CN113956720A - Preparation method of flexible conductive film - Google Patents
Preparation method of flexible conductive film Download PDFInfo
- Publication number
- CN113956720A CN113956720A CN202111428438.6A CN202111428438A CN113956720A CN 113956720 A CN113956720 A CN 113956720A CN 202111428438 A CN202111428438 A CN 202111428438A CN 113956720 A CN113956720 A CN 113956720A
- Authority
- CN
- China
- Prior art keywords
- solvent
- conductive film
- graphene
- method comprises
- 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
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 82
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 40
- 238000009835 boiling Methods 0.000 claims abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 22
- 238000000926 separation method Methods 0.000 claims abstract description 15
- 238000005516 engineering process Methods 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000007641 inkjet printing Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims abstract description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 124
- 238000000034 method Methods 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000008096 xylene Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 38
- 239000000976 ink Substances 0.000 description 37
- 230000000052 comparative effect Effects 0.000 description 8
- 229920000139 polyethylene terephthalate Polymers 0.000 description 8
- 239000005020 polyethylene terephthalate Substances 0.000 description 8
- -1 graphite alkene Chemical class 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000007639 printing Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000010409 thin film Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 1
- AWFYPPSBLUWMFQ-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,6,7-tetrahydropyrazolo[4,3-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=C2 AWFYPPSBLUWMFQ-UHFFFAOYSA-N 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000011960 computer-aided design Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002277 temperature effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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
- C09D11/36—Inkjet printing inks based on non-aqueous solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention belongs to the technical field of optical materials, and particularly discloses a preparation method of a flexible conductive film, which comprises the following steps: step 1, firstly, dispersing graphene in a first solvent, wherein the boiling point of the first solvent is higher than 150 ℃, carrying out heating ultrasonic stirring, heating the dispersed solution to be higher than the boiling point of the first solvent, and then adding a second solvent into the solution, wherein the boiling point of the second solvent is lower than 150 ℃; carrying out centrifugal separation on the remaining solution, and carrying out ultrasonic stirring to obtain graphene conductive ink; step 2: coating conductive ink on a flexible transparent substrate by adopting an ink-jet printing electronic technology; and step 3: stretching the substrate in the transverse direction or the longitudinal direction to obtain a film-shaped flexible conductive film; and then drying the conductive film. The conductive ink obtained by the scheme of the invention has moderate viscosity, does not block a nozzle, has moderate contact angle with a substrate, has good wettability and is beneficial to coating the conductive ink on the substrate.
Description
Technical Field
The invention belongs to the technical field of optical materials, and particularly relates to a preparation method of a flexible conductive film.
Background
The flexible conductive film is a film with a conductive function, is widely applied to various fields such as solar cells, displays, photoelectrons and the like, and is the focus of research of various large research institutions in the field.
Inkjet Printing Electronic Technology (IPET) is a non-contact material spraying process which is drop-on-demand, can directly print out a circuit with a complex geometric shape from a computer aided design, has the potential of simplifying a circuit manufacturing process and rapidly providing a personalized electronic pattern besides high material utilization rate and low manufacturing cost and being capable of large-scale manufacturing compared with a traditional method, and is a new trend of the development of the electronic manufacturing industry. Based on this, IPET has been successfully applied to the development of various electronic devices, and is also one of the important ways to prepare flexible conductive films.
When the IPET technology is adopted to prepare the flexible conductive film, the conductive ink is a key factor influencing the product performance and quality, and the requirement on the stability of the conductive ink is particularly high. Since graphene has good conductivity and mechanical flexibility and strong stability, graphene is developed as a raw material of conductive ink. And when the graphene conductive ink is prepared, the graphene is well dispersed, which is a very critical ring. However, researchers find that if graphene prepared at present needs to have better dispersibility, and finally has better viscosity and wettability when a conductive film is prepared by printing, some solvents with certain toxicity need to be added, so that the graphene conductive ink cannot be widely applied and popularized in industrial production. If the addition of the toxic solvents is avoided, other nontoxic alternative solvents are added instead, so that the graphene cannot be well dispersed under the same condition (such as the same dispersion time), and the viscosity and wettability are poor when the conductive film is finally prepared by printing, so that the performance of the finished conductive film is influenced.
