CN114891399A - Graphene ink used for printing flexible devices and free of high-temperature post-treatment and preparation method thereof - Google Patents
Graphene ink used for printing flexible devices and free of high-temperature post-treatment and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 140
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000007639 printing Methods 0.000 title claims abstract description 14
- 239000006185 dispersion Substances 0.000 claims abstract description 43
- 239000007788 liquid Substances 0.000 claims abstract description 38
- 239000004094 surface-active agent Substances 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- FVTCRASFADXXNN-SCRDCRAPSA-N flavin mononucleotide Chemical compound OP(=O)(O)OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O FVTCRASFADXXNN-SCRDCRAPSA-N 0.000 claims description 27
- 229950001574 riboflavin phosphate Drugs 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 238000004108 freeze drying Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 8
- 239000001099 ammonium carbonate Substances 0.000 claims description 8
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000000020 Nitrocellulose Substances 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229920001220 nitrocellulos Polymers 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 1
- 229920001046 Nanocellulose Polymers 0.000 description 1
- -1 Polydimethylsiloxane Polymers 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229960003964 deoxycholic acid Drugs 0.000 description 1
- KXGVEGMKQFWNSR-LLQZFEROSA-N deoxycholic acid Chemical compound C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)[C@@H](O)C1 KXGVEGMKQFWNSR-LLQZFEROSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention relates to a graphene ink without high-temperature post-treatment for flexible device printing and a preparation method thereof. The graphene ink with extremely low surfactant content and high dispersion stability can be prepared by selecting parameters such as proper feed ratio, ultrasonic time, ultrasonic power, solvent ratio and the like. The content of the finally prepared ink surfactant is 0.05mg/mL at the lowest, the ratio of the surfactant to graphene is 1:20, the absolute value of Zeta potential is as high as 50-70mV, the transverse size of graphene sheet layers in dispersion liquid is 3-10 micrometers, the thickness is only 1-1.5nm, the lapping among two-dimensional graphene sheet layers is not influenced by a trace amount of surfactant, the conductivity of a graphene pattern is not influenced, and high-temperature post-treatment is not needed.
Description
Technical Field
The invention belongs to the field of 3D printing materials, and relates to a preparation method of graphene ink for uniform droplet ejection without high-temperature post-treatment, in particular to a preparation method of graphene ink with ultralow-concentration riboflavin sodium phosphate dispersion facing a flexible substrate.
Background
Due to the excellent conductivity and flexibility, high light transmittance and huge specific surface area, the graphene has great advantages in the aspect of preparing flexible photoelectric functional devices with high flexibility and scalability. The uniform graphene microdroplet spraying technology has the advantages of low cost, customization, direct molding on various substrates and the like, and is a preparation method of a flexible microstructure functional device with great advantages and development potentials. The development of ink which faces to a flexible substrate, is stably dispersed and is suitable for spraying is the key for realizing the rapid preparation of the graphene flexible functional device.
Due to inherent chemical inertness and hydrophobicity of the surface of graphene, graphene ink is extremely prone to agglomeration and sedimentation, a large amount of non-conductive surfactant is often added to keep the graphene ink stably dispersed in the existing method, and then the surfactant is removed in a post-treatment mode to restore the conductivity of a printed pattern. At present, the decomposition temperature of the graphene surfactant is generally 300-450 ℃, however, the tolerance temperature of common substrates of flexible photoelectric devices, such as Polydimethylsiloxane (PDMS), nanocellulose (CNF), and the like, is below 200 ℃, the removal temperature of the surfactant in the graphene pattern and the tolerance temperature of the flexible substrate are mutually restricted, and the practical application of the graphene in the flexible photoelectric devices is influenced. A new surfactant which does not need high-temperature post-treatment is sought, the solution dispersibility is improved, the conductivity is considered, and the method is an effective method for solving the problem of the graphene ink for uniform micro-droplet jetting at present.
The Chinese invention patent with the application publication number of CN 111748242A discloses a printing nitrocellulose graphene ink and a preparation method thereof, and the prepared ink has the advantages of environmental stability and printing adaptability and can be used for ink-jet printing of flexible graphene films. However, since the ink contains a large amount of non-conductive nitrocellulose, the graphene film can restore conductivity after being annealed at a high temperature of 350 ℃.
