurry or the amount of filler of nitrogen doped carbon nanotube than carrying out
Further restriction, concrete reason had elaborated in above method embodiment, were no longer repeated here.
The following examples are the optimization or further limit to above-mentioned carbon nanotube-nano graphite flake composite conducting slurry
It is fixed, be also appreciated that it is restriction to above-mentioned electrocondution slurry method prepare because the raw material of electrocondution slurry and match with preparation side
Method is related.
In some alternative embodiments, the solvent of electrocondution slurry is water or N-Methyl pyrrolidone (1-Methyl-2-
Pyrrolidinone, NMP).
Currently, the slurry research of waterborne conductive carbon is less, it should be noted that in the scheme that the present embodiment provides, solvent can be with
Using water, and without carrying out specially treated to carbon nanotube, draped over one's shoulders in such as Chinese patent CN104766645B reported at present
The method of dew needs to carry out carbon nanotube to mix sulphur or p-doped processing.Furthermore it is compared for organic solvent using water as solvent,
It is more environmentally protective.The selection of solvent is in addition to above two, it is also an option that other solvents, such as diethylene glycol, glycol dimethyl ether
Deng.In the selection of solvent, selection is less toxic as far as possible, inexpensive a kind of solvent.
Preferably, after grinding, the average diameter of the dispersate of electrocondution slurry is less than 10 microns.
During the grinding of embodiment of the method, the average grain diameter of dispersate is ground to as far as possible micro- less than 10
Rice, particle is smaller, and grinding effect is better, and particle is finer and smoother uniformly in slurry, and the carbon film quality formed after coating is higher.In addition,
Measurement method can carry out grain diameter measurement using Hegman grind gage.
Specifically, in the above-described embodiments, additive includes surfactant；
Surfactant is polyvinylpyrrolidone (Polyvinyl pyrrolidone, PVP), dodecyl sodium sulfate
(Sodium dodecyl sulfate, SDS), methylcellulose (Carboxyl Methyl Cellulose, CMC) and tween-
One of 80 or a variety of compositions.
Through this embodiment it is recognized that while the type of additive has very much, but for this system, surfactant
It is necessary, and give preferred several surfactants.
Preferably, surfactant PVP, with carbon nanotube/nitrogen doped carbon nanotube-nano graphite flakes composite conducting slurry
Total weight be 100% meter, the content of PVP is 0.5%~2%.
Wherein, the content of PVP surfactant is fewer, and conductivity can be higher.But the content of PVP cannot be very few, otherwise carbon film
Poor adhesive force.When PVP content is lower than 0.5%, carbon film poor adhesive force after coating, but after PVP content is beyond 2%, it is right
The performance of carbon film will cause the conductivity decline of carbon film without being obviously improved instead.
Optionally, additive further includes one of levelling agent, defoaming agent and binder or a variety of.
Specifically, nano graphite flakes can be prepared using the methods of mechanical stripping, electrochemical intercalation, chemical graft.It is preferred that
, the particle size range of nano graphite flakes is 10~200 microns.
Several specific embodiments are named above-described embodiment is further detailed:
In the examples below, electrocondution slurry is specifically prepared with the following method:
Step 1, it is formed according to parts by weight, PVP is added in deionized water, form the first mixed liquor；
Step 2, nano graphite flakes and carbon nanotube/nitrogen doped carbon nanotube are added in the first mixed liquor, mechanical stirring
30 minutes, form the second mixed liquor；
Step 3, the second mixed liquor is put into sand mill, be sanded until product average particle size less than 10 microns,
Obtain electrocondution slurry.
Wherein, nano graphite flakes can be made by electrochemistry/chemical graft.
As demonstration example, the ammonium sulfate of 0.5M is can be used as electrolyte, by graphite rod in+10V electricity in when electrochemical intercalation
After 0.5~3h of pressure electrolysis, nano graphite flakes are obtained by filtration in the solution after electrolysis.For chemical graft, crystalline flake graphite is set
In the concentrated sulfuric acid/ATS (Ammonium thiosulphate) mixed liquor, products therefrom obtains nano graphite flakes by filtering ultrasound.
Fig. 1 gives typical chemical graft and obtains the scanning electron microscope (scanning of nano graphite flakes
Electron microscope, SEM), thermogravimetric curve and Raman Raman map.Such as Fig. 1 a and 1b, it can be seen that and receive from SEM
Rice graphite flake is sufficiently expanded, and subsequent sand milling is conducive to.Weightlessness only has 12% when showing such as Fig. 1 c thermogravimetric to 700 DEG C, shows to receive
Oxygen-containing functional group is less in rice graphite flake, and oxygen-containing functional group is the component part that defect is important in carbon material, therefore thermogravimetric is said
Defect is less in bright nano graphite flakes.If Fig. 1 d, Raman show that the D/G average specific at the peak D and the peak G is 0.4 (6 sampled point), into
One step shows that defect is less in nano graphite flakes.
Carbon nanotube used is the Floutube 7000 of Tian Nai company production, nitrating carbon tube preparation method are as follows: will be a certain amount of
Floutube 7000 be uniformly mixed with melamine, by the mixture as in tube furnace under nitrogen atmosphere 1000 DEG C forge
2h is burnt, nitrating carbon pipe can be obtained, general itrogen content of getter with nitrogen doped is between 1~3%.
Weight (wt%) such as table 1 of different component in specific embodiment A-E:
Table 1
Note a:A-E solvent is NMP, and F-G solvent is water.
B: carbon pipe used is nitrating carbon pipe, solvent NMP.
Conductivity test is carried out to the electrocondution slurry that each embodiment in table 1 is prepared；
Test method is as follows:
1, carbon film conductivity is tested；
Above-mentioned electrocondution slurry is coated with 300 microns of scrapers to polyethylene terephthalate (polyethylene
Glycol terephthalate, PET) dielectric bases such as/polyimides (Polyimide, PI), 120 in air dry oven
DEG C drying 30min, by obtained carbon film after roller process use four probe method testing film conductivity.Four probes test when
Film at least takes six different location data, is then averaged, to reduce experimental error.
2, sample stability is tested；
Slurry is placed 3 months in room temperature environment, tests the conductivity of carbon film after its coating, is obtained after placing 3 months
Electrocondution slurry coats the conductivity of carbon film, calculates it relative to initial conductivity changing value and accounts for initial conductivity percentage, i.e. table 2
In Stability of Slurry value.
In the test process of conductivity, the purpose of roll-in is: 1 be promoted conductivity because roll-in can get rid of it is thin
Gap etc. in film, and reinforce contacting with each other between nano graphite flakes and carbon nanotube；2 be to keep the film of preparation more soft
It is tough.
Table 2 shows the test result of each embodiment in table 1:
Table 2
As shown in Table 2, when the use of NMP being solvent, the stability of the conductivity of the carbon film of electrocondution slurry and electrocondution slurry is all
When being better than water as solvent.Main cause is that the surface of NMP can be closer with carbon material, therefore NMP is as solvent Shi Gengrong
It is easy to get to fine and smooth uniform carbon slurry.It is contemplated that the higher boiling and cost of NMP, certain characteristic occasion water as solvent more
Favorably.In the following, above-mentioned test result is further analyzed so that solvent is NMP as an example:
When solvent select NMP when, with the gross mass of dispersate be 100% when, the filler weight percentage of nano graphite flakes
When being 50%, 75% and 83.3%, the filler weight percentage of corresponding carbon nanotube is respectively 50%, 25% and 16.7%,
The conductivity measured is successively are as follows: 873S/cm, 1780S/cm and 2300S/cm.With the gross mass of dispersate be 100% when, nanometer
When the filler weight percentage of graphite flake is 50%, 25% and 16.7%, the filler weight percentage score of corresponding carbon nanotube
Not Wei 50%, 75% and 83.3%, the conductivity measured is successively are as follows: 873S/cm, 240S/cm and 140S/cm.It is mixed in addition, introducing
Nitrogen carbon pipe can also improve the conductivity of slurry.At identical conditions, introduce nitrating carbon pipe after slurry conductivity respectively from
2300S/cm and 140S/cm are promoted to 2400S/cm and 300S/cm.It can be seen that:
1, with the increase of nano graphite flakes content, the conductivity of electrocondution slurry rises；
2, the filler weight percentage of carbon nanotube had better not be greater than 50%, after being greater than 50%, the electricity of electrocondution slurry
Conductance is lower；
Although slurry conductivity can be improved by 3, introducing nitrating carbon pipe, occupy an leading position (nitrating carbon in nano graphite flakes
Pipe: nano graphite flakes=1:5) when, conductivity only improves about 4%.Only occupy an leading position in nitrating carbon pipe (nitrating carbon pipe:
Nano graphite flakes=5:1) when, conductivity just has a distinct increment about 100%.Due to working as carbon nanotube or nitrogen doped carbon nanotube content
When lower than 12.5%, the carbon film of electrocondution slurry coating is excessively crisp, poor mechanical property, therefore carbon nanotube or nitrogen doped carbon nanotube
Content must not drop below 12.5%.In addition, carbon nanotube or the content of nitrogen doped carbon nanotube cannot be greater than 50%, this is because working as
When content is greater than 50%, the conductivity of carbon film is lower.
