CN106634221A - Graphene conductive ink, preparation method therefor and inkjet-printed flexible paper-based conductive line - Google Patents
Graphene conductive ink, preparation method therefor and inkjet-printed flexible paper-based conductive line Download PDFInfo
- Publication number
- CN106634221A CN106634221A CN201610964875.2A CN201610964875A CN106634221A CN 106634221 A CN106634221 A CN 106634221A CN 201610964875 A CN201610964875 A CN 201610964875A CN 106634221 A CN106634221 A CN 106634221A
- Authority
- CN
- China
- Prior art keywords
- graphene
- paper
- conducting wire
- inkjet printing
- conductive ink
- 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.)
- Pending
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0386—Paper sheets
-
- H—ELECTRICITY
- 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
- H05K3/12—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 using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
- H05K3/1241—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 using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by ink-jet printing or drawing by dispensing
- H05K3/125—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 using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by ink-jet printing or drawing by dispensing by ink-jet printing
Abstract
The invention discloses a method for preparing an inkjet-printed flexible paper-based conductive line. The inkjet-printed flexible paper-based conductive line is prepared through carrying out inkjet printing on graphene conductive ink. The method comprises the steps of preparing the graphene conductive ink in a manner of taking graphene and carbon black as conductive fillers, taking a mixture solution of ethanol, ethylene glycol, glycerol and deionized water as a solvent and taking sodium carboxymethyl cellulose as a binder and a stabilizer, and carrying out inkjet printing on a paper-based material by using an inkjet printer, thereby obtaining the flexible paper-based conductive line. According to the method, the process is simple, and the inkjet-printed flexible paper-based conductive line has good acid resistance, uniformity, flexibility, bendability and conductivity. The method is in line with the general development trends, i.e., large batch, large area, low cost and flexibility of printed electronic products.
Description
Technical field
The present invention relates to Graphene conductive ink, inkjet printing flexible-paper-base conducting wire and preparation method thereof, belong to material
Material scientific domain.
Background technology
The preparation method of conventional printed circuit is usually serigraphy etc., and printing process is complicated, and discarded printed circuit
Plate recycles difficulty, makes increasingly serious with the contaminated wastewater during scrap concrete.Quick with printed electronic sends out
Exhibition, ink jet printing is of increased attention.Realize that the inkjet printing of printed circuit not only has work using electrically conductive ink
The advantages of skill is simple, printing precision is high, electric conductivity is good, and after can reducing in printed circuit board manufacturing process and being discarded
The environmental pollution for being brought.Electrically conductive ink and ink-jet printing technology are combined, is manufactured and designed microelectronic circuit and is applied to soft
On property substrate, conducting wire will be led to develop towards efficient, pollution-free, process is simple direction.Graphene is used as in recent years
International research focus, with excellent electric conductivity, mechanical property, corrosion resistance and non-oxidizability.This conventional pilot of carbon black
The electric conductivity of electric material is not high, and the electric conductivity of carbon black base electrically conductive ink is not good, but its low cost, light weight, stable performance.
The content of the invention
It is an object of the invention to provide a kind of preparation method of Graphene conductive ink, its Graphene conductive ink for preparing
Electric conductivity and good stability, inkjet printing can be realized.
The preparation method of Graphene conductive ink of the present invention, is combined grinding after carbon black and Graphene mixing
Conductive filler；Ethanol, ethylene glycol, glycerine, the deionized water of 10-14mL, 28-32mL, 28-32mL, 49-53mL are measured respectively
Mixing obtains mixed solvent；Complex conductive fillerses 580-620mg and sodium carboxymethylcellulose are added to enter in mixed solvent
Row is ultrasonically treated, is then centrifuged for separating, and gained supernatant is Graphene conductive ink；Graphene accounts for the matter of complex conductive fillerses
Amount is than being 1%～30%.
The preparation method of above-mentioned Graphene conductive ink, sodium carboxymethylcellulose be complex conductive fillerses quality 40～
80%.
The preparation method of above-mentioned Graphene conductive ink, the Graphene is prepared as follows：
With natural graphite powder as raw material, graphene oxide is prepared using Hummers methods, using reducing agent reduction-oxidation graphite
Alkene, obtains redox graphene.
When preparing graphene oxide using Hummers methods, graphite powder, potassium peroxydisulfate, phosphorus pentoxide, sodium nitrate, Gao Meng
The mass ratio of sour potassium is 3：4：4：1：10.
The preparation method of above-mentioned Graphene conductive ink, when preparing Graphene, reducing agent is vitamin C, glucose, fruit
Sugar.
The preparation method of above-mentioned Graphene conductive ink, during the redox graphene, the recovery time is 2～4h,
Reduction temperature is 90 DEG C～95 DEG C, and reducing agent is 1 with the mass ratio of graphene oxide：10～20.
Present invention also offers a kind of electric conductivity and good stability, the Graphene conductive ink of inkjet printing can be realized.
Graphene conductive ink of the present invention, it is prepared according to the preparation method of described Graphene conductive ink
.