Disclosure of Invention
In order to solve the problems that the dispersing agent content of the ink for flexible substrate printing is high and the ink needs to be removed at high temperature, the invention provides a preparation method of graphene ink for uniform droplet jetting, which does not need high-temperature post-treatment. The method utilizes efficient surfactant riboflavin sodium phosphate to disperse graphene in ultra-low concentration (1:20), and regulates and controls ink fluid parameters through the synergistic action of a mixed solvent and a surfactant, so that the ink parameters are in an ejectable range. The extremely low content of surfactant in the graphene pattern has no significant effect on the conductivity of the pattern, so that a high-temperature post-treatment step is not required.
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a graphene ink which is used for printing a flexible device and does not need high-temperature post-treatment and a preparation method thereof.
Technical scheme
The graphene ink used for printing of flexible devices and free of high-temperature post-treatment is characterized in that riboflavin sodium phosphate is used for efficiently dispersing graphene to form graphene dispersion liquid, wherein the final concentration of the riboflavin sodium phosphate in the graphene dispersion liquid is 0.05-0.5 mg/mL; and adding ethanol, wherein the ratio of the ethanol to the graphene dispersion liquid is 1:0.1-50, and obtaining the graphene ink for droplet jetting.
The ink surfactant content of the graphene ink is 0.05mg/mL at the lowest, the ratio of the ink surfactant to graphene is 1:20, the Zeta potential absolute value is 50-70mV, the transverse size of a graphene sheet layer in dispersion liquid is 3-10 micrometers, and the thickness of the graphene sheet layer is 1-1.5nm, so that the trace amount of surfactant does not influence the lap joint between two-dimensional graphene sheet layers, does not influence the conductivity of a graphene pattern, and does not need high-temperature post-treatment.
A method for preparing the graphene ink for printing flexible-oriented devices without high-temperature post-treatment is characterized by comprising the following steps:
adding the graphene powder into deionized water, carrying out ultrasonic treatment for 0.5-20h, and keeping the temperature of the mixed liquid to be less than 30 ℃ in the ultrasonic process;
during ultrasonic treatment, the ultrasonic power is gradient power from high to low, and the power range is 30-700W;
adding a riboflavin sodium phosphate aqueous solution for multiple times in the graphene ultrasonic process to prepare a graphene dispersion solution with the concentration of 1-10mg/mL, and storing the graphene dispersion solution in a brown reagent bottle;
the final concentration of the riboflavin sodium phosphate in the graphene dispersion liquid is 0.05-0.5 mg/mL;
the concentration of the riboflavin sodium phosphate aqueous solution is 0.1-1 mg/mL;
step 2: adding ethanol into the graphene dispersion liquid, wherein the ratio of the ethanol to the graphene dispersion liquid is 1:0.1-50, and obtaining the graphene ink for micro-droplet jetting.
The ultrasonic power is set to be 1-5 in power gradient from high to low.
The riboflavin sodium phosphate aqueous solution is added for 1-20 times.
The ink viscosity interval is 1-5 mPa.s, and the surface tension interval is 22-72 mN/m.
The preparation of the graphene powder comprises the following steps: mixing 1g of crystalline flake graphite with a strong oxidant, reacting at a gradient temperature, and freeze-drying to obtain graphene oxide powder; mixing graphene oxide and a reducing agent in a ratio of 1:10-100, placing the mixed solution into a reaction kettle, carrying out hydrothermal reaction at the temperature of 100 ℃ and 250 ℃ for 6-12h, and carrying out freeze drying to obtain primary reduced graphene powder; and (3) putting the primary reduced graphene into a tubular furnace, introducing argon for protection, setting the temperature programming of the tubular furnace to 200-1500 ℃, and keeping the temperature for 0.5-10h to obtain secondary reduced graphene powder.
The gradient temperature reaction is set to be 1-3, the temperature range is 0-200 ℃, and the reaction time is 1-30 h.
The strong oxidant can be a mixed oxidant of 20-50mL of concentrated sulfuric acid and 6-10g of potassium permanganate.
The reducing agent may be ammonium carbonate, hydrazine hydrate or melamine.
The flow rate of the argon gas is 10-20 mL/min.