Further using embodiment A as sample, the variation of its viscosity under different shear rate is had studied, as a result as shown in Figure 2.
The slurry shows as pseudoplastic fluid, has apparent shear thinning, is suitable for the industrial printing technologies such as silk-screen printing.
In order to further probe into why nano graphite flakes can bring excellent technical effect, through researching and analysing, it is understood that there may be
Following reason:
1,1D, 2D and 3D material have synergistic effect in electricity, mechanical property, and laminated film electric conductivity is better than bill of materials
The superposition of only Use Limitation fruit.
2, the specific surface area of graphene will be much higher than nano graphite flakes, therefore have more multiple solutions when it constructs film,
Increase the probability of Carrier recombination.And nano-graphite sector-meeting reduces interface, reduces the probability of Carrier recombination.
In fact, in the prior art if constructing highly conductive/thermally conductive carbon film by graphene oxide and graphene, it is necessary to pass through
Cross high-temperature process.And its X-ray diffraction (X-ray diffraction, XRD) map is shown as graphite after high-temperature process
XRD spectrum, this demonstrate the processes that graphite is returned by graphene.To sum up, it may be obtained using nano graphite flakes compared with graphene
More excellent electric property.
The electrocondution slurry as described in above-described embodiment has excellent electric conductivity, can be used for Radio Frequency Identification Technology
High-end fields such as (Radio Frequency Identification, RFID).For the conduction described in the embodiment of the present invention
Application prospect of the slurry in RFID is illustrated, and uses carbon nanotube described in embodiment A: nano graphite flakes 1:5 below
Electrocondution slurry be prepared for half-wave dipole antenna such as Fig. 3, design parameter as shown in figure 3, straight wire length L be 70mm, width w
For 3mm, the miniature A of radio (Sub-Miniature-A, SMA) adapter, the spacing of two straight wires are equipped between two straight wires
G is 3mm.Dependence test is carried out to half-wave dipole antenna shown in Fig. 3, as shown in Figure 4.As shown in fig. 4 a, when frequency is
When 910MHz, reflection power gain -15.7dBi, only 2.3% power is reflected at this time, and up to 97.7% power is reflected.
As shown in Figure 4 b, highest-gain is 1.36dBi (910MHz), and the gain in 850MHz~950MHz is all larger than 1dBi.
Currently, for mutually isostructural half-wave dipole minor structure as shown in Figure 3, the maximum of carbon material half-wave dipole reported in the literature
Gain is -0.6dBi.And when ideal half-wave dipole, i.e. conductivity infinity, gain be 2.14dBi.From above-mentioned analysis
It is found that the half-wave dipole of electrocondution slurry preparation provided in this embodiment has very high conductivity, upon receipt of the signals
Most of power can be emitted.Fig. 4 c and 4d be respectively half-wave dipole in 910MHz in the radiation direction in the direction E and the direction H
Figure.As shown in Fig. 4 c and 4d, it is known that the half-wave dipole of electrocondution slurry preparation has the side of typical RFID half-wave dipole
Xiang Tu is round in the direction E, is totally in the figure of eight in the direction H as far as possible.To sum up, as every test result of Fig. 4 shows this
The electrocondution slurry of inventive embodiments has fairly good application prospect in RFID.
Table 3
Note: 1 is original carbon pipe/compound carbon film of nano graphite flakes；2 be nitrating carbon pipe/compound carbon film of nano graphite flakes.
In addition, the carbon film of above-mentioned electrocondution slurry preparation also has high anisotropic heat conductivity.With high thermal conductivity respectively to different
Property thin-film material have in microelectronic component and be widely applied: on the one hand thermal conductivity can pass heat from hot spot in high face
It walks；On the other hand low longitudinal thermal conductivity can prevent device from being heated by external heat source.As known from Table 3, original carbon pipe/nanometer stone
The lateral thermal conductivity K of the compound carbon film of ink sheet is 132.8W/ (m K), and its longitudinal thermal conductivity only has 0.4, anisotropic index (K/K⊥)
Up to 332；Though nitrating can promote carbon film conductivity (seing above conductivity part), it is clear that nitrating reduces thermal conductivity.
Because nitrogen-atoms can be understood as hetero atom, the scattering of phonon and compound is increased, therefore reduce thermal conductivity.Nitrating carbon
The K/K of pipe carbon film⊥=117.9.It should be pointed out that the K/K of non-nitrating carbon film⊥Much higher than pertinent literature data (ACS Nano,
2011,5,2392,K/K⊥=62~76；Carbon,2011,49,773,K/K⊥=139；ACS Appl.Mater.Inter.,
2017,9,2924,K/K⊥=279), therefore it is expected to the heat dissipation applied to electronic device.
To sum up, technical solution provided in an embodiment of the present invention can include the following benefits:
1, conductive carbon paste has high conductivity, is suitable for the high-end fields such as Radio Frequency Identification Technology；
2, electrocondution slurry has excellent thermally conductive anisotropic, is expected to be used for dissipation from electronic devices；
3, conductive carbon paste has apparent shear thinning, is suitable for the industrial printing technologies such as silk-screen printing；
4, conductive carbon paste is free of binder, but has splendid film forming；
5, conductive carbon paste performance is stablized, easily stored；
6, conductive carbon paste material is simple, preparation process is simple, is suitable for industrialization large scale preparation.
It should be understood that the invention is not limited to the process and structure that are described above and are shown in the accompanying drawings,
And various modifications and changes may be made without departing from the scope thereof.The scope of the present invention is only limited by the attached claims
System.
Claims (7)
1. a kind of carbon nanotube/nitrogen doped carbon nanotube-nano graphite flakes composite conducting slurry, which is characterized in that with the conduction
The total weight of slurry is 100% meter, which includes 3%~12% dispersate and 88%~97% dispersing agent；
The dispersate includes: carbon nanotube or nitrogen doped carbon nanotube and nano graphite flakes；
The dispersing agent includes: additive and solvent, wherein the solvent is water or N-Methyl pyrrolidone NMP；
The nano graphite flakes are made by electrochemical intercalation or chemical graft, and the particle size range before being dispersed is 10~
200 microns；It, will using 0.5M ammonium sulfate as electrolyte if the nano graphite flakes are made by the electrochemical intercalation
Graphite rod carries out 0.5~3h of electrolysis under the voltage greater than 10V, and the solution after crossing filtration and electrolysis unit obtains the nano graphite flakes；If
The nano graphite flakes are made by the chemical graft, then crystalline flake graphite are placed in the concentrated sulfuric acid and sodium thiosulfate mixed liquor
In, and ultrasound is filtered to products therefrom and obtains the nano graphite flakes.
2. slurry as described in claim 1, which is characterized in that in terms of the total weight 100% of the dispersate, the nanometer stone
The content of ink sheet is 50%~87.5%, and the content of the carbon nanotube or the nitrogen doped carbon nanotube is 12.5%~50%.
3. slurry as claimed in claim 2, which is characterized in that the additive includes surfactant；The surface-active
Agent is one of polyvinylpyrrolidone PVP, dodecyl sodium sulfate SDS, methylcellulose CMC, Tween-80, siloxanes
Or it is a variety of.
4. slurry as claimed in claim 3, which is characterized in that the average diameter of the dispersate is less than 10 microns.
5. slurry as claimed in claim 3, which is characterized in that the surfactant is PVP, with the total of the electrocondution slurry
Weight is 100% meter, and the content of the PVP is 0.5%~2%.
6. slurry as claimed in claim 5, which is characterized in that the additive further includes levelling agent, defoaming agent and binder
One of or it is a variety of.
7. a kind of carbon nanotube/nitrogen doped carbon nanotube-nano graphite flakes composite conducting slurry preparation method, is used to prepare right and wants
Seek electrocondution slurry described in any one of 1-6, which comprises the following steps:
Dispersate is added in dispersing agent, mechanical stirring is uniform, obtains mixture；
The mixture is sanded, the electrocondution slurry is obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710457271.3A CN107331439B (en) | 2017-06-16 | 2017-06-16 | Carbon nanotube/nitrogen doped carbon nanotube-nano graphite flakes electrocondution slurry and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710457271.3A CN107331439B (en) | 2017-06-16 | 2017-06-16 | Carbon nanotube/nitrogen doped carbon nanotube-nano graphite flakes electrocondution slurry and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107331439A CN107331439A (en) | 2017-11-07 |
| CN107331439B true CN107331439B (en) | 2019-04-16 |
Family
ID=60195500
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710457271.3A Expired - Fee Related CN107331439B (en) | 2017-06-16 | 2017-06-16 | Carbon nanotube/nitrogen doped carbon nanotube-nano graphite flakes electrocondution slurry and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107331439B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107963625B (en) * | 2017-11-09 | 2020-09-01 | 温州大学 | Silicon-crosslinked three-dimensional porous graphene and preparation method thereof |
| CN110247051A (en) * | 2019-05-29 | 2019-09-17 | 常熟理工学院 | A kind of carbon nanotube mill base and preparation method thereof and the application in lithium battery |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101123351B1 (en) * | 2008-10-09 | 2012-03-23 | 주식회사 엑사이엔씨 | High conductive paste composition and method of high conductive paste composition |
| CN102093774B (en) * | 2010-12-31 | 2013-11-06 | 清华大学 | Conductive ink and preparation method thereof |
| CN102180458B (en) * | 2011-03-25 | 2013-03-06 | 深圳市贝特瑞纳米科技有限公司 | Nano-carbon material dispersion liquid and preparation method and equipment thereof |
| CN104766645B (en) * | 2015-03-24 | 2017-02-01 | 潍坊昊晟碳材料有限公司 | Carbon nanotube-graphene composite electric conduction slurry and preparation method and application thereof |
| CN105428657A (en) * | 2015-11-17 | 2016-03-23 | 天津市捷威动力工业有限公司 | High-energy-density quick charge type polymer lithium ion battery and manufacturing method therefor |
| CN105895193A (en) * | 2016-06-05 | 2016-08-24 | 李科 | Silver conductive coating material of lithium ion battery, preparation method of silver conductive coating material and lithium ion battery |
-
2017
- 2017-06-16 CN CN201710457271.3A patent/CN107331439B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN107331439A (en) | 2017-11-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Bhattacharya et al. | Graphene decorated with hexagonal shaped M-type ferrite and polyaniline wrapper: a potential candidate for electromagnetic wave absorbing and energy storage device applications | |
| US8248305B2 (en) | Antennas based on a conductive polymer composite and methods for production thereof | |
| Li et al. | An ultrahigh energy density flexible asymmetric microsupercapacitor based on Ti3C2Tx and PPy/MnO2 with wide voltage window | |
| CN109456645B (en) | Surfactant-free graphene composite conductive ink | |
| CN107331439B (en) | Carbon nanotube/nitrogen doped carbon nanotube-nano graphite flakes electrocondution slurry and preparation method | |
| CN109817382B (en) | Preparation method of high-stability graphene conductive paste | |
| CN103273056B (en) | A kind of flake copper and preparation method thereof | |
| US20230142469A1 (en) | Carbon-based conducting inks | |
| KR102238443B1 (en) | Method for coating an electrically conductive substrate, and a related electrodepositable composition comprising graphene carbon particles | |
| US20220363931A1 (en) | Nano-inks of carbon nanomaterials for printing and coating | |
| CN106971855A (en) | A kind of nickel ferrite based magnetic loaded nanoparticle electrode material and preparation method and purposes | |
| CN107746628A (en) | A kind of water-based carbon nano conductive printing ink, preparation method and its heating product | |
| CN107221458B (en) | Nickel complex is the carbon dope nickel oxide combination electrode material and preparation method thereof of precursor | |
| CN102964571B (en) | Preparation method of barium ferrite/carbon nanotube/poly(3-methylthiophene) composite wave-absorbing material | |
| Senapati et al. | Flowerlike Fe2O3–polyaniline nanocomposite as electrode for supercapacitor | |
| CN109437880B (en) | Method for preparing Ce-Sm-Fe composite solid electrolyte ceramic material by ultrasonic-microwave sol-gel method | |
| Pawar et al. | Cobalt ferrite nanoparticles for supercapacitor application | |
| Miao et al. | Passive RFID microstrip antenna sensor for temperature monitoring | |
| CN109509570A (en) | With the preparation method of surface modification graphene modified carbon electrode | |
| Li et al. | A facile strategy to in situ synthesize metal oxide/conductive polymer hybrid electrodes for supercapacitors | |
| CN113068390B (en) | Two-dimensional magnetic Fe3GeTe2Composite material of nanosheet and graphene nanosheet as well as preparation method and application thereof | |
| CN110322986B (en) | Preparation method of high-fluidity graphene conductive paste | |
| Pan et al. | Simplified synthesis of 3D flexible reduced graphene oxide-wrapped NiCo2O4 nanowires for high-performance supercapacitor | |
| Wang et al. | Facile fabrication of nanostructured NiCo 2 O 4 supported on Ni foam for high performance electrochemical energy storage | |
| Yang et al. | Preparation and characterization of coaxial mullite/polypyrrole fibrous nanocomposites via self‐assembling and in situ surface‐initiated polymerization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190416 Termination date: 20200616 |