Present invention also offers a kind of good conductivity, the inkjet printing flexible-paper-base conducting wire that can be crimped.
Inkjet printing flexible-paper-base conducting wire of the present invention, it is to be prepared from by the following method：Graphite
Alkene electrically conductive ink loads ink-jet printer, and inkjet printing is carried out on paper substrate printed material, obtains flexible-paper-base conducting wire.Paper
Base printed material can be common paper, bloom printing paper, weight pound cartridge paper or other types paper.
Above-mentioned inkjet printing flexible-paper-base conducting wire, keeps constant to the width of same conducting wire, repeatedly many
Secondary printing, and printing times are less than 10 times.As the number of times for carrying out duplicate printing increases, conductive network is gradually formed, layer of ink
Thickness increase, it is totally continuous between ink droplet and ink droplet to contact with each other to form current path, therefore ensure that conducting wire is good
Good conductive capability.
Above-mentioned inkjet printing flexible-paper-base conducting wire, the paper substrate after inkjet printing is placed in baking oven, to flexible paper
Base conducting wire is sintered.
Above-mentioned inkjet printing flexible-paper-base conducting wire, during sintering, sintering temperature is 50 DEG C～100 DEG C, sintering time
For 5～10min.Before electrically conductive ink sintering curing, conductive filler is contacted not closely in ink, and electric conductivity is poor.By heat
Sintering can make the solvent in electrically conductive ink thoroughly volatilize, and conducting particles contact is more tight, connect into the conduction of continuous densification
Path.
The present invention adopts oxide-reduction method, with vitamin C, glucose, fructose as reducing agent, prepares electric conductivity good
Redox graphene, environment friendly is strong, is adapted to the large-scale production of Graphene.Graphene is combined with carbon black,
On the one hand, it is therefore prevented that the reunion of graphene film, the electric conductivity of compound oil ink system is improved；On the other hand, compound oil ink body is improved
The stability of system.Inkjet printing can be realized using the Graphene conductive ink, and inkjet printing flexible-paper-base conducting wire is led
Electrical property is good.
Description of the drawings
Fig. 1 is the Raman spectrum of Graphene obtained in embodiment 1.
Fig. 2 is the X-ray diffraction spectra figure of Graphene obtained in embodiment 1.
Fig. 3 is the electron microscopic picture on inkjet printing flexible-paper-base conducting wire surface obtained in embodiment 1.
Fig. 4 is the electron microscopic picture of inkjet printing flexible-paper-base conducting wire section obtained in embodiment 1.
Fig. 5 is the picture before the bending of obtained inkjet printing flexible-paper-base conducting wire.
Fig. 6 is the picture after bending of obtained inkjet printing flexible-paper-base conducting wire.
Fig. 7 is the circuit arrangement figure of inkjet printing flexible-paper-base conducting wire obtained in embodiment 1.
Embodiments of the present invention are described further below in conjunction with the accompanying drawings.
Specific embodiment
Embodiment 1：
1. redox graphene is prepared：
Graphene oxide is prepared first：The concentrated sulfuric acid (25mL) is placed in into beaker (250mL), sequentially add graphite powder (3g),
Potassium peroxydisulfate (4g), phosphorus pentoxide (4g), in being placed in water-bath (80 DEG C).Mixture is filtered, water Jing after magneton stirring 5h
Neutrality is washed till, drying in baking oven (60 DEG C) is placed in.Under condition of ice bath, the concentrated sulfuric acid (100mL) is slowly added to place above-mentioned dry
The beaker of dry mixture and sodium nitrate (1g), and potassium permanganate (10g) is slowly added in batches, after strong stirring 2h, it is warming up to 35
DEG C, react 4h.Deionized water (800mL) is slow added into, 30min is stirred, then is warming up to 90 DEG C, continuation stirring 30min.Add
Hydrogen peroxide (20mL), now solution presentation glassy yellow.Deionized water dilutes aforesaid liquid, and with decantation acid is gone repeatedly, then
Load bag filter to dialyse 2 weeks, to remove the foreign ion in solution, until solution is in neutrality.Finally solution is diluted into concentration
For 0.04mg/mL, and under condition of ice bath after ultrasonically treated 2h (power 960W), then centrifugation (15min), supernatant is taken,
As graphene oxide suspension.
Redox graphene is prepared again：Vitamin C (vitamin C and oxidation stone are added in graphene oxide suspension
The mass ratio of black alkene is 10：1) pH value for, and using ammoniacal liquor adjusting solution is allowed to be maintained in the range of 9-10.Water under the conditions of 95 DEG C
Bath 2h.By said mixture Jing filtering with microporous membrane, and neutrality is washed till using deionized water.Remaining solid is placed in into 60 DEG C of baking ovens
In be dried 12h, and obtain redox graphene with agate mortar grinding.
From the Raman spectrum (Fig. 1) of redox graphene, the D peaks of redox graphene and the strength ratio at G peaks
(ID/IG) up to 1.15, this shows that the conjugated structure of Graphene is rebuild.From the X-ray diffraction spectra of redox graphene
Figure (Fig. 2) is visible, and 2 θ positions of Graphene are located at 24.58 °, correspondence interlamellar spacing only 0.362nm, the thickness in monolayer with Graphene
Theoretical value (0.335nm) it is close, show prepare the Graphene number of plies be about 1 layer.