In view of the above, the present application provides a method for preparing a flexible conductive film using an IPET with an improved conductive ink.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a method for preparing a flexible conductive film by using IPET (interpenetrating polymer network) of improved conductive ink.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a flexible conductive film comprises the following steps:
step 1: preparing conductive ink, namely dispersing graphene in a first solvent, heating and ultrasonically stirring the first solvent, heating the dispersed solution to be above the boiling point of the first solvent, and adding a second solvent into the solution, wherein the boiling point of the second solvent is lower than 150 ℃; carrying out centrifugal separation on the remaining solution, and carrying out ultrasonic stirring to obtain graphene conductive ink;
step 2: coating the conductive ink obtained in the step 1 on a flexible transparent substrate by adopting an ink-jet printing electronic technology;
and step 3: performing transverse or longitudinal stretching treatment on the substrate in the step 2 to obtain a film-shaped flexible conductive film; and then drying the conductive film.
Compared with the prior art, the technical scheme has the following beneficial effects:
1. by adopting the technical scheme, the obtained conductive ink has moderate viscosity, so that when the final conductive film is prepared by adopting an ink jet printing technology, the phenomenon of nozzle blockage caused by overhigh viscosity can be avoided, and the problem of unfavorable printing caused by insufficient viscosity can be avoided; the contact angle between the conductive ink and the substrate is moderate, good wettability is shown, printing of the conductive ink on the substrate is facilitated, and the finally formed conductive film has good performance; in addition, the conductive ink has few toxic components, so that the whole conductive film is more environment-friendly and safer to prepare, and is beneficial to popularization and application in industrial production.
2. In fact, through continuous research and experimental analysis, the inventors find that solvents with good dispersibility and toxicity generally have higher boiling points, and solvents with no toxicity and poor dispersibility generally have lower boiling points. Then, the inventor vigorously tries to share the two types of solvents, skillfully utilizes the boiling point difference of the two types of solvents, and finally obtains the technical scheme through experimental grope. The analysis obtains, in this scheme, owing to adopt the higher first solvent of boiling point, make graphite alkene can obtain abundant dispersion, simultaneously through heating to above the boiling point of first solvent, make first solvent volatilize fast, and add the lower second solvent of boiling point, the second solvent is when replacing first solvent, also constantly volatilize under the high temperature effect, operate like this, guarantee that graphite alkene obtains high dispersion under the effect of first solvent on the one hand, and guarantee that the solution has sufficient tension, on the other hand, first solvent is under the boiling effect, the low temperature second solvent that gets into can replace first solvent fast, guarantee that first solvent is when volatilizing, graphite alkene can also keep good dispersibility, and then let the conductive ink of preparation have better viscidity and wettability, it has good performance to guarantee that the last conducting film of printing has.
Further, the first solvent in step 1 is dimethylformamide. Dimethylformamide has a good dispersing effect on graphene, and can be quickly volatilized after boiling, so that the second solvent can quickly replace the solvent function of the second solvent.
Further, in the step 1, the second solvent is one of xylene or toluene. Xylene or toluene is used as a replacement solvent, and experiments prove that the short-term stability of the conductive ink is strong, but the conductive ink can be slightly sunk after being placed for a long time.
Further, in the step 1, the second solvent is one of ethanol or acetone. Ethanol or acetone is used as a substitute solvent, so that the stability is good, the problem of bottom precipitation of the ink after long-time standing is avoided, and the method is suitable for industrial batch production.
Further, in the step 1, the heating temperature is 90-110 ℃, and the ultrasonic stirring time is not less than 30 min. This enables the graphene to be rapidly dispersed in the first solvent.
Further, in the step 1, the mass ratio of the graphene to the sum of the first solvent and the second solvent is (4-7): (93-96), wherein the volume ratio of the first solvent to the second solvent is 1: 1. experiments prove that the viscosity and the wetting angle of the conductive ink obtained by selection can meet the requirements of ink jet printing, and the nozzle cannot be blocked.
Further, in the step 1, the rotation speed of centrifugal separation is not lower than 3000 r/min, and the centrifugal time is not lower than 15 min. This ensures that large particles in the solution are separated out.
Further, in the step 1, after the second solvent is added, the mixture is cooled to room temperature. This arrangement slows the evaporation of the second solvent.
Further, in the step 3, the drying temperature of the conductive film is not more than 80 ℃, and the drying time is not more than 15 min.
Detailed Description
The present invention will be described in further detail below, and specific embodiments thereof will be described.