Advantageous effects
According to the graphene ink used for printing of the flexible device and without high-temperature post-treatment and the preparation method thereof, the graphene raw material is prepared through a two-step reduction method, and the graphene is efficiently dispersed by using the ultrasonic-assisted riboflavin sodium phosphate by utilizing the principle that riboflavin sodium phosphate molecules have large conjugated carbon skeleton structures (dimethyl-iso-uracil rings) and can generate strong adsorption with the side wall of the graphene. The graphene ink with extremely low surfactant content and high dispersion stability can be prepared by selecting parameters such as proper feed ratio, ultrasonic time, ultrasonic power, solvent ratio and the like. The content of the finally prepared ink surfactant is 0.05mg/mL at the lowest, the ratio of the surfactant to graphene is 1:20, the absolute value of Zeta potential is as high as 50-70mV, the transverse size of graphene sheet layers in dispersion liquid is 3-10 micrometers, the thickness is only 1-1.5nm, the lapping among two-dimensional graphene sheet layers is not influenced by a trace amount of surfactant, the conductivity of a graphene pattern is not influenced, and high-temperature post-treatment is not needed.
The invention has the beneficial effects that: by selecting a proper surfactant and a proper mixed solvent, efficient and stable dispersion of graphene is realized, the graphene ink which does not need high-temperature annealing and has controllable physical and chemical parameters is prepared, and the problem that the surfactant is difficult to remove at low temperature in common graphene ink is solved. The graphene ink prepared by the invention has the advantages of low surfactant content, good dispersion stability and the like, so that the surfactant is not required to be removed at high temperature, and the graphene ink can be directly used for printing flexible graphene conductive patterns.
Drawings
Fig. 1 is a flow chart of graphene ink preparation.
Fig. 2 photo of graphene ink.
FIG. 3 is a scanning electron micrograph of the evaporated graphene ink. In the figure, the dotted line frame is riboflavin sodium phosphate, and the two-dimensional sheet is graphene.
Fig. 4 atomic force microscope photograph of graphene ink after evaporation.
Fig. 5 is a photograph size measurement of fig. 4.
FIG. 6 comparison graph of graphene printed line resistance (a) dispersion of sodium deoxycholate, a common surfactant; (b) dispersing ultra-low concentration riboflavin sodium phosphate.
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
example 1:
(1) adding 1g of flake graphite into 24mL of concentrated sulfuric acid, adding 6g of potassium permanganate into the mixture for 5 times under the ice bath condition, reacting for 1 hour, heating to 50-60 ℃, and reacting for 6 hours; and (5) freeze-drying to obtain graphene oxide powder.
(2) Adding graphene oxide powder into deionized water, wherein the concentration is 2mg/mL, and uniformly mixing; and adding ammonium carbonate into the mixed solution, putting the mixed solution into a reaction kettle, and freeze-drying to obtain primary reduced graphene powder.
In the step (2), the mass ratio of the graphene oxide to the ammonium carbonate is 1:10, the hydrothermal reaction temperature is set to 100 ℃, and the reaction time is set to 10 hours.
(3) And (3) putting the primary reduced graphene into a tube furnace, introducing argon for protection, setting the flow rate of the argon to be 10-15mL/min, setting the program to heat to 200 ℃, setting the heating rate to be 2-10 ℃/min, keeping the temperature for 0.5h, and then cooling to room temperature to obtain secondary reduced graphene powder.
(1) Under the condition of keeping out of the sun, preparing a riboflavin sodium phosphate aqueous solution with the concentration of 0.1 mg/mL.
(2) And (3) adding the secondary reduced graphene powder obtained in the step (1) into deionized water, carrying out ultrasonic treatment, setting gradient power, and keeping the temperature of the mixed liquid to be less than 30 ℃ in the ultrasonic process.
The ultrasonic power is gradient power from high to low, the power gradients are set to be 3, the power gradients are 300W, 200W and 100W in sequence, and the total ultrasonic time is 5 h.
(3) Adding the riboflavin sodium phosphate solution in the graphene ultrasonic process for 3 times to prepare graphene dispersion liquid with the concentration of 1mg/mL, and storing the graphene dispersion liquid in a brown reagent bottle;
the final concentration of the riboflavin sodium phosphate in the system is 0.05 mg/mL.
And (3) adding ethanol into the graphene dispersion liquid obtained in the step (2), wherein the ratio of the ethanol to the graphene dispersion liquid is 1: 0.1.
Example 2:
(1) Adding 1g of flake graphite into 46mL of concentrated sulfuric acid, adding 6g of potassium permanganate for 4 times under an ice bath condition, reacting for 1h, heating to 40-50 ℃, and reacting for 8 h; and (5) freeze-drying to obtain graphene oxide powder.
(2) Adding graphene oxide powder into deionized water, wherein the concentration is 2mg/mL, and uniformly mixing; and adding ammonium carbonate into the mixed solution, putting the mixed solution into a reaction kettle, and freeze-drying to obtain the primary reduced graphene powder.
In the step (2), the mass ratio of the graphene oxide to the ammonium carbonate is 1:5, the hydrothermal reaction temperature is set to 180 ℃, and the reaction time is set to 8 hours.
(3) And (2) putting the primary reduced graphene into a tube furnace, introducing argon for protection, setting the flow rate of the argon to be 15-20mL/min, setting the program to heat to 500 ℃, setting the heating rate to be 10-20 ℃/min, preserving the heat for 1h, and cooling to room temperature to obtain secondary reduced graphene powder.
(1) Under the condition of keeping out of the sun, preparing a riboflavin sodium phosphate aqueous solution with the concentration of 0.5 mg/mL.
(2) And (3) adding the secondary reduced graphene powder obtained in the step (1) into deionized water, carrying out ultrasonic treatment, setting gradient power, and keeping the temperature of the mixed liquid to be less than 30 ℃ in the ultrasonic process.
The ultrasonic power is gradient power from high to low, the power gradients are set to be 5, the power gradients are 300W, 240W, 180W, 120W and 60W in sequence, and the total ultrasonic time is 3 h.
(3) Adding the riboflavin sodium phosphate solution into the system by 10 times to prepare graphene dispersion liquid with the concentration of 3mg/mL, and storing the graphene dispersion liquid in a brown reagent bottle.
The final concentration of the riboflavin sodium phosphate in the system is 0.15 mg/mL.
And (3) adding ethanol into the graphene dispersion liquid obtained in the step (2), wherein the ratio of the ethanol to the graphene dispersion liquid is 2: 1.
Example 3:
(1) Adding 1g of flake graphite into 24mL of concentrated sulfuric acid, adding 6g of potassium permanganate for 5 times under the ice bath condition, reacting for 2 hours, heating to 30-40 ℃, and reacting for 12 hours; and (5) freeze-drying to obtain graphene oxide powder.
(2) Adding graphene oxide powder into deionized water, wherein the concentration is 2mg/mL, and uniformly mixing; and adding ammonium carbonate into the mixed solution, putting the mixed solution into a reaction kettle, and freeze-drying to obtain the primary reduced graphene powder.
In the step (2), the mass ratio of the graphene oxide to the ammonium carbonate is 1:10, the hydrothermal reaction temperature is set to 200 ℃, and the reaction time is set to 6 hours.
(3) And (3) putting the primary reduced graphene into a tube furnace, introducing argon for protection, setting the flow rate of the argon to be 10-20mL/min, setting the temperature to be 800 ℃ by a program, keeping the temperature for 5 hours at the temperature rise rate of 5-10 ℃/min, and cooling to room temperature to obtain secondary reduced graphene powder.
(1) Under the condition of keeping out of the sun, preparing a riboflavin sodium phosphate aqueous solution with the concentration of 0.1 mg/mL.
(2) And (3) adding the secondary reduced graphene powder obtained in the step (1) into deionized water, carrying out ultrasonic treatment, setting gradient power, and keeping the temperature of the mixed liquid to be less than 30 ℃ in the ultrasonic process.
The ultrasonic power is gradient power from high to low, the power gradients are set to be 3, the power gradients are 700W, 300W and 100W in sequence, and the total ultrasonic time is 0.5 h.
(3) Adding the riboflavin sodium phosphate solution into the system by 10 times to prepare graphene dispersion liquid with the concentration of 3mg/mL, and storing the graphene dispersion liquid in a brown reagent bottle.
The final concentration of the riboflavin sodium phosphate in the system is 0.1 mg/mL.
And (3) adding ethanol into the graphene dispersion liquid obtained in the step (2), wherein the ratio of the ethanol to the graphene dispersion liquid is 1: 2.
Claims (10)
1. The graphene ink used for printing of flexible devices and free of high-temperature post-treatment is characterized in that riboflavin sodium phosphate is used for efficiently dispersing graphene to form graphene dispersion liquid, wherein the final concentration of the riboflavin sodium phosphate in the graphene dispersion liquid is 0.05-0.5 mg/mL; and adding ethanