CN107686688A - Graphene/polypyrrole/carbon black conductive ink and preparation method and flexible-paper-base writing conducting wire - Google Patents
Graphene/polypyrrole/carbon black conductive ink and preparation method and flexible-paper-base writing conducting wire Download PDFInfo
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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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
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- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
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- C09D11/00—Inks
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- C09D11/14—Printing inks based on carbohydrates
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
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- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
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Abstract
The invention discloses a kind of preparation method of graphene/polypyrrole/carbon black conductive ink.The compound formed with polypyrrole and graphene in-situ polymerization is mixed to form complex conductive fillerses with carbon black, using ethanol, ethylene glycol, glycerine, deionized water mixed solution as solvent, using sodium carboxymethylcellulose as adhesive and stabilizer, this product is obtained by simple miscible legal system.The present invention provides a kind of graphene/polypyrrole/carbon black hybrid conductive filler, make full use of the cooperative effect between graphene, polypyrrole, carbon black three, the ink of preparation has satisfactory electrical conductivity and writing smoothness, solid content is low, viscosity is small, good fluidity, and its flexible-paper-base writes solvent resistance, uniformity, adhesive force, bending resistance and the excellent conductivity of conducting wire.Present invention process is simple, is expected to the structure applied to conducting wire.
Description
Technical field
The present invention relates to graphene/polypyrrole/carbon black conductive ink and preparation method thereof, belong to materials science field.
Background technology
Cost degradation, multifunction, high performance have turned into the development trend of current printed electronic, and electrically conductive ink is as print
The core material used in electronic technology processed, its many advantages receive the extensive concern of people.Pure carbon black conductive ink cost
Low, light weight, stable performance, but its electric conductivity is bad；Graphene has excellent electric conductivity, is to prepare high conductivity oil
The ideal conducting phase of ink, but its price is high, easily reunites.Theoretically see, graphene is mutually prepared with carbon black as composite conducting
Graphene-based electrically conductive ink, the reunion of graphene can be not only prevented, and the high conductivity conductive oil of stable performance can be prepared
Ink.At present, the electronation in oxidation-reduction method be it is a kind of can obtain High-performance graphene, and can be adapted to industrialized production
Graphene production technology.In chemical reduction method, it is ripe to prepare the technology of redox graphene using hydrazine reducing agent,
But the toxicity problem of reducing agent receives the extensive query of environmentalist.Using ascorbic acid（VC）Prepared Deng green reducing agent
Redox graphene is the study hotspot that in recent years prepared by graphene, can not only prevent hydrazine toxicity reducing agent using this method
Injury to environment, and resulting redox graphene still has a small amount of hydrophilic oxy radical, so as to be divided
Dissipate the good redox graphene aqueous solution, the conductive phase particularly suitable as water-based ink.However, also just because of this portion
Divide the presence of oxy radical, the electric conductivity of the redox graphene prepared using green reducing agent can not reach graphene reason
Think electric conductivity.Polypyrrole is a kind of excellent in stability, is easy to in-situ polymerization film forming, has high conductivity, biocompatibility etc.
The conducting polymer of advantage.The compound two-component of polypyrrole/carbon-based material even report of multi-component material have been related at present,
Such as can be as carbon-based polypyrrole/carbon mano-tube composite of electrode material for super capacitor, for high efficiency dye sensitization
Polypyrrole/graphite sheet composite material of solar cell etc..Research shows that the C atoms in polypyrrole/c-based nanomaterial are gathered around
There is localized network conducting structure, electronics can increase electrical conductance by tunnel-effect.For carbon-based materials such as graphite flakes, no spy
Graphene/the Pt/Polypyrrole composite material for the looks that shape is in the equal table of the various fields such as machinery, electricity, sensor, super capacitor material
Reveal excellent properties.But so far, had no using research of the graphene/Pt/Polypyrrole composite material as electrically conductive ink conductive phase
Report.The present invention gives full play to the collaboration conductive effect of polypyrrole, graphene and carbon black, with polypyrrole and graphene in-situ polymerization
The composite formed is compounded to form conductive phase with carbon black, takes simple miscible method, the excellent electrically conductive ink of processability.
The content of the invention
It is an object of the invention to provide a kind of preparation method of graphene/polypyrrole/carbon black conductive ink, its oil prepared
Black electric conductivity and have good stability, be expected to the structure applied to conducting wire.
To reach above-mentioned purpose, the technical solution adopted by the present invention is：With graphene/Pt/Polypyrrole composite material and carbon black
Mixture as conductive filler, using ethanol, ethylene glycol, glycerine, deionized water mixed solution as solvent, with carboxymethyl cellulose
Plain sodium prepares electrically conductive ink as adhesive and stabilizer.
The preparation method of graphene/polypyrrole/carbon black conductive ink of the present invention, comprises the following steps：
A, it is fully ground to obtain hybrid conductive filler after mixing carbon black and graphene/Pt/Polypyrrole composite material；
B, ethanol, ethylene glycol, glycerine and deionized water mixed solvent are prepared；
C, mixed solvent made from complex conductive fillerses made from A, B is mixed with sodium carboxymethylcellulose, and sonicated,
Centrifuge, gained supernatant is graphene/polypyrrole/carbon black conductive ink.
Further, the mass ratio that graphene/Pt/Polypyrrole composite material described in step A accounts for hybrid conductive filler is 1 %-
40 %。
Further, it is respectively 10-15 that ethanol, ethylene glycol, glycerine, the amount of deionized water are measured described in step B
ML, 28-32 mL, 28-32 mL, 50-55 mL,
Further, sodium carboxymethylcellulose described in step C is the 50-80 % of complex conductive fillerses quality.
The preparation method of above-mentioned graphene/polypyrrole/carbon black conductive ink, the graphene are prepared as follows：
Using natural graphite powder as raw material, graphene oxide is prepared using improved Hummers methods, utilizes reducing agent oxygen reduction fossil
Black alkene, obtains redox graphene.
Further, when preparing graphene, reducing agent is vitamin C, glucose and fructose.
Further, during the redox graphene, the recovery time is no more than 5 h, and reduction temperature is 80 DEG C -100
DEG C, the mass ratio of reducing agent and graphene oxide is 1:5-15.
The preparation method of above-mentioned graphene/polypyrrole/carbon black conductive ink, the graphene/Pt/Polypyrrole composite material
Prepare as follows：
Using graphene and pyrrole monomer as raw material, using situ aggregation method, graphene/Pt/Polypyrrole composite material is obtained.
Further, when preparing graphene/Pt/Polypyrrole composite material using situ aggregation method, graphene, pyrroles, six hydrations
The mass ratio of ferric trichloride is 1:9-11:68-75, preferably 1:10:70.
Further, described when preparing graphene/Pt/Polypyrrole composite material, the reaction time is no more than 5 h, and reduction temperature is
80 ℃-100 ℃。
Further, condition is ultrasonically treated in the step C is：Power is 800-1000 W, and ultrasonic time is no more than 1
h；Centrifugation condition is：Rotating speed is 7000-9000 r/min, the time is no more than 1 h.