Example 1:
a preparation method of a flexible conductive film comprises the following steps:
step 1: the conductive ink is prepared by adopting an electrochemical stripping technology to prepare graphene used as a raw material in the embodiment, wherein a first solvent is Dimethylformamide (DMF), and a second solvent is xylene (boiling point is 140 ℃).
Firstly, graphene is dispersed in a Dimethylformamide (DMF) solvent, the dispersed solution is heated at 100 ℃ and ultrasonically stirred for 30min, then the solution is heated to the boiling point (153 ℃) of the DMF, xylene is added when the DMF is boiled, and the solution is naturally cooled to the room temperature, wherein the mass ratio of the graphene to the solvent (DMF: xylene) is 5: 95, and the volume ratio of DMF to xylene is 1: 1.
and (3) carrying out centrifugal separation on the residual graphene and the solvent, wherein the rotating speed of the separation is 3000 r/min, centrifuging for 15min, removing large particles, and ultrasonically stirring the centrifuged solution at room temperature for 30min to obtain a solution with a DMF (dimethyl formamide): graphene conductive ink of xylene.
Step 2: the conductive ink prepared in the step 1 is coated on a flexible transparent substrate by adopting an ink jet printing electronic technology, wherein the flexible transparent substrate is polyethylene terephthalate (PET).
And step 3: and (3) stretching the substrate in the step (2) transversely or longitudinally to form a thin film flexible conductive film, and drying the conductive film at 80 ℃ for 15min, wherein the prepared conductive film can be applied to the fields of Liquid Crystal Displays (LCDs), solar cells, microelectronic ITO conductive film glass, photoelectrons and the like.
Example 2:
the difference from embodiment 1 is that a method for manufacturing a flexible conductive film includes the steps of:
step 1: the conductive ink is prepared by adopting an electrochemical stripping technology to prepare graphene used as a raw material in the embodiment, and Dimethylformamide (DMF) and toluene are used as solvents.
Firstly, graphene is dispersed in a Dimethylformamide (DMF) solvent, the dispersed solution is heated at 100 ℃ and ultrasonically stirred for 30min, then the solution is heated to the boiling point (153 ℃) of the DMF, toluene is added after the DMF is boiled, and the solution is naturally cooled to the room temperature, wherein the mass ratio of the graphene to the solvent (DMF: toluene) is 0.5: 95, and the volume ratio of DMF to toluene is 1: 1.
and (3) carrying out centrifugal separation on the residual graphene and the solvent, wherein the rotating speed of the separation is 3000 r/min, centrifuging for 15min, removing large particles, and ultrasonically stirring the centrifuged solution at room temperature for 30min to obtain a solution with a DMF (dimethyl formamide): toluene in graphene conductive ink.
Step 2: the conductive ink prepared in the step 1 is coated on a flexible transparent substrate by adopting an ink jet printing electronic technology, wherein the flexible transparent substrate is polyethylene terephthalate (PET).
And step 3: and (3) stretching the substrate in the step 2 in the transverse direction or the longitudinal direction to form a thin film flexible conductive film, and drying the conductive film at 80 ℃ for 15 min.
Example 3:
the difference from example 1 is that: a preparation method of a flexible conductive film comprises the following steps:
step 1: the conductive ink is prepared by adopting an electrochemical stripping technology to prepare graphene used as a raw material in the embodiment, and dimethyl formamide (DMF) and ethanol are used as solvents.
Firstly, graphene is dispersed in a Dimethylformamide (DMF) solvent, the dispersed solution is heated at 100 ℃ and ultrasonically stirred for 30min, then the solution is heated to the boiling point (153 ℃) of the DMF, ethanol is added after the DMF is boiled, and the solution is naturally cooled to the room temperature, wherein the mass ratio of the graphene to the solvent (DMF: ethanol) is 5: 95, and the volume ratio of DMF to ethanol is 1: 1.
and (3) carrying out centrifugal separation on the residual graphene and the solvent, wherein the rotating speed of the separation is 3000 r/min, centrifuging for 15min, removing large particles, and ultrasonically stirring the centrifuged solution at room temperature for 30min to obtain a solution with a DMF (dimethyl formamide): graphene conductive ink of ethanol.
Step 2: the conductive ink prepared in the step 1 is coated on a flexible transparent substrate by adopting an ink jet printing electronic technology, wherein the flexible transparent substrate is polyethylene terephthalate (PET).
And step 3: and (3) stretching the substrate in the step 2 in the transverse direction or the longitudinal direction to form a thin film flexible conductive film, and drying the conductive film at 80 ℃ for 15 min.
Example 4:
the difference from example 1 is that: a preparation method of a flexible conductive film comprises the following steps:
step 1: the conductive ink is prepared by adopting an electrochemical stripping technology to prepare graphene used as a raw material in the embodiment, and dimethyl formamide (DMF) and acetone are used as solvents.
Firstly, graphene is dispersed in a Dimethylformamide (DMF) solvent, the dispersed solution is heated at 100 ℃ and ultrasonically stirred for 30min, then the solution is heated to the boiling point (153 ℃) of the DMF, acetone is added when the DMF is boiled, and the temperature is reduced to room temperature, wherein the mass ratio of the graphene to the solvent (DMF: acetone) is 5: 95, and the volume ratio of DMF to acetone is 1: 1.
and (3) carrying out centrifugal separation on the residual graphene and the solvent, wherein the rotating speed of the separation is 3000 r/min, centrifuging for 15min, removing large particles, and ultrasonically stirring the centrifuged solution at room temperature for 30min to obtain a solution with a DMF (dimethyl formamide): acetone graphene conductive ink.
Step 2: the conductive ink prepared in the step 1 is coated on a flexible transparent substrate by adopting an ink jet printing electronic technology, wherein the flexible transparent substrate is polyethylene terephthalate (PET).
And step 3: and (3) stretching the substrate in the step 2 in the transverse direction or the longitudinal direction to form a thin film flexible conductive film, and drying the conductive film at 80 ℃ for 15 min.
Example 5 to example 7:
the difference from the embodiment 1 is that the mass ratio of the graphene to the solvent in the embodiment 5 is 4: 96; the mass ratio of graphene to solvent in example 6 was 6: 94; the mass ratio of graphene to solvent in example 7 was 7: 93.
Example 8:
the difference from the embodiment 3 is that after boiling DMF for 2min in the step 1, the temperature is reduced to more than 70 ℃, then the second solvent ethanol is added, and the centrifugal separation is carried out after natural cooling to the room temperature.
Example 9:
the difference from the embodiment 4 is that after boiling DMF for 2min in the step 1, the temperature is reduced to over 55 ℃, then the second solvent acetone is added, and the centrifugal separation is carried out after natural cooling to the room temperature.
Comparative example 1:
the difference from example 1 is that the conductive ink contains only DMF as one solvent, i.e. DMF is not heated to boiling in step 1 and no second solvent is added.
Comparative example 2:
the difference from example 1 is that in step 1 the DMF was not heated to boiling, but the second solvent was added directly.
The conductive inks obtained in examples 1 to 9 and comparative examples 1 to 2 were examined for viscosity and contact angle.
The experimental results are as follows:
table 1 shows the viscosity and contact angle of the conductive inks obtained in examples 1 to 9 and comparative examples 1 to 2
| Viscosity of the oil | Contact angle | |
| Example 1 | 9 | 42 |
| Example 2 | 12 | 38 |
| Example 3 | 10 | 24 |
| Example 4 | 10 | 22 |
| Example 5 | 9 | 40 |
| Example 6 | 10 | 42 |
| Example 7 | 11 | 43 |
| Example 8 | 10 | 22 |
| Example 9 | 10 | 20 |
| Comparative example 1 | 8 | 48 |
| Comparative example 2 | 6 | 50 |
As can be seen from Table 1 above, the conductive inks prepared in examples 1-9 exhibited low contact angles and moderate viscosities (9-12), and when inkjet printing was used, the nozzle clogging phenomenon was not observed due to excessive viscosity, and the adhesion degradation problem due to insufficient viscosity was not observed.
In addition, the conductive film samples obtained in examples 1 to 9 and comparative examples 1 to 2 were subjected to a bending cycle test for 10 times, and the resistance change of the conductive film before and after 10 times of bending was detected, and it was found that the resistance change rates obtained in examples 1 to 2 and examples 5 to 7 were 0.01% to 0.02%, the resistance change rates obtained in examples 3 to 4 and examples 8 to 9 were 0.02% to 0.03%, the resistance change rates indicating the stability of the electrical connection performance of the conductive film were all lower than 0.04%, and the resistance change rates of the conductive films in comparative examples 1 to 2 were all higher than 0.05%, and the stability was lowered.
Therefore, as shown in table 1, although the conductive inks obtained in examples 1 to 2 and 5 to 7 have relatively high contact angles and slightly lower wettability than the conductive inks obtained in examples 3 to 4 and 8 to 9 in the coating operation, the stability of the electrical connection performance is high, and therefore, the component of the second solvent can be selected according to the practical application of the conductive film.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (9)
1. A preparation method of a flexible conductive film is characterized by comprising the following steps: the method comprises the following steps:
step 1: preparing conductive ink, namely dispersing graphene in a first solvent, heating and ultrasonically stirring the first solvent, heating the dispersed solution to be above the boiling point of the first solvent, and adding a second solvent into the solution, wherein the boiling point of the second solvent is lower than 150 ℃; carrying out centrifugal separation on the remaining solution, and carrying out ultrasonic stirring to obtain graphene conductive ink;
step 2: coating the conductive ink obtained in the step 1 on a flexible transparent substrate by adopting an ink-jet printing electronic technology;
and step 3: performing transverse or longitudinal stretching treatment on the substrate in the step 2 to obtain a film-shaped flexible conductive film; and then drying the conductive film.
2. The method of claim 1, wherein the method comprises: the first solvent in the step 1 is dimethylformamide.
3. The method of claim 1, wherein the method comprises: in the step 1, the second solvent is one of xylene or toluene.
4. The method of claim 1, wherein the method comprises: in the step 1, the second solvent is one of ethanol or acetone.
5. The method of claim 1, wherein the method comprises: in the step 1, the heating temperature is 90-110 ℃, and the ultrasonic stirring time is not less than 30 min.
6. The method of claim 1, wherein the method comprises: in the step 1, the mass ratio of the graphene to the sum of the first solvent and the second solvent is (4-7): (93-96), wherein the volume ratio of the first solvent to the second solvent is 1: 1.
7. the method of claim 1, wherein the method comprises: in the step 1, the rotating speed of centrifugal separation is not lower than 3000 r/min, and the centrifugal time is not lower than 15 min.
8. The method of claim 1, wherein the method comprises: and in the step 1, after the second solvent is added, cooling to room temperature.
9. The method of claim 1, wherein the method comprises: in the step 3, the drying temperature of the conductive film is not more than 80 ℃, and the drying time is not more than 15 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111428438.6A CN113956720A (en) | 2021-11-26 | 2021-11-26 | Preparation method of flexible conductive film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111428438.6A CN113956720A (en) | 2021-11-26 | 2021-11-26 | Preparation method of flexible conductive film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113956720A true CN113956720A (en) | 2022-01-21 |
Family
ID=79472338
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111428438.6A Pending CN113956720A (en) | 2021-11-26 | 2021-11-26 | Preparation method of flexible conductive film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113956720A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130108932A (en) * | 2012-03-26 | 2013-10-07 | 한국화학연구원 | Manufacturing method of graphene compound with excellent dispersability in solvent and thereof product |
| CN103449420A (en) * | 2013-08-22 | 2013-12-18 | 中国科学院金属研究所 | High-quality graphene dispersion method and film preparation method |
| CN104071778A (en) * | 2014-06-20 | 2014-10-01 | 宁波墨西科技有限公司 | Graphene dispersion liquid and method for preparing graphene material power |
| CN106349923A (en) * | 2016-08-26 | 2017-01-25 | 中国科学院上海硅酸盐研究所 | Preparation method of grapheme-containing fluorinated polyimide composite corrosive-resisting coating |
| CN106928773A (en) * | 2017-05-08 | 2017-07-07 | 华侨大学 | It is a kind of to can be used for graphene composite conductive ink of inkjet printing and preparation method thereof |
| CN108251907A (en) * | 2017-12-05 | 2018-07-06 | 重庆石墨烯研究院有限公司 | A kind of High-performance graphene-polyvinyl alcohol composite fiber preparation method |
| CN108610743A (en) * | 2018-04-18 | 2018-10-02 | 长沙新材料产业研究院有限公司 | A kind of conductive ink composition and preparation method thereof |
| WO2021102523A1 (en) * | 2019-11-29 | 2021-06-03 | Royal Melbourne Institute Of Technology | Water-redispersible graphene powder |