2. Graphene conductive ink is prepared：
96mg Graphenes are taken, it is uniform with agate mortar grinding 15min, 504mg carbon blacks are then mixed into, continue to grind 15min
Obtain complex conductive fillerses.Ethanol, ethylene glycol, glycerine, the deionized water of 12mL, 30mL, 30mL, 51mL are measured respectively, are mixed
Close stirring 10min and obtain mixed solvent.Complex conductive fillerses and sodium carboxymethylcellulose are sequentially added in above-mentioned mixed solvent
(480mg), it is placed in carrying out ultrasonically treated (ultrasonically treated condition in ultrasonic wave plant cell pulverizer：Ice bath, power 960W,
30min).Subsequently, above-mentioned solution is placed in supercentrifuge and is centrifuged (centrifugation condition：Rotating speed 8000r/
Min, time 15min), gained supernatant is Graphene conductive ink.
3. inkjet printing flexible-paper-base conducting wire：
First, according to experiment, the demand of test, using software Adobe Illustrator (CS6, Adobe system house)
Design the discernible bitmap file of printer；Then, 60ml Graphene conductive inks are measured, the company for loading ink-jet printer supplies
In device, and device will be even supplied to install on a printer；It is with bloom printing paper (C13S041860, Chinese Epson Co., Ltd)
Base material, installs paper substrate printed material；Finally, the width of same conducting wire keeps constant, inkjet printing 1 time, obtains ink-jet
Print flexible-paper-base conducting wire (length × wide, 50mm × 2mm).
4. the post processing of inkjet printing flexible-paper-base conducting wire
Inkjet printing flexible-paper-base conducting wire is placed in into sintering processes 10min in 50 DEG C of baking ovens.
The surface topography and cross-section morphology of obtained inkjet printing flexible-paper-base conducting wire is shown in respectively Fig. 3 and Fig. 4.Can be with
Find out, be in close contact between carbon black pellet together, define dense conductive network.Upper and lower two triangular signs in Fig. 4
Region between note is the section of inkjet printing flexible-paper-base conducting wire (10mm × 2mm × 0.03338mm), and thickness is
33.38 μm, the coating two ends resistance of measurement is 9.9 × 104Ω, according to resistivity formula (1), calculates carbon black/Graphene and leads
The resistivity of electric ink is 0.661 Ω m.
Fig. 5,6 be 5 inkjet printing flexible-paper-base conducting wires bending before and after test figure, after external force is by sintering
Two-dimentional inkjet printing flexible-paper-base conducting wire curling is 3 D stereo conducting wire, and result of the test shows even across 10 circle volumes
Song, without departing from paper base material, significant change in resistance to the layer of ink after sintering there is no.This shows inkjet printing flexible-paper-base
Conducting wire has good mechanical flexibility, has a wide range of applications in electronic applications.
Fig. 7 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, imports ink-jet printer, using inkjet printing
Mode, accesses voltage 3V's by LED 1 (LMY-5MMB2R02,20mA, 3～3.4V, Lv Mayuan Photoelectric Co., Ltd.s of Shenzhen)
In the circuit of power supply 2, connect conducting wire 3 (length × wide, 20mm × 2mm) of the inkjet printing on flexible-paper-base 4 as conductive element
Part.Closing of circuit, LED sends light, and this shows to have defined conductive path inside ink circuit.
Embodiment 2：
1. redox graphene is prepared：
Graphene oxide is prepared first：The concentrated sulfuric acid (25mL) is placed in into beaker (250mL), sequentially add graphite powder (3g),
Potassium peroxydisulfate (4g), phosphorus pentoxide (4g), in being placed in water-bath (80 DEG C).Mixture is filtered, water Jing after magneton stirring 5h
Neutrality is washed till, drying in baking oven (60 DEG C) is placed in.Under condition of ice bath, the concentrated sulfuric acid (100mL) is slowly added to place above-mentioned dry
The beaker of dry mixture and sodium nitrate (1g), and potassium permanganate (10g) is slowly added in batches, after strong stirring 2h, it is warming up to 35
DEG C, react 4h.Deionized water (800mL) is slow added into, 30min is stirred, then is warming up to 90 DEG C, continuation stirring 30min.Add
Hydrogen peroxide (20mL), now solution presentation glassy yellow.Deionized water dilutes aforesaid liquid, and with decantation acid is gone repeatedly, then
Load bag filter to dialyse 2 weeks, to remove the foreign ion in solution, until solution is in neutrality.Finally solution is diluted into concentration
For 0.04mg/mL, and under condition of ice bath after ultrasonically treated 2h (power 960W), then centrifugation (15min), supernatant is taken,
As graphene oxide suspension.
Redox graphene is prepared again：Vitamin C (vitamin C and oxidation stone are added in graphene oxide suspension
The mass ratio of black alkene is 10：1) pH value for, and using ammoniacal liquor adjusting solution is allowed to be maintained in the range of 9-10.Water under the conditions of 95 DEG C
Bath 4h.By said mixture Jing filtering with microporous membrane, and neutrality is washed till using deionized water.Remaining solid is placed in into 60 DEG C of baking ovens
In be dried 12h, and obtain redox graphene with agate mortar grinding.
2. Graphene conductive ink is prepared：
54mg Graphenes are taken, it is uniform with agate mortar grinding 15min, 546mg carbon blacks are then mixed into, continue to grind 15min
Obtain complex conductive fillerses.Ethanol, ethylene glycol, glycerine, the deionized water of 12mL, 30mL, 30mL, 51mL are measured respectively, are mixed
Close stirring 10min and obtain mixed solvent.Complex conductive fillerses and sodium carboxymethylcellulose are sequentially added in above-mentioned mixed solvent
(480mg), it is placed in carrying out ultrasonically treated (ultrasonically treated condition in ultrasonic wave plant cell pulverizer：Ice bath, power 960W,
30min).Subsequently, above-mentioned solution is placed in supercentrifuge and is centrifuged (centrifugation condition：Rotating speed 8000r/
Min, time 15min), gained supernatant is Graphene conductive ink.
3. inkjet printing flexible-paper-base conducting wire：
First, according to experiment, the demand of test, using software Adobe Illustrator (CS6, Adobe system house)
Design the discernible bitmap file of printer；Then, 60ml Graphene conductive inks are measured, the company for loading ink-jet printer supplies
In device, and device will be even supplied to install on a printer；With common paper (APYVQ959, Shanghai M ＆ G Stationery Inc.)
For base material, paper substrate printed material is installed；Finally, the width of same conducting wire keeps constant, and repeatedly inkjet printing 5 times, obtain
To inkjet printing flexible-paper-base conducting wire (length × wide, 50mm × 1mm).
Tested using the circuit arrangement figure shown in Fig. 7 in embodiment 1, connected inkjet printing flexible-paper-base conducting wire
3 (length × wide, 20mm × 1mm) are used as conducting element.Closing of circuit, LED sends light.But LED brightness is relative to enforcement
Than dark for example 1.
Embodiment 3：
1. redox graphene is prepared：
Graphene oxide is prepared first：The concentrated sulfuric acid (25mL) is placed in into beaker (250mL), sequentially add graphite powder (3g),
Potassium peroxydisulfate (4g), phosphorus pentoxide (4g), in being placed in water-bath (80 DEG C).Mixture is filtered, water Jing after magneton stirring 5h
Neutrality is washed till, drying in baking oven (60 DEG C) is placed in.Under condition of ice bath, the concentrated sulfuric acid (100mL) is slowly added to place above-mentioned dry
The beaker of dry mixture and sodium nitrate (1g), and potassium permanganate (10g) is slowly added in batches, after strong stirring 2h, it is warming up to 35
DEG C, react 4h.Deionized water (800mL) is slow added into, 30min is stirred, then is warming up to 90 DEG C, continuation stirring 30min.Add
Hydrogen peroxide (20mL), now solution presentation glassy yellow.Deionized water dilutes aforesaid liquid, and with decantation acid is gone repeatedly, then
Load bag filter to dialyse 2 weeks, to remove the foreign ion in solution, until solution is in neutrality.Finally solution is diluted into concentration
For 0.04mg/mL, and under condition of ice bath after ultrasonically treated 2h (power 960W), then centrifugation (15min), supernatant is taken,
As graphene oxide suspension.
Redox graphene is prepared again：Vitamin C (vitamin C and oxidation stone are added in graphene oxide suspension
The mass ratio of black alkene is 20：1) pH value for, and using ammoniacal liquor adjusting solution is allowed to be maintained in the range of 9-10.Water under the conditions of 95 DEG C
Bath 2h.By said mixture Jing filtering with microporous membrane, and neutrality is washed till using deionized water.Remaining solid is placed in into 60 DEG C of baking ovens
In be dried 12h, and obtain redox graphene with agate mortar grinding.
2. Graphene conductive ink is prepared：
138mg Graphenes are taken, it is uniform with agate mortar grinding 15min, 462mg carbon blacks are then mixed into, continue to grind 15min
Obtain complex conductive fillerses.Ethanol, ethylene glycol, glycerine, the deionized water of 12mL, 30mL, 30mL, 51mL are measured respectively, are mixed
Close stirring 10min and obtain mixed solvent.Complex conductive fillerses and sodium carboxymethylcellulose are sequentially added in above-mentioned mixed solvent
(480mg), it is placed in carrying out ultrasonically treated (ultrasonically treated condition in ultrasonic wave plant cell pulverizer：Ice bath, power 960W,
30min).Subsequently, above-mentioned solution is placed in supercentrifuge and is centrifuged (centrifugation condition：Rotating speed 8000r/
Min, time 15min), gained supernatant is Graphene conductive ink.
3. inkjet printing flexible-paper-base conducting wire：
First, according to experiment, the demand of test, using software Adobe Illustrator (CS6, Adobe system house)
Design the discernible bitmap file of printer；Then, 60ml Graphene conductive inks are measured, the company for loading ink-jet printer supplies
In device, and device will be even supplied to install on a printer；It is with weight pound cartridge paper (S041259, Chinese Epson Co., Ltd)
Base material, installs paper substrate printed material；Finally, finally, the width of same conducting wire keeps constant, repeatedly inkjet printing 10
It is secondary, obtain inkjet printing flexible-paper-base conducting wire (length × wide, 50mm × 2mm).
4. the post processing of inkjet printing flexible-paper-base conducting wire：
Inkjet printing flexible-paper-base conducting wire is placed in into sintering processes 5min in 100 DEG C of baking ovens.
Tested using the circuit arrangement figure shown in Fig. 7 in embodiment 1, connected inkjet printing flexible-paper-base conducting wire
3 (length × wide, 20mm × 2mm) are used as conducting element.Closing of circuit, LED sends light.LED brightness is compared with Example 1
It is brighter.
Embodiment 4：
1. redox graphene is prepared：
Graphene oxide is prepared first：The concentrated sulfuric acid (25mL) is placed in into beaker (250mL), sequentially add graphite powder (3g),
Potassium peroxydisulfate (4g), phosphorus pentoxide (4g), in being placed in water-bath (80 DEG C).Mixture is filtered, water Jing after magneton stirring 5h
Neutrality is washed till, drying in baking oven (60 DEG C) is placed in.Under condition of ice bath, the concentrated sulfuric acid (100mL) is slowly added to place above-mentioned dry
The beaker of dry mixture and sodium nitrate (1g), and potassium permanganate (10g) is slowly added in batches, after strong stirring 2h, it is warming up to 35
DEG C, react 4h.Deionized water (800mL) is slow added into, 30min is stirred, then is warming up to 90 DEG C, continuation stirring 30min.Add
Hydrogen peroxide (20mL), now solution presentation glassy yellow.Deionized water dilutes aforesaid liquid, and with decantation acid is gone repeatedly, then
Load bag filter to dialyse 2 weeks, to remove the foreign ion in solution, until solution is in neutrality.Finally solution is diluted into concentration
For 0.04mg/mL, and under condition of ice bath after ultrasonically treated 2h (power 960W), then centrifugation (15min), supernatant is taken,
As graphene oxide suspension.
Redox graphene is prepared again：Glucose (glucose and graphite oxide are added in graphene oxide suspension
The mass ratio of alkene is 10：1) pH value for, and using ammoniacal liquor adjusting solution is allowed to be maintained in the range of 9-10.Water-bath under the conditions of 95 DEG C
2h.By said mixture Jing filtering with microporous membrane, and neutrality is washed till using deionized water.Remaining solid is placed in 60 DEG C of baking ovens
12h is dried, and redox graphene is obtained with agate mortar grinding.
2. Graphene conductive ink is prepared：
186mg Graphenes are taken, it is uniform with agate mortar grinding 15min, 434mg carbon blacks are then mixed into, continue to grind 15min
Obtain complex conductive fillerses.Ethanol, ethylene glycol, glycerine, the deionized water of 12mL, 30mL, 30mL, 51mL are measured respectively, are mixed
Close stirring 10min and obtain mixed solvent.Complex conductive fillerses and sodium carboxymethylcellulose are sequentially added in above-mentioned mixed solvent
(372mg), it is placed in carrying out ultrasonically treated (ultrasonically treated condition in ultrasonic wave plant cell pulverizer：Ice bath, power 960W,
30min).Subsequently, above-mentioned solution is placed in supercentrifuge and is centrifuged (centrifugation condition：Rotating speed 8000r/
Min, time 15min), gained supernatant is Graphene conductive ink.
3. inkjet printing flexible-paper-base conducting wire：
First, according to experiment, the demand of test, using software Adobe Illustrator (CS6, Adobe system house)
Design the discernible bitmap file of printer；Then, 60ml Graphene conductive inks are measured, the company for loading ink-jet printer supplies
In device, and device will be even supplied to install on a printer；It is with bloom printing paper (C13S041860, Chinese Epson Co., Ltd)
Base material, installs paper substrate printed material；Finally, finally, the width of same conducting wire keeps constant, repeatedly inkjet printing 10
It is secondary, obtain inkjet printing flexible-paper-base conducting wire (length × wide, 50mm × 1mm).
4. the post processing of inkjet printing flexible-paper-base conducting wire：
Inkjet printing flexible-paper-base conducting wire is placed in into sintering processes 5min in 100 DEG C of baking ovens.
Tested using the circuit arrangement figure shown in Fig. 7 in embodiment 1, connected inkjet printing flexible-paper-base conducting wire
3 (length × wide, 20mm × 1mm) are used as conducting element.Closing of circuit, LED sends light.LED brightness is compared with Example 1
It is slightly bright.
Embodiment 5：
1. redox graphene is prepared：
Graphene oxide is prepared first：The concentrated sulfuric acid (25mL) is placed in into beaker (250mL), sequentially add graphite powder (3g),
Potassium peroxydisulfate (4g), phosphorus pentoxide (4g), in being placed in water-bath (80 DEG C).Mixture is filtered, water Jing after magneton stirring 5h
Neutrality is washed till, drying in baking oven (60 DEG C) is placed in.Under condition of ice bath, the concentrated sulfuric acid (100mL) is slowly added to place above-mentioned dry
The beaker of dry mixture and sodium nitrate (1g), and potassium permanganate (10g) is slowly added in batches, after strong stirring 2h, it is warming up to 35
DEG C, react 4h.Deionized water (800mL) is slow added into, 30min is stirred, then is warming up to 90 DEG C, continuation stirring 30min.Add
Hydrogen peroxide (20mL), now solution presentation glassy yellow.Deionized water dilutes aforesaid liquid, and with decantation acid is gone repeatedly, then
Load bag filter to dialyse 2 weeks, to remove the foreign ion in solution, until solution is in neutrality.Finally solution is diluted into concentration
For 0.04mg/mL, and under condition of ice bath after ultrasonically treated 2h (power 960W), then centrifugation (15min), supernatant is taken,
As graphene oxide suspension.
Redox graphene is prepared again：Fructose (fructose and graphene oxide are added in graphene oxide suspension
Mass ratio is 20：1) pH value for, and using ammoniacal liquor adjusting solution is allowed to be maintained in the range of 9-10.Water-bath 2h under the conditions of 95 DEG C.
By said mixture Jing filtering with microporous membrane, and neutrality is washed till using deionized water.Remaining solid is placed in 60 DEG C of baking ovens and is done
Dry 12h, and obtain redox graphene with agate mortar grinding.
2. Graphene conductive ink is prepared：
5.8mg Graphenes are taken, it is uniform with agate mortar grinding 15min, 574.2mg carbon blacks are then mixed into, continue to grind
15min obtains complex conductive fillerses.Ethanol, ethylene glycol, glycerine, the deionization of 12mL, 30mL, 30mL, 51mL are measured respectively
Water, mixes 10min and obtains mixed solvent.Complex conductive fillerses and carboxymethyl cellulose are sequentially added in above-mentioned mixed solvent
Plain sodium (232mg), is placed in carrying out ultrasonically treated (ultrasonically treated condition in ultrasonic wave plant cell pulverizer：Ice bath, power
960W、30min).Subsequently, above-mentioned solution is placed in supercentrifuge and is centrifuged (centrifugation condition：Rotating speed
8000r/min, time 15min), gained supernatant is Graphene conductive ink.
3. inkjet printing flexible-paper-base conducting wire：
First, according to experiment, the demand of test, using software Adobe Illustrator (CS6, Adobe system house)
Design the discernible bitmap file of printer；Then, 60ml Graphene conductive inks are measured, the company for loading ink-jet printer supplies
In device, and device will be even supplied to install on a printer；It is with weight pound cartridge paper (S041259, Chinese Epson Co., Ltd)
Base material, installs paper substrate printed material；Finally, finally, the width of same conducting wire keeps constant, repeatedly inkjet printing 10
It is secondary, obtain inkjet printing flexible-paper-base conducting wire (length × wide, 50mm × 2mm).
4. the post processing of inkjet printing flexible-paper-base conducting wire：
Inkjet printing flexible-paper-base conducting wire is placed in into sintering processes 5min in 100 DEG C of baking ovens.
Tested using the circuit arrangement figure shown in Fig. 7 in embodiment 1, connected inkjet printing flexible-paper-base conducting wire
3 (length × wide, 20mm × 2mm) are used as conducting element.Closing of circuit, LED sends light.LED brightness is basic with embodiment 1
It is identical.
Graphene is prepared electrically conductive ink by the present invention, can not only make full use of the good of Graphene
Electric conductivity, and appropriate carbon black can prevent the reunion of graphene film in ink system, so as to ensure the good of ink system
Good electric conductivity.In addition, conductive particle is uniformly distributed in ink so that conductive particle forms stable dispersion with solvent
System, and then improve the printing stability of compound oil ink system.The invention by the use of Graphene and carbon black mixture as conductive oil
The conductive filler of ink, preparation obtains the excellent Graphene conductive ink of electric conductivity, and realizes that inkjet printing flexible-paper-base is conductive
The preparation of circuit.Present invention process is simple, the flexible-paper-base conducting wire of inkjet printing have good acid resistance, uniformity,
Bendability, bending property and electric conductivity.The invention is expected to be applied in printed electronic product, meets the batch of printed electronic product
The development trend of change, large area, low cost and flexibility, with higher economic benefit and environmental benefit.
Claims (10)
1. the preparation method of Graphene conductive ink, it is characterised in that：Grinding after carbon black and Graphene mixing is obtained into composite guide
Electric filler；Measure the ethanol of 10-14mL, 28-32mL, 28-32mL, 49-53mL, ethylene glycol, glycerine, deionized water respectively to mix
Close stirring and obtain mixed solvent；Complex conductive fillerses 580-620mg and sodium carboxymethylcellulose are added to be carried out in mixed solvent
It is ultrasonically treated, it is then centrifuged for separating, gained supernatant is Graphene conductive ink；Graphene accounts for the quality of complex conductive fillerses
Than for 1%～30%.
2. the preparation method of Graphene conductive ink according to claim 1, it is characterised in that：Sodium carboxymethylcellulose is
The 40～80% of complex conductive fillerses quality.
3. the preparation method of Graphene conductive ink according to claim 1, it is characterised in that：The Graphene is by following
It is prepared by method：
With natural graphite powder as raw material, graphene oxide is prepared using Hummers methods, using reducing agent redox graphene,
Obtain redox graphene.
When preparing graphene oxide using Hummers methods, graphite powder, potassium peroxydisulfate, phosphorus pentoxide, sodium nitrate, potassium permanganate
Mass ratio be 3：4：4：1：10.
4. the preparation method of Graphene conductive ink according to claim 3, it is characterised in that：When preparing Graphene, also
Former agent is vitamin C, glucose, fructose.
5. the preparation method of Graphene conductive ink according to claim 3, it is characterised in that：The reduction-oxidation graphite
During alkene, the recovery time is 2～4h, and reduction temperature is 90 DEG C～95 DEG C, and reducing agent is 1 with the mass ratio of graphene oxide：10～
20。
6. the graphene conductive oil that prepared by a kind of preparation method of Graphene conductive ink according to described in any claim 1-5
Ink.
7. inkjet printing flexible-paper-base conducting wire, is characterized in that：It is to be prepared from by the following method：Graphene conductive
Ink loads ink-jet printer, and inkjet printing is carried out on paper substrate printed material, obtains flexible-paper-base conducting wire.
8. inkjet printing flexible-paper-base conducting wire according to claim 7, it is characterised in that：To same conducting wire
Width keep constant, repeated multiple times printing, and printing times be less than 10 times.
9. inkjet printing flexible-paper-base conducting wire according to claim 7, it is characterised in that：By the paper after inkjet printing
Base is placed in baking oven, and flexible-paper-base conducting wire is sintered.
10. inkjet printing flexible-paper-base conducting wire according to claim 9, it is characterised in that：During sintering, sintering temperature
For 50 DEG C～100 DEG C, sintering time is 5～10min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610964875.2A CN106634221A (en) | 2016-10-28 | 2016-10-28 | Graphene conductive ink, preparation method therefor and inkjet-printed flexible paper-based conductive line |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610964875.2A CN106634221A (en) | 2016-10-28 | 2016-10-28 | Graphene conductive ink, preparation method therefor and inkjet-printed flexible paper-based conductive line |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106634221A true CN106634221A (en) | 2017-05-10 |
Family
ID=58820757
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610964875.2A Pending CN106634221A (en) | 2016-10-28 | 2016-10-28 | Graphene conductive ink, preparation method therefor and inkjet-printed flexible paper-based conductive line |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106634221A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107686688A (en) * | 2017-09-23 | 2018-02-13 | 南京林业大学 | Graphene/polypyrrole/carbon black conductive ink and preparation method and flexible-paper-base writing conducting wire |
| CN108359307A (en) * | 2018-03-23 | 2018-08-03 | 南京林业大学 | High dispersive graphene heat conduction water paint and preparation method thereof |
| CN109559851A (en) * | 2018-11-15 | 2019-04-02 | 中南大学 | A kind of graphene electrocardioelectrode and preparation method thereof |
| CN109618433A (en) * | 2018-12-20 | 2019-04-12 | 四川省安德盖姆石墨烯科技有限公司 | A kind of graphene safe voltage heating film |
| CN110499072A (en) * | 2019-08-20 | 2019-11-26 | 株洲市长明石墨烯材料有限公司 | A kind of watersoluble plumbago alkene electrically conductive ink and preparation method thereof |
| CN112261801A (en) * | 2020-10-27 | 2021-01-22 | 惠州市特创电子科技有限公司 | Manufacturing method of multilayer circuit board and multilayer circuit board |
| CN113429836A (en) * | 2021-07-28 | 2021-09-24 | 陕西科技大学 | Graphene/carbon black conductive ink and preparation method and application thereof |
| US20220007515A1 (en) * | 2019-08-29 | 2022-01-06 | Hewlett-Packard Development Company, L.P. | Flexible printed articles |
| CN114989472A (en) * | 2021-03-02 | 2022-09-02 | 天津理工大学 | Application of conductive ink in reducing resistivity of flexible polar plate after being bent for multiple times |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103834235A (en) * | 2014-02-20 | 2014-06-04 | 江苏格美高科技发展有限公司 | Conductive graphene carbon slurry printing ink and preparation method thereof |
-
2016
- 2016-10-28 CN CN201610964875.2A patent/CN106634221A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103834235A (en) * | 2014-02-20 | 2014-06-04 | 江苏格美高科技发展有限公司 | Conductive graphene carbon slurry printing ink and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 凌云星等: "《实用油墨技术指南》", 30 November 2007, 印刷工业出版社 * |
| 石小梅等: "石墨烯导电油墨的研究进展", 《包装工程》 * |
| 阎素斋等: "《特种印刷油墨》", 31 May 2004, 化学工业出版社 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107686688A (en) * | 2017-09-23 | 2018-02-13 | 南京林业大学 | Graphene/polypyrrole/carbon black conductive ink and preparation method and flexible-paper-base writing conducting wire |
| CN108359307A (en) * | 2018-03-23 | 2018-08-03 | 南京林业大学 | High dispersive graphene heat conduction water paint and preparation method thereof |
| CN109559851A (en) * | 2018-11-15 | 2019-04-02 | 中南大学 | A kind of graphene electrocardioelectrode and preparation method thereof |
| CN109618433A (en) * | 2018-12-20 | 2019-04-12 | 四川省安德盖姆石墨烯科技有限公司 | A kind of graphene safe voltage heating film |
| CN109618433B (en) * | 2018-12-20 | 2022-04-08 | 四川省中科烯捷石墨烯科技有限公司 | Graphene safe voltage heating film |
| CN110499072A (en) * | 2019-08-20 | 2019-11-26 | 株洲市长明石墨烯材料有限公司 | A kind of watersoluble plumbago alkene electrically conductive ink and preparation method thereof |
| US20220007515A1 (en) * | 2019-08-29 | 2022-01-06 | Hewlett-Packard Development Company, L.P. | Flexible printed articles |
| CN112261801A (en) * | 2020-10-27 | 2021-01-22 | 惠州市特创电子科技有限公司 | Manufacturing method of multilayer circuit board and multilayer circuit board |
| CN114989472A (en) * | 2021-03-02 | 2022-09-02 | 天津理工大学 | Application of conductive ink in reducing resistivity of flexible polar plate after being bent for multiple times |
| CN114989472B (en) * | 2021-03-02 | 2023-04-14 | 天津理工大学 | Application of conductive ink in reducing resistivity of flexible polar plate after being bent for multiple times |
| CN113429836A (en) * | 2021-07-28 | 2021-09-24 | 陕西科技大学 | Graphene/carbon black conductive ink and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106634221A (en) | Graphene conductive ink, preparation method therefor and inkjet-printed flexible paper-based conductive line | |
| CN105348967B (en) | A kind of aqueous highly conductive coating of carbon system and its application | |
| CN101805538B (en) | Lower-temperature sintered conductive ink | |
| CN106128555B (en) | A kind of highly conductive crystal silicon solar batteries front electrode silver slurry and preparation method thereof | |
| WO2018228407A1 (en) | Graphene/metal nanobelt composite conductive ink, preparation method therefor and application thereof | |
| Pasta et al. | Aqueous supercapacitors on conductive cotton | |
| Mou et al. | Facile preparation of stable reactive silver ink for highly conductive and flexible electrodes | |
| CN108046338B (en) | A kind of cobalt doped molybdenum disulfide original position electrode and preparation method thereof | |
| CN107686688A (en) | Graphene/polypyrrole/carbon black conductive ink and preparation method and flexible-paper-base writing conducting wire | |
| CN103923529B (en) | A kind of compound oil ink, flexible super capacitor electrode and preparation method thereof | |
| CN103440901B (en) | Low cost crystal silicon solar energy battery unleaded back silver paste and preparation method | |
| CN104445138B (en) | A kind of hydro-thermal method prepares the method for high conductivity Carbon Materials | |
| CN107936686A (en) | A kind of compound carbon-based water-based electric heating ink of graphene and preparation method thereof | |
| Kim et al. | Investigations into the electrochemical characteristics of nickel oxide hydroxide/multi-walled carbon nanotube nanocomposites for use as supercapacitor electrodes | |
| CN105556617A (en) | Conductive filler, method for producing same, conductive paste and method for producing conductive paste | |
| CN110862716A (en) | Graphene composite conductive ink and preparation method thereof | |
| CN111799449A (en) | Preparation method of composite negative electrode material and composite negative electrode material for lithium secondary battery | |
| CN105694594A (en) | An aqueous graphene conductive printing ink suitable for screen printing and a preparing method thereof | |
| CN104009159A (en) | Perovskite-based thin-film solar cell and manufacturing method thereof | |
| CN106986331B (en) | A kind of graphene-tin-antiomony oxide composite conducting material and preparation method thereof | |
| CN105374568B (en) | Graphite-phase C3N4The preparation method of/CNT combined counter electrode | |
| CN102114546A (en) | Method for preparing spherical silver powder | |
| CN108962425A (en) | A kind of preparation method of graphene conductive slurry | |
| WO2011021773A2 (en) | Method for manufacturing carbon nanotube micro-balls, carbon nanotube micro-balls manufactured by same, and method for manufacturing an electrode using the carbon nanotube micro-balls | |
| CN109841426B (en) | Graphene-based flexible electrode and preparation method thereof |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170510 |
|
| RJ01 | Rejection of invention patent application after publication |