Invention also provides a kind of electric conductivity and having good stability, can be used in building the graphene of conducting wire/
Polypyrrole/carbon black conductive ink, it is prepared according to above-mentioned preparation method.
Present invention also offers a kind of flexible-paper-base to write conducting wire, and flexible-paper-base writing conducting wire is with above-mentioned
Electrically conductive ink is write directly on flexible-paper-base and formed, construction method is simple as ink.
Flexible-paper-base of the present invention writes conducting wire, and it is to prepare by the following method：
Graphene/polypyrrole/carbon black conductive ink is fitted into lettering pen, is directly write on paper base material, obtains flexible paper
Base conducting wire.
Further, constant, repeated multiple times writing, and same conductor wire road book are kept to the width of same conducting wire
Number is write no more than 10 times.
Further, the paper substrate after electrically conductive ink is write is placed in baking oven, heat is carried out to flexible-paper-base conducting wire
Sintering processes.
Further, during sintering processes, sintering temperature is 80 DEG C -100 DEG C, and sintering time is no more than 1 h.
Beneficial effects of the present invention：The compound that the present invention is formed with polypyrrole and graphene in-situ polymerization mixes with carbon black
Formed complex conductive fillerses, using ethanol, ethylene glycol, glycerine, deionized water mixed solution as solvent, with carboxymethyl cellulose
Sodium obtains graphene/polypyrrole/carbon black conductive ink as adhesive and stabilizer by simple miscible legal system.The electrically conductive ink
Middle graphene/polypyrrole/carbon black hybrid conductive the filler used, makes full use of the association between graphene, polypyrrole, carbon black three
Same effect, the ink of preparation have satisfactory electrical conductivity and writing smoothness, and solid content is low, viscosity is small, good fluidity.With lettering pen
It is the solvent resistance of the flexible-paper-base writing conducting wire that diameter is write to obtain on paper base material, uniformity, adhesive force, resistant to bending
Property and excellent conductivity, the structure available for conducting wire.
Brief description of the drawings
Fig. 1 is FTIR Fourier infrared spectrum figures.
Fig. 2 is influence figure of the different ratio to electrically conductive ink electrical conductivity.
Fig. 3 is picture before lettering pen assembling.
Fig. 4 is picture after lettering pen assembling.
Fig. 5 is conductive ink trace line section electron microscope made from embodiment 1.
Fig. 6 is conductive ink trace line section electron microscope made from embodiment 2.
Fig. 7 is conductive ink trace line section electron microscope made from embodiment 3.
Fig. 8 is conductive ink trace line section electron microscope made from embodiment 4.
Fig. 9 is conductive ink trace line section electron microscope made from embodiment 5.
Figure 10 is conductive ink trace line section electron microscope made from embodiment 6.
Figure 11 is conductive ink trace line section electron microscope made from embodiment 7.
Figure 12 is the solvent resistance test sample figure before the covering of filter paper bar.
Figure 13 is the solvent resistance test sample figure after test terminates.
Figure 14 is the contaminated situation map that solvent resistance test terminates rear upper strata filter paper bar.
Figure 15 is graphene/polypyrrole/carbon black conductive ink uniformity test sample schematic diagram.
Figure 16 is the resistance value of the electrically conductive ink direct write conducting wire of different length.
Figure 17 is influence of the bending number to graphene/polypyrrole/carbon black conductive ink traces resistance value.
Picture before the bending of Figure 18 flexible-paper-bases conducting wire.
Figure 19 flexible-paper-base conducting wires picture after bending.
Figure 20 is the circuit arrangement figure of flexible-paper-base conducting wire.
Embodiment
Embodiment 1：
1. prepare redox graphene：
Graphene oxide is prepared first：By the concentrated sulfuric acid（30 mL）It is placed in beaker, sequentially adds graphite powder（5 g）, potassium peroxydisulfate
（4 g）, phosphorus pentoxide（4 g）, it is subsequently placed in digital display magnetic force oil bath pan（80 ℃）In, mixture is through magnetite strong stirring 5
h.Then beaker is placed in digital display thermostat water bath, pot is adjusted to 20 DEG C, and deionized water is added along wall（600 mL）, stirring change
It is cold.Filter, be washed to neutrality and compared with test paper, be placed in electric drying oven with forced convection（50 ℃）Middle drying.In water bath condition（20
℃）Under, by the concentrated sulfuric acid（240 mL）It is slowly added to be placed with above-mentioned drying composite（2 g）Beaker in, and be slowly added in batches
Potassium permanganate（15 g）After the h of strong stirring 2,35 DEG C are warming up to, reacts 4 h.Water-bath is adjusted to 10 DEG C, is slowly added to 500
ML deionized waters；50 DEG C are warming up to again, react 2 h；Solution and magnetite are shifted in large beaker after end, are slow added into
Ionized water（1000 mL）, it is placed in agitator（The r/min of rotating speed 20,50 DEG C of temperature）, stir 30 min；Add hydrogen peroxide
（30 %, 5 mL）, now solution be changed into glassy yellow from dark brown, be cooled to 20 DEG C, stand a night after stirring 10 min, outwell
Supernatant liquor, it is reloaded into bag filter and dialyses 2 weeks, the impurity in solution is removed with this, until solution PH test is in neutrality.Finally will
It is 0.8 mg/mL that solution, which is diluted to concentration, and 40 min are ultrasonically treated under condition of ice bath（The % of power 80）Afterwards, graphite oxide is obtained
Alkene solution.
Redox graphene is prepared again：Graphene oxide made from selection（250 mL）Solution, add vitamin C（2
g）, ammoniacal liquor is then slowly added dropwise into mixed solution, pH value is adjusted to 8.0 ~ 9.0.In water bath condition（95 ℃）Under, reaction 2
H, it is cooled to room temperature and makes Ammonia valatilization, obtain redox graphene solution.
2. prepare graphene/Pt/Polypyrrole composite material：
Restore All graphene oxide solution and pyrrole monomer made from selection（2 mL）, 1 h is mixed under condition of ice bath.Will
FeCl3•6H2O（14.5 g）It is dissolved in hydrochloric acid（0.1 mol/L, 145 mL）, it is slowly added dropwise into mixed solution.Continue ice bath to stir
24 h are mixed, by said mixture through filtering with microporous membrane, and neutrality are washed till using deionized water.Remaining solid is placed in 40 DEG C
24 h are dried in baking oven, and are ground with agate mortar to obtain graphene/Pt/Polypyrrole composite material powder.
3. prepare graphene/polypyrrole/carbon black conductive ink：
Take 12 mg graphenes/Pt/Polypyrrole composite material（2 wt%）, it is uniform with 15 min of agate mortar grinding, it is then mixed into 588
Mg carbon blacks, continue 15 min of grinding and obtain complex conductive fillerses.Measure respectively 12 mL, 30 mL, 30 mL, 51 mL ethanol,
Ethylene glycol, glycerine, deionized water, mix 10 min and obtain mixed solvent.Composite guide is sequentially added in the mixed solvent
Electric filler and sodium carboxymethylcellulose（CMC, 480 mg）, it is subsequently placed in ultrasonic wave plant cell pulverizer and is ultrasonically treated
So as to scattered gained slurry, supersound process condition is：Ice bath, 960 W, 45 min.By the obtained solution of ultrasound be placed at a high speed from
It is centrifuged in scheming, centrifugation condition is：The r/min of rotating speed 8000, the min of time 15.Obtained by centrifuging
Supernatant liquor is graphene/polypyrrole/carbon black conductive ink.
FTIR Fourier infrared spectrum figures（Fig. 1）In, from graphene（c）Infrared spectrogram on observe, 1682cm-1Place
Characteristic absorption peak correspond to C=O stretching vibration, 1646cm-1Corresponding to C-OH flexural vibrations, 1516cm-1There is graphite
C-C characteristic absorption peaks in alkene skeleton, and complete anaerobic graphene is not present in theory, therefore graphene prepared by this experiment
Still there is part oxygen-containing functional group.And in graphene/Pt/Polypyrrole composite material（b）In infrared figure, polypyrrole can be found respectively
Characteristic peak：1433cm-1、1275cm-1、1124cm-1、829cm-1, may indicate that graphene is compound successful with polypyrrole.In charcoal
It is black（d）In, there is 2092cm-1、1990cm-1、1488cm-1Deng characteristic absorption peak and in sodium carboxymethylcellulose（e）In, go out
Existing COO- characteristic peak 587cm-1（Asymmetric stretching vibration absorbs）And 1413cm-1（Symmetrical stretching vibration absorbs）, it is able to
In electrically conductive ink（a）Corresponding peak value is found in infrared spectrogram.To sum up show, formed with polypyrrole and graphene in-situ polymerization
Composite mixes with carbon black, formed conductive filler, using ethanol, ethylene glycol, glycerine, deionized water mixed solution to be molten
Agent, using sodium carboxymethylcellulose as adhesive and stabilizer, it can successfully prepare graphene/polypyrrole/carbon black conductive ink.
Fig. 2 is the image that the electrical conductivity of electrically conductive ink changes with the change of component proportion.The present embodiment is shown in Fig. 2
The electrical conductivity of graphene/polypyrrole/carbon black conductive ink made from 1 is 123 μ S/cm, and electric conductivity is good.
4. prepare lettering pen：
Take a diameter of 0.5 mm of nib refill of gel-ink pen（MG-6149, Shanghai M ＆ G Stationery Inc.）, use deionization
Water washes away the ink inside pen core, and pen core and nib is cleaned multiple times with ethanol, referring to Fig. 3, then uses syringe（1 mL,
Changzhou return of spring medical equipment Co., Ltd）0.5 mL graphenes/polypyrrole/carbon black conductive ink is injected into clean pen core
Water, and pen core and nib are re-assemblied, as shown in figure 4, obtaining graphene/polypyrrole/carbon black lettering pen.
5. direct write flexible-paper-base conducting wire：
Graphene/polypyrrole/carbon black conductive ink is fitted into lettering pen, in bloom printing paper（C13S041860, China's love are general
Raw Co., Ltd）It is upper directly to write, obtain flexible-paper-base conducting wire.
6. the post processing of direct write flexible-paper-base conducting wire：
Direct write flexible-paper-base conducting wire is placed in the min of sintering processes 20 in 100 DEG C of baking ovens.
The cross-section morphology of obtained direct write paper substrate conducting wire is shown in Fig. 5.As can be seen that in figure up and down two warning triangles it
Between region be paper substrate conducting wire（10 mm×1 mm×12.11 um）Section, thickness is 12.11 μm, electrically conductive ink
It can be adhering closely on the resin bed of base material, opposed flattened coating is formed on base material.
Figure 12-14 is that paper substrate conducting wire carries out the front and rear layer of ink of solvent resistance test and filter paper variation diagram.Specific experiment
Step is as follows：First, four filter paper bars are totally immersed in test reagent H2O、1%NaOH 5%HCL、5%HAC 5%H2SO4
In, then dry, until there is no drop freely to drip on filter paper.The filter paper bar of two saturations is placed on the glass sheet, test
Sample is placed on filter paper bar, then is covered with the filter paper bar of two other saturation, and test sample is between two filter paper bars.It is another
Block sheet glass lid pressure, and place 1 kg counterweight pressurization of weighing, after pressing time 20min, remove the sub- sheet glass of lid and with survey
The upper strata filter paper bar that conducting wire contacts on test agent.Figure 12 is the test sample figure before the covering of filter paper bar, and Figure 13 is test knot
Test sample figure after beam, Figure 14 are the contaminated situation maps that test terminates rear upper strata filter paper bar.Test before and after comparative test
Sample, sour test oil layer of ink is apparent not to be changed, and filter paper receiving surface does not have stain yet.And sodium hydroxide takes off ink layer surface
Color, layer of ink gloss disappear.To sum up show, graphene/polypyrrole/carbon black conductive ink made from experiment have good acid resistance and
Water resistance, but be not suitable for contacting alkali lye.
Figure 15 and Figure 16 is that graphene/polypyrrole/carbon black conductive ink direct write conducting wire uniformity of different length is surveyed
Attempt.All in all, when the length of direct write conducting wire is 10 mm, 20 mm, 30 mm, 40 mm and 50 mm, electrically conductive ink
Line resistance value is linear with length, illustrates that electrically conductive ink has good uniform continuity.
Figure 17 is the bending test chart of direct write conducting wire.Result of the test shows to bend even across multiple, after sintering
Layer of ink without departing from paper base material, significant change does not occur for resistance.This shows that paper substrate conducting wire has good machine
Tool pliability, has a wide range of applications in electronic applications.
Figure 18,19 be flexible-paper-base conducting wire bending before and after test figure, by external force by the two-dimentional paper substrate after sintering
Conducting wire curling is 3 D stereo conducting wire, and result of the test shows to crimp even across multiple, and the layer of ink after sintering is not
Depart from paper base material, significant change does not occur for resistance.This shows that flexible-paper-base conducting wire has well mechanical flexible
Property, had a wide range of applications in electronic applications.
Figure 20 is the circuit arrangement figure of direct write flexible-paper-base conducting wire, it is seen that direct write flexible-paper-base conducting wire has good
Good application prospect.This experiment designed, designed paper substrate circuit：By LED3（LMY-5MMB2R02,20mA, 4.5V, Shenzhen are green
Ma Yuan Photoelectric Co., Ltd.s）Access in the circuit 5 of voltage 5V power supply 4, and connect the conducting wire being written on bloom printing paper 2
1（It is long × wide, the mm of 10 mm × 1）As conducting element.Closing of circuit, LED send light, and this shows inside ink circuit shape
Into conductive path.
Embodiment 2：
1. prepare redox graphene：With embodiment 1.
2. prepare graphene/Pt/Polypyrrole composite material：
Restore All graphene oxide solution and pyrrole monomer made from selection（2 mL）, 1 h is mixed under condition of ice bath.Will
FeCl3•6H2O（14.5 g）It is dissolved in hydrochloric acid（0.1 mol/L, 145 mL）, it is slowly added dropwise into mixed solution.Continue ice bath to stir
24 h are mixed, by said mixture through filtering with microporous membrane, and neutrality are washed till using deionized water.Remaining solid is placed in 40 DEG C
24 h are dried in baking oven, and are ground with agate mortar to obtain graphene/Pt/Polypyrrole composite material powder.
3. prepare graphene/polypyrrole/carbon black conductive ink：
Take 54 mg graphenes/Pt/Polypyrrole composite material（9 wt%）, it is uniform with 15 min of agate mortar grinding, it is then mixed into 546
Mg carbon blacks, continue 15 min of grinding and obtain complex conductive fillerses.Measure respectively 12 mL, 30 mL, 30 mL, 51 mL ethanol,
Ethylene glycol, glycerine, deionized water, mix 10 min and obtain mixed solvent.Composite guide is sequentially added in the mixed solvent
Electric filler and sodium carboxymethylcellulose（CMC, 480 mg）, it is subsequently placed in ultrasonic wave plant cell pulverizer and is ultrasonically treated
So as to scattered gained slurry, supersound process condition is：Ice bath, 960 W, 45 min.By the obtained solution of ultrasound be placed at a high speed from
It is centrifuged in scheming, centrifugation condition is：The r/min of rotating speed 8000, the min of time 15.Obtained by centrifuging
Supernatant liquor is graphene/polypyrrole/carbon black conductive ink.
Fig. 2 is the image that the electrical conductivity of electrically conductive ink changes with the change of component proportion.The present embodiment is shown in Fig. 2
The electrical conductivity of graphene/polypyrrole/carbon black conductive ink made from 2 is 146.3 μ S/cm, and electric conductivity is good.
4. prepare lettering pen：With embodiment 1.
5. direct write flexible-paper-base conducting wire：With embodiment 1.
6. the post processing of direct write flexible-paper-base conducting wire：
Direct write flexible-paper-base conducting wire is placed in the min of sintering processes 20 in 100 DEG C of baking ovens.
The cross-section morphology of obtained direct write paper substrate conducting wire is shown in Fig. 6.As can be seen that in figure up and down two warning triangles it
Between region be paper substrate conducting wire（10 mm×1 mm×8.08 um）Section, thickness is 8.08 μm, electrically conductive ink energy
Enough it is adhering closely on the resin bed of base material, opposed flattened coating is formed on base material.
Figure 12-14 is that paper substrate conducting wire carries out the front and rear layer of ink of solvent resistance test and filter paper variation diagram, test procedure
With embodiment 1.Test sample before and after comparative test, sour test oil layer of ink is apparent not to be changed, and filter paper receiving surface does not have yet
Stain.And sodium hydroxide makes ink layer surface fade, layer of ink gloss disappears.To sum up show, graphene made from experiment/poly- pyrrole
Cough up/carbon black conductive ink has good acid resistance and water resistance, but be not suitable for contacting alkali lye.
Figure 15 and Figure 16 is that graphene/polypyrrole/carbon black conductive ink direct write conducting wire uniformity of different length is surveyed
Attempt.All in all, when the length of direct write conducting wire is 10 mm, 20 mm, 30 mm, 40 mm and 50 mm, electrically conductive ink
Line resistance value is linear with length, illustrates that electrically conductive ink has good uniform continuity.
Figure 17 is the bending test chart of direct write conducting wire.Result of the test shows to bend even across multiple, after sintering
Layer of ink without departing from paper base material, significant change does not occur for resistance.This shows that paper substrate conducting wire has good machine
Tool pliability, has a wide range of applications in electronic applications.
Figure 18,19 be flexible-paper-base conducting wire bending before and after test figure, by external force by the two-dimentional paper substrate after sintering
Conducting wire curling is 3 D stereo conducting wire, and result of the test shows to crimp even across multiple, and the layer of ink after sintering is not
Depart from paper base material, significant change does not occur for resistance.This shows that flexible-paper-base conducting wire has well mechanical flexible
Property, had a wide range of applications in electronic applications.
Figure 20 is the circuit arrangement figure of direct write flexible-paper-base conducting wire, it is seen that direct write flexible-paper-base conducting wire has good
Good application prospect.This experiment designed, designed paper substrate circuit：By LED3（LMY-5MMB2R02,20mA, 4.5V, Shenzhen are green
Ma Yuan Photoelectric Co., Ltd.s）Access in the circuit 5 of voltage 5V power supply 4, and connect the conducting wire being written on bloom printing paper 2
1（It is long × wide, the mm of 10 mm × 1）As conducting element.Closing of circuit, LED send light, brighter relative to embodiment 1.
Embodiment 3：
1. prepare redox graphene：With embodiment 1.
2. prepare graphene/Pt/Polypyrrole composite material：
Restore All graphene oxide solution and pyrrole monomer made from selection（2 mL）, 1 h is mixed under condition of ice bath.Will
FeCl3•6H2O（14.5 g）It is dissolved in hydrochloric acid（0.1 mol/L, 145 mL）, it is slowly added dropwise into mixed solution.Continue ice bath to stir
24 h are mixed, by said mixture through filtering with microporous membrane, and neutrality are washed till using deionized water.Remaining solid is placed in 40 DEG C
24 h are dried in baking oven, and are ground with agate mortar to obtain graphene/Pt/Polypyrrole composite material powder.
3. prepare graphene/polypyrrole/carbon black conductive ink：
Take 96 mg graphenes/Pt/Polypyrrole composite material（16 wt%）, it is uniform with 15 min of agate mortar grinding, it is then mixed into 504
Mg carbon blacks, continue 15 min of grinding and obtain complex conductive fillerses.Measure respectively 12 mL, 30 mL, 30 mL, 51 mL ethanol,
Ethylene glycol, glycerine, deionized water, mix 10 min and obtain mixed solvent.Composite guide is sequentially added in the mixed solvent
Electric filler and sodium carboxymethylcellulose（CMC, 480 mg）, it is subsequently placed in ultrasonic wave plant cell pulverizer and is ultrasonically treated
So as to scattered gained slurry, supersound process condition is：Ice bath, 960 W, 45 min.By the obtained solution of ultrasound be placed at a high speed from
It is centrifuged in scheming, centrifugation condition is：The r/min of rotating speed 8000, the min of time 15.Obtained by centrifuging
Supernatant liquor is graphene/polypyrrole/carbon black conductive ink.
Fig. 2 is the image that the electrical conductivity of electrically conductive ink changes with the change of component proportion.The present embodiment is shown in Fig. 2
The electrical conductivity of graphene/polypyrrole/carbon black conductive ink made from 3 is 170.3 μ S/cm, and electric conductivity is good.
4. prepare lettering pen：With embodiment 1.
5. direct write flexible-paper-base conducting wire：With embodiment 1.
6. the post processing of direct write flexible-paper-base conducting wire：
Direct write flexible-paper-base conducting wire is placed in the min of sintering processes 20 in 100 DEG C of baking ovens.
The cross-section morphology of obtained direct write paper substrate conducting wire is shown in Fig. 7.As can be seen that in figure up and down two warning triangles it
Between region be paper substrate conducting wire（10 mm×1 mm×44.29 um）Section, thickness is 44.29 μm, electrically conductive ink
It can be adhering closely on the resin bed of base material, opposed flattened coating is formed on base material.
Figure 12-14 is that paper substrate conducting wire carries out the front and rear layer of ink of solvent resistance test and filter paper variation diagram, test procedure
With embodiment 1.Test sample before and after comparative test, sour test oil layer of ink is apparent not to be changed, and filter paper receiving surface does not have yet
Stain.And sodium hydroxide makes ink layer surface fade, layer of ink gloss disappears.To sum up show, graphene made from experiment/poly- pyrrole
Cough up/carbon black conductive ink has good acid resistance and water resistance, but be not suitable for contacting alkali lye.
Figure 15 and Figure 16 is that graphene/polypyrrole/carbon black conductive ink direct write conducting wire uniformity of different length is surveyed
Attempt.All in all, when the length of direct write conducting wire is 10 mm, 20 mm, 30 mm, 40 mm and 50 mm, electrically conductive ink
Line resistance value is linear with length, illustrates that electrically conductive ink has good uniform continuity.
Figure 17 is the bending test chart of direct write conducting wire.Result of the test shows to bend even across multiple, after sintering
Layer of ink without departing from paper base material, significant change does not occur for resistance.This shows that paper substrate conducting wire has good machine
Tool pliability, has a wide range of applications in electronic applications.
Figure 18,19 be flexible-paper-base conducting wire bending before and after test figure, by external force by the two-dimentional paper substrate after sintering
Conducting wire curling is 3 D stereo conducting wire, and result of the test shows to crimp even across multiple, and the layer of ink after sintering is not
Depart from paper base material, significant change does not occur for resistance.This shows that flexible-paper-base conducting wire has well mechanical flexible
Property, had a wide range of applications in electronic applications.
Figure 20 is the circuit arrangement figure of direct write flexible-paper-base conducting wire, it is seen that direct write flexible-paper-base conducting wire has good
Good application prospect.This experiment designed, designed paper substrate circuit：By LED3（LMY-5MMB2R02,20mA, 4.5V, Shenzhen are green
Ma Yuan Photoelectric Co., Ltd.s）Access in the circuit 5 of voltage 5V power supply 4, and connect the conducting wire being written on bloom printing paper 2
1（It is long × wide, the mm of 10 mm × 1）As conducting element.Closing of circuit, LED send light, and brightness is similar to Example 1.
Embodiment 4：
1. prepare redox graphene：With embodiment 1.
2. prepare graphene/Pt/Polypyrrole composite material：
Restore All graphene oxide solution and pyrrole monomer made from selection（2 mL）, 1 h is mixed under condition of ice bath.Will
FeCl3•6H2O（14.5 g）It is dissolved in hydrochloric acid（0.1 mol/L, 145 mL）, it is slowly added dropwise into mixed solution.Continue ice bath to stir
24 h are mixed, by said mixture through filtering with microporous membrane, and neutrality are washed till using deionized water.Remaining solid is placed in 40 DEG C
24 h are dried in baking oven, and are ground with agate mortar to obtain graphene/Pt/Polypyrrole composite material powder.
3. prepare graphene/polypyrrole/carbon black conductive ink：
Take 138 mg graphenes/Pt/Polypyrrole composite material（23 wt%）, it is uniform with 15 min of agate mortar grinding, it is then mixed into
462 mg carbon blacks, continue 15 min of grinding and obtain complex conductive fillerses.12 mL, 30 mL, 30 mL, 51 mL second are measured respectively
Alcohol, ethylene glycol, glycerine, deionized water, mix 10 min and obtain mixed solvent.Sequentially added in the mixed solvent compound
Conductive filler and sodium carboxymethylcellulose（CMC, 480 mg）, it is subsequently placed in ultrasonic wave plant cell pulverizer and carries out ultrasonic place
To disperse gained slurry, supersound process condition is reason：Ice bath, 960 W, 45 min.The solution that ultrasound obtains is placed at a high speed
It is centrifuged in centrifuge, centrifugation condition is：The r/min of rotating speed 8000, the min of time 15.Obtained by centrifugation
Supernatant liquor be graphene/polypyrrole/carbon black conductive ink.
Fig. 2 is the image that the electrical conductivity of electrically conductive ink changes with the change of component proportion.The present embodiment is shown in Fig. 2
The electrical conductivity of graphene/polypyrrole/carbon black conductive ink made from 4 is 194.3 μ S/cm, and electric conductivity is good.
4. prepare lettering pen：With embodiment 1.
5. direct write flexible-paper-base conducting wire：With embodiment 1.
6. the post processing of direct write flexible-paper-base conducting wire：
Direct write flexible-paper-base conducting wire is placed in the min of sintering processes 20 in 100 DEG C of baking ovens.
The cross-section morphology of obtained direct write paper substrate conducting wire is shown in Fig. 8.As can be seen that in figure up and down two warning triangles it
Between region be paper substrate conducting wire（10 mm×1 mm×78.57 um）Section, thickness is 78.57 μm, electrically conductive ink
It can be adhering closely on the resin bed of base material, opposed flattened coating is formed on base material.
Figure 12-14 is that paper substrate conducting wire carries out the front and rear layer of ink of solvent resistance test and filter paper variation diagram, test procedure
With embodiment 1.Test sample before and after comparative test, sour test oil layer of ink is apparent not to be changed, and filter paper receiving surface does not have yet
Stain.And sodium hydroxide makes ink layer surface fade, layer of ink gloss disappears.To sum up show, graphene made from experiment/poly- pyrrole
Cough up/carbon black conductive ink has good acid resistance and water resistance, but be not suitable for contacting alkali lye.
Figure 15 and Figure 16 is that graphene/polypyrrole/carbon black conductive ink direct write conducting wire uniformity of different length is surveyed
Attempt.All in all, when the length of direct write conducting wire is 10 mm, 20 mm, 30 mm, 40 mm and 50 mm, electrically conductive ink
Line resistance value is linear with length, illustrates that electrically conductive ink has good uniform continuity.
Figure 17 is the bending test chart of direct write conducting wire.Result of the test shows to bend even across multiple, after sintering
Layer of ink without departing from paper base material, significant change does not occur for resistance.This shows that paper substrate conducting wire has good machine
Tool pliability, has a wide range of applications in electronic applications.
Figure 18,19 be flexible-paper-base conducting wire bending before and after test figure, by external force by the two-dimentional paper substrate after sintering
Conducting wire curling is 3 D stereo conducting wire, and result of the test shows to crimp even across multiple, and the layer of ink after sintering is not
Depart from paper base material, significant change does not occur for resistance.This shows that flexible-paper-base conducting wire has well mechanical flexible
Property, had a wide range of applications in electronic applications.
Figure 20 is the circuit arrangement figure of direct write flexible-paper-base conducting wire, it is seen that direct write flexible-paper-base conducting wire has good
Good application prospect.This experiment designed, designed paper substrate circuit：By LED3（LMY-5MMB2R02,20mA, 4.5V, Shenzhen are green
Ma Yuan Photoelectric Co., Ltd.s）Access in the circuit 5 of voltage 5V power supply 4, and connect the conducting wire being written on bloom printing paper 2
1（It is long × wide, the mm of 10 mm × 1）As conducting element.Closing of circuit, LED send light, and brightness is dark compared with Example 1.
Embodiment 5：
1. prepare redox graphene：With embodiment 1.
2. prepare graphene/Pt/Polypyrrole composite material：
Restore All graphene oxide solution and pyrrole monomer made from selection（2 mL）, 1 h is mixed under condition of ice bath.Will
FeCl3•6H2O（14.5 g）It is dissolved in hydrochloric acid（0.1 mol/L, 145 mL）, it is slowly added dropwise into mixed solution.Continue ice bath to stir
24 h are mixed, by said mixture through filtering with microporous membrane, and neutrality are washed till using deionized water.Remaining solid is placed in 40 DEG C
24 h are dried in baking oven, and are ground with agate mortar to obtain graphene/Pt/Polypyrrole composite material powder.
3. prepare graphene/polypyrrole/carbon black conductive ink：
Take 180 mg graphenes/Pt/Polypyrrole composite material（30 wt%）, it is uniform with 15 min of agate mortar grinding, it is then mixed into
420 mg carbon blacks, continue 15 min of grinding and obtain complex conductive fillerses.12 mL, 30 mL, 30 mL, 51 mL second are measured respectively
Alcohol, ethylene glycol, glycerine, deionized water, mix 10 min and obtain mixed solvent.Sequentially added in the mixed solvent compound
Conductive filler and sodium carboxymethylcellulose（CMC, 480 mg）, it is subsequently placed in ultrasonic wave plant cell pulverizer and carries out ultrasonic place
To disperse gained slurry, supersound process condition is reason：Ice bath, 960 W, 45 min.The solution that ultrasound obtains is placed at a high speed
It is centrifuged in centrifuge, centrifugation condition is：The r/min of rotating speed 8000, the min of time 15.Obtained by centrifugation
Supernatant liquor be graphene/polypyrrole/carbon black conductive ink.
Fig. 2 is the image that the electrical conductivity of electrically conductive ink changes with the change of component proportion.The present embodiment is shown in Fig. 2
The electrical conductivity of graphene/polypyrrole/carbon black conductive ink made from 5 is 205 μ S/cm, and electric conductivity is good.
4. prepare lettering pen：With embodiment 1.
5. direct write flexible-paper-base conducting wire：With embodiment 1.
6. the post processing of direct write flexible-paper-base conducting wire：
Direct write flexible-paper-base conducting wire is placed in the min of sintering processes 20 in 100 DEG C of baking ovens.
The cross-section morphology of obtained direct write paper substrate conducting wire is shown in Fig. 9.As can be seen that in figure up and down two warning triangles it
Between region be paper substrate conducting wire（10 mm×1 mm×40 um）Section, thickness is 40 μm, and electrically conductive ink can be tight
It is close to be attached on the resin bed of base material, opposed flattened coating is formed on base material.
Figure 12-14 is that paper substrate conducting wire carries out the front and rear layer of ink of solvent resistance test and filter paper variation diagram, test procedure
With embodiment 1.Test sample before and after comparative test, sour test oil layer of ink is apparent not to be changed, and filter paper receiving surface does not have yet
Stain.And sodium hydroxide makes ink layer surface fade, layer of ink gloss disappears.To sum up show, graphene made from experiment/poly- pyrrole
Cough up/carbon black conductive ink has good acid resistance and water resistance, but be not suitable for contacting alkali lye.
Figure 15 and Figure 16 is that graphene/polypyrrole/carbon black conductive ink direct write conducting wire uniformity of different length is surveyed
Attempt.All in all, when the length of direct write conducting wire is 10 mm, 20 mm, 30 mm, 40 mm and 50 mm, electrically conductive ink
Line resistance value is linear with length, illustrates that electrically conductive ink has good uniform continuity.
Figure 17 is the bending test chart of direct write conducting wire.Result of the test shows with the increase of bending number, conductive
Line resistance is unstable, illustrates that bending property is poor.
Figure 18,19 be flexible-paper-base conducting wire bending before and after test figure, by external force by the two-dimentional paper substrate after sintering
Conducting wire curling is 3 D stereo conducting wire, and result of the test shows to crimp even across multiple, and the layer of ink after sintering is not
Depart from paper base material, significant change does not occur for resistance.This shows that flexible-paper-base conducting wire has well mechanical flexible
Property, had a wide range of applications in electronic applications.
Figure 20 is the circuit arrangement figure of direct write flexible-paper-base conducting wire, it is seen that direct write flexible-paper-base conducting wire has good
Good application prospect.This experiment designed, designed paper substrate circuit：By LED3（LMY-5MMB2R02,20mA, 4.5V, Shenzhen are green
Ma Yuan Photoelectric Co., Ltd.s）Access in the circuit 5 of voltage 5V power supply 4, and connect the conducting wire being written on bloom printing paper 2
1（It is long × wide, the mm of 10 mm × 1）As conducting element.Closing of circuit, LED do not send light, illustrate conductive logical without being formed
Road.
Embodiment 6：
1. prepare redox graphene：With embodiment 1.
2. prepare graphene/Pt/Polypyrrole composite material：
Restore All graphene oxide solution and pyrrole monomer made from selection（2 mL）, 1 h is mixed under condition of ice bath.Will
FeCl3•6H2O（14.5 g）It is dissolved in hydrochloric acid（0.1 mol/L, 145 mL）, it is slowly added dropwise into mixed solution.Continue ice bath to stir
24 h are mixed, by said mixture through filtering with microporous membrane, and neutrality are washed till using deionized water.Remaining solid is placed in 40 DEG C
24 h are dried in baking oven, and are ground with agate mortar to obtain graphene/Pt/Polypyrrole composite material powder.
3. prepare graphene/polypyrrole/carbon black conductive ink：
Take 222 mg graphenes/Pt/Polypyrrole composite material（37 wt%）, it is uniform with 15 min of agate mortar grinding, it is then mixed into
378 mg carbon blacks, continue 15 min of grinding and obtain complex conductive fillerses.12 mL, 30 mL, 30 mL, 51 mL second are measured respectively
Alcohol, ethylene glycol, glycerine, deionized water, mix 10 min and obtain mixed solvent.Sequentially added in the mixed solvent compound
Conductive filler and sodium carboxymethylcellulose（CMC, 480 mg）, it is subsequently placed in ultrasonic wave plant cell pulverizer and carries out ultrasonic place
To disperse gained slurry, supersound process condition is reason：Ice bath, 960 W, 45 min.The solution that ultrasound obtains is placed at a high speed
It is centrifuged in centrifuge, centrifugation condition is：The r/min of rotating speed 8000, the min of time 15.Obtained by centrifugation
Supernatant liquor be graphene/polypyrrole/carbon black conductive ink.
Fig. 2 is the image that the electrical conductivity of electrically conductive ink changes with the change of component proportion.The present embodiment is shown in Fig. 2
The electrical conductivity of graphene/polypyrrole/carbon black conductive ink made from 6 is 243.7 μ S/cm, and electric conductivity is good.
4. prepare lettering pen：With embodiment 1.
5. direct write flexible-paper-base conducting wire：With embodiment 1.
6. the post processing of direct write flexible-paper-base conducting wire：
Direct write flexible-paper-base conducting wire is placed in the min of sintering processes 20 in 100 DEG C of baking ovens.
The cross-section morphology of obtained direct write paper substrate conducting wire is shown in Figure 10.As can be seen that two warning triangles above and below in figure
Between region be paper substrate conducting wire（10 mm×1 mm×34.29 um）Section, thickness is 34.29 μm, conductive oil
Ink can be adhering closely on the resin bed of base material, and opposed flattened coating is formed on base material.
Figure 12-14 is that paper substrate conducting wire carries out the front and rear layer of ink of solvent resistance test and filter paper variation diagram, test procedure
With embodiment 1.Test sample before and after comparative test, sour test oil layer of ink is apparent not to be changed, and filter paper receiving surface does not have yet
Stain.And sodium hydroxide makes ink layer surface fade, layer of ink gloss disappears.To sum up show, graphene made from experiment/poly- pyrrole
Cough up/carbon black conductive ink has good acid resistance and water resistance, but be not suitable for contacting alkali lye.
Figure 15 and Figure 16 is that graphene/polypyrrole/carbon black conductive ink direct write conducting wire uniformity of different length is surveyed
Attempt.All in all, when the length of direct write conducting wire is 10 mm, 20 mm, 30 mm, 40 mm and 50 mm, electrically conductive ink
Line resistance value is linear with length, illustrates that electrically conductive ink has good uniform continuity.
Figure 17 is the bending test chart of direct write conducting wire.Result of the test shows to bend even across multiple, after sintering
Layer of ink without departing from paper base material, significant change does not occur for resistance.This shows that paper substrate conducting wire has good machine
Tool pliability, has a wide range of applications in electronic applications.
Figure 18,19 be flexible-paper-base conducting wire bending before and after test figure, by external force by the two-dimentional paper substrate after sintering
Conducting wire curling is 3 D stereo conducting wire, and result of the test shows to crimp even across multiple, and the layer of ink after sintering is not
Depart from paper base material, significant change does not occur for resistance.This shows that flexible-paper-base conducting wire has well mechanical flexible
Property, had a wide range of applications in electronic applications.
Figure 20 is the circuit arrangement figure of direct write flexible-paper-base conducting wire, it is seen that direct write flexible-paper-base conducting wire has good
Good application prospect.This experiment designed, designed paper substrate circuit：By LED3（LMY-5MMB2R02,20mA, 4.5V, Shenzhen are green
Ma Yuan Photoelectric Co., Ltd.s）Access in the circuit 5 of voltage 5V power supply 4, and connect the conducting wire being written on bloom printing paper 2
1（It is long × wide, the mm of 10 mm × 1）As conducting element.Closing of circuit, LED do not send light, illustrate conductive logical without being formed
Road.
Embodiment 7：
1. prepare redox graphene：
Graphene oxide is prepared first：By the concentrated sulfuric acid（25 mL）It is placed in beaker（250 mL）, sequentially add graphite powder（3 g）, mistake
Potassium sulfate（4 g）, phosphorus pentoxide（4 g）, it is placed in water-bath（80 ℃）In.Mixture is after magneton stirs 5 h, filtering,
Neutrality is washed to, is placed in baking oven（60 ℃）Middle drying.Under condition of ice bath, by the concentrated sulfuric acid（100 mL）It is slowly added in placement
State drying composite and sodium nitrate（1 g）Beaker, and be slowly added to potassium permanganate in batches（10 g）, after the h of strong stirring 2, rise
Temperature reacts 4 h to 35 DEG C.It is slow added into deionized water（800 mL）, 30 min are stirred, then 90 DEG C are warming up to, continue to stir
Mix 30 min.Add hydrogen peroxide（20 mL）, now solution presentation glassy yellow.Aforesaid liquid is diluted with deionized water, with coming down in torrents
Method removes acid repeatedly, is reloaded into bag filter and dialyses 2 weeks, to remove the foreign ion in solution, until solution is in neutrality.Finally will be molten
It is 0.04 mg/mL that liquid, which is diluted to concentration, and 2 h are ultrasonically treated under condition of ice bath（The W of power 960）Afterwards, then centrifuge（15
min）, take supernatant, as graphene oxide suspension.
Vitamin C is added into graphene oxide suspension（The mass ratio of vitamin C and graphene oxide is 10：1）,
And it is allowed to be maintained in the range of 9 ~ 10 using the pH value of ammoniacal liquor regulation solution.The h of water-bath 2 under the conditions of 95 DEG C.By said mixture
Neutrality is washed till through filtering with microporous membrane, and using deionized water.Remaining solid is placed in 60 DEG C of baking ovens and dries 12 h, and uses agate
Nao bowls grind to obtain redox graphene.
2. prepare Graphene conductive ink：
96 mg graphenes are taken, it is uniform with 15 min of agate mortar grinding, 504 mg carbon blacks are then mixed into, continue to grind 15 min
Obtain complex conductive fillerses.12 mL, 30 mL, 30 mL, 51 mL ethanol, ethylene glycol, glycerine, deionization are measured respectively
Water, mix 10 min and obtain mixed solvent.Complex conductive fillerses are sequentially added to above-mentioned in the mixed solvent and carboxymethyl is fine
Tie up plain sodium（480 mg）, it is placed in being ultrasonically treated in ultrasonic wave plant cell pulverizer（Supersound process condition：Ice bath, work(
The W of rate 960,30 min）.Then, above-mentioned solution is placed in supercentrifuge and be centrifuged（Centrifugation condition：Rotating speed
8000 r/min, the min of time 15）, gained supernatant is Graphene conductive ink.
Fig. 2 is the image that the electrical conductivity of electrically conductive ink changes with the change of component proportion.The present embodiment is shown in Fig. 2
The electrical conductivity of graphene/polypyrrole/carbon black conductive ink made from 7 is 122.4 μ S/cm, and electric conductivity is good.
3. inkjet printing flexible-paper-base conducting wire：
First, according to the demand of experiment, test, software Adobe Illustrator are utilized（CS6, Adobe system house）Meter
Go out the recognizable bitmap file of printer；Then, 60 ml Graphene conductive inks are measured, load the company of ink-jet printer for dress
In putting, and even it will be installed on a printer for device；With bloom printing paper（C13S041860, Chinese Epson Co., Ltd）For
Base material, paper substrate printed material is installed；Finally, the width of same conducting wire is kept constant, inkjet printing 1 time, obtains ink-jet
Print flexible-paper-base conducting wire（It is long × wide, the mm of 50 mm × 2）.
4. the post processing of inkjet printing flexible-paper-base conducting wire
Inkjet printing flexible-paper-base conducting wire is placed in the min of sintering processes 10 in 50 DEG C of baking ovens.
The cross-section morphology of obtained inkjet printing flexible-paper-base conducting wire is shown in Figure 11.Two warning triangles above and below in Figure 11
Between region be inkjet printing flexible-paper-base conducting wire（10 mm×2 mm×0.03338 mm）Section, thickness is
33.38 μm。
Figure 15 and Figure 16 is that graphene/polypyrrole/carbon black conductive ink direct write conducting wire uniformity of different length is surveyed
Attempt.All in all, when the length of direct write conducting wire is 10 mm, 20 mm, 30 mm, 40 mm and 50 mm, electrically conductive ink
Line resistance value is linear with length, illustrates that electrically conductive ink has good uniform continuity.
Figure 18,19 be flexible-paper-base conducting wire bending before and after test figure, by external force by the two-dimentional paper substrate after sintering
Conducting wire curling is 3 D stereo conducting wire, and result of the test shows to crimp even across multiple, and the layer of ink after sintering is not
Depart from paper base material, significant change does not occur for resistance.This shows that flexible-paper-base conducting wire has well mechanical flexible
Property, had a wide range of applications in electronic applications.
Figure 20 is the circuit arrangement figure of inkjet printing flexible-paper-base conducting wire, it is seen that inkjet printing flexible-paper-base conductor wire
Road has a good application prospect.Designed, designed of the present invention conducting wire pattern, ink-jet printer is imported, using inkjet printing
Mode, by LED 3（LMY-5MMB2R02,20mA, 3 ~ 3.4V, Lv Mayuan Photoelectric Co., Ltd.s of Shenzhen）Access voltage 3V's
In the circuit 5 of power supply 4, conducting wire 1 of the connection inkjet printing on flexible-paper-base 2（It is long × wide, the mm of 20 mm × 2）As conduction
Element.Closing of circuit, LED send light, and this shows to have formd conductive path inside ink circuit.
Summarize：
The sample of embodiment 1 ~ 6 for add polypyrrole graphene/polypyrrole/carbon black conductive ink, flexible-paper-base conducting wire
Building mode for directly writing；The sample of embodiment 7 is not add graphene/carbon black conductive ink of polypyrrole, flexible paper
The building mode of base conducting wire is inkjet printing.Research shows that after adding polypyrrole, ink conductivity has very big carry
Rise, illustrate that polypyrrole can preferably improve the electric conductivity of graphene/carbon black composite conducting ink.By stone produced by the present invention
Black alkene/polypyrrole/carbon black conductive ink is fitted into lettering pen, is directly write on paper base material, obtains flexible-paper-base conductor wire
Road, it has excellent water resistance and acid resistance, while uniformity, and bending property resistant to bending is good, is expected to be applied to conductor wire
The structure on road.Compared with inkjet printing mode, the mode directly write is simple to operate, and cost is cheap, green, available for pushing away
It is wide to use.
Claims (10)
1. the preparation method of graphene/polypyrrole/carbon black conductive ink, it is characterised in that：Comprise the following steps：
A, grinding obtains hybrid conductive filler after mixing carbon black and graphene/Pt/Polypyrrole composite material；
B, ethanol, ethylene glycol, glycerine and deionized water mixed solvent are prepared；
C, mixed solvent made from complex conductive fillerses made from A, B is mixed with sodium carboxymethylcellulose, and sonicated,
Centrifuge, gained supernatant is graphene/polypyrrole/carbon black conductive ink.
2. the preparation method of graphene/polypyrrole/carbon black conductive ink according to claim 1, it is characterised in that：Mixing
Conductive filler 580-620mg；The mass ratio that graphene/Pt/Polypyrrole composite material accounts for hybrid conductive filler is 1 %-40 %；Mixing
Ethanol in solvent, ethylene glycol, the dosage of glycerine and deionized water are respectively 10-15 mL, 28-32 mL, 28-32 mL and 50-
55 mL；Sodium carboxymethylcellulose is the 50-80 % of complex conductive fillerses quality.
3. the preparation method of graphene/polypyrrole/carbon black conductive ink according to claim 1, it is characterised in that：It is described
Graphene/Pt/Polypyrrole composite material is prepared as follows：
Using graphene and pyrrole monomer as raw material, using situ aggregation method, graphene/Pt/Polypyrrole composite material is obtained.
4. the preparation method of graphene/polypyrrole/carbon black conductive ink according to claim 3, it is characterised in that：Using
When situ aggregation method prepares graphene/Pt/Polypyrrole composite material, graphene, pyrroles, the mass ratio of Iron(III) chloride hexahydrate are 1:
9-11:68-75。
5. the preparation method of graphene/polypyrrole/carbon black conductive ink according to claim 1, it is characterised in that：Step
Condition is ultrasonically treated in C is：Power is 800-1000 W, and ultrasonic time is no more than 1 h；Centrifugation condition is：Rotating speed is
7000-9000 r/min, time are no more than 1 h.
6. prepared by a kind of preparation method of graphene/polypyrrole/carbon black conductive ink according to described in any claim 1-5
Graphene/polypyrrole/carbon black conductive ink.
7. flexible-paper-base writes conducting wire, it is characterized in that：It is to prepare by the following method：
Graphene/polypyrrole/carbon black conductive ink is fitted into lettering pen, is directly write on paper base material, obtains flexible paper
Base conducting wire.
8. flexible-paper-base according to claim 7 writes conducting wire, it is characterised in that：To the width of same conducting wire
Degree keeps constant, and repeated writing number is no more than 10 times.
9. flexible-paper-base according to claim 7 writes conducting wire, it is characterised in that：Paper substrate after writing is placed in baking oven
In, thermal sintering processing is carried out to flexible-paper-base conducting wire.
10. flexible-paper-base according to claim 9 writes conducting wire, it is characterised in that：During sintering processes, sintering temperature
For 80 DEG C -100 DEG C, sintering time is no more than 1 h.
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| CN108847359A (en) * | 2018-06-27 | 2018-11-20 | 暨南大学 | A kind of preparation method and application of direct write CNT/Ag flexible super capacitor |
| CN109627849A (en) * | 2018-11-22 | 2019-04-16 | 武汉纺织大学 | A kind of carbon nano-tube/poly pyrroles nanotube composite electron ink and preparation method thereof |
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| CN110414652A (en) * | 2018-04-28 | 2019-11-05 | 华瑞墨石丹阳有限公司 | A kind of vulnerable graphite alkene RFID label tag |
| CN108847359A (en) * | 2018-06-27 | 2018-11-20 | 暨南大学 | A kind of preparation method and application of direct write CNT/Ag flexible super capacitor |
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| CN114792605B (en) * | 2021-07-02 | 2023-11-03 | 河北北塑管业有限公司 | Ink direct-writing zinc ion mixed miniature super capacitor and preparation method and application thereof |
| WO2023002244A1 (en) * | 2021-07-21 | 2023-01-26 | Indian Institute Of Technology Kanpur | Eco-friendly ink formulation of resistive ink for roller ball pen |
| CN115626818A (en) * | 2022-11-01 | 2023-01-20 | 福建星海通信科技有限公司 | Ceramic slurry preparation method and precision direct-writing 3D printing method |
| CN115626818B (en) * | 2022-11-01 | 2023-05-05 | 福建星海通信科技有限公司 | Ceramic slurry preparation method and precise direct-writing 3D printing method |
| CN116144097A (en) * | 2023-02-17 | 2023-05-23 | 四川大学 | Preparation method and application of semiconductive shielding material for high-voltage alternating-current cable |
| CN116285504A (en) * | 2023-03-24 | 2023-06-23 | 北京印刷学院 | Polypyrrole/conductive carbon black/polyvinyl alcohol conductive ink and preparation method and application thereof |
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Application publication date: 20180213 |