| CN113061369A (en) * | 2020-01-02 | 2021-07-02 | 中国科学院福建物质结构研究所 | Graphene conductive ink, graphene conductive film, and preparation methods and applications of graphene conductive ink and graphene conductive film |
-
2021
- 2021-11-26 CN CN202111428438.6A patent/CN113956720A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130108932A (en) * | 2012-03-26 | 2013-10-07 | 한국화학연구원 | Manufacturing method of graphene compound with excellent dispersability in solvent and thereof product |
| CN103449420A (en) * | 2013-08-22 | 2013-12-18 | 中国科学院金属研究所 | High-quality graphene dispersion method and film preparation method |
| CN104071778A (en) * | 2014-06-20 | 2014-10-01 | 宁波墨西科技有限公司 | Graphene dispersion liquid and method for preparing graphene material power |
| CN106349923A (en) * | 2016-08-26 | 2017-01-25 | 中国科学院上海硅酸盐研究所 | Preparation method of grapheme-containing fluorinated polyimide composite corrosive-resisting coating |
| CN106928773A (en) * | 2017-05-08 | 2017-07-07 | 华侨大学 | It is a kind of to can be used for graphene composite conductive ink of inkjet printing and preparation method thereof |
| CN108251907A (en) * | 2017-12-05 | 2018-07-06 | 重庆石墨烯研究院有限公司 | A kind of High-performance graphene-polyvinyl alcohol composite fiber preparation method |
| CN108610743A (en) * | 2018-04-18 | 2018-10-02 | 长沙新材料产业研究院有限公司 | A kind of conductive ink composition and preparation method thereof |
| WO2021102523A1 (en) * | 2019-11-29 | 2021-06-03 | Royal Melbourne Institute Of Technology | Water-redispersible graphene powder |
| CN113061369A (en) * | 2020-01-02 | 2021-07-02 | 中国科学院福建物质结构研究所 | Graphene conductive ink, graphene conductive film, and preparation methods and applications of graphene conductive ink and graphene conductive film |
Non-Patent Citations (2)
| Title |
|---|
| JIANTONG LI: "Efficient Inkjet Printing of Graphene", 《ADVANCED MATERIALS》 * |
| 邱欣斌等: "石墨烯导电油墨的研究进展", 《化工进展》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106782769B (en) | Flexible and transparent conductive laminated film of low roughness low square resistance and preparation method thereof | |
| CN103113786B (en) | Graphene conductive ink and preparation method thereof | |
| CN108770194B (en) | Preparation method of conductive silver paste for printed circuit | |
| TWI353808B (en) | Method for fabricating conductive pattern on flexi | |
| CN106251946B (en) | A kind of compound transparent electricity conductive film and preparation method thereof | |
| CN106992040A (en) | A kind of novel processing step of PEDOT flexible transparent electrodes | |
| CN103571275A (en) | Conductive ink composition, manufacturing method of conductive pattern and conductive circuit | |
| DE102016225051A1 (en) | INTERMEDIATE COMPOSITION FOR ELECTRONIC PRINTING | |
| US20110083886A1 (en) | Method of manufacturing electrode substrate | |
| CN113956720A (en) | Preparation method of flexible conductive film | |
| CA2852341C (en) | Conductive metal inks with polyvinylbutyral binder | |
| CN101976591B (en) | Transparent conductive film | |
| CN106297964A (en) | A kind of compound transparent electricity conductive film and preparation method thereof | |
| CN106298986A (en) | Negative electrode and preparation method thereof, solar units, compositions, thin film | |
| CN101665616B (en) | Liquid composition of polythienyl-based conducting polymer, conducting polymer film and application thereof | |
| CN108912845A (en) | A kind of quantum dot-doped silver ink and preparation method thereof | |
| CN108089366A (en) | A kind of color membrane substrates and preparation method thereof | |
| CN107545949A (en) | Transparent conductivity piece and its manufacture method | |
| CN105489313B (en) | High conductivity substrate and preparation method thereof | |
| CN103224761B (en) | The screen printing type conductive resin of adhesion strength excellence | |
| JP5046977B2 (en) | Conductive film and method for producing the same | |
| CN113498427B (en) | High conductivity printable inks for highly stretchable soft electronic devices and high conductivity superstretchable conductors obtainable therefrom | |
| JP2005530351A (en) | Materials for functional films of organic electronic devices, manufacturing methods thereof, and uses thereof | |
| CN110070957A (en) | High optical transmission and the flexible metal nano thin-film of electric conductivity and preparation method thereof | |
| CN111883286A (en) | Preparation method of transparent conductive film and transparent conductive film |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220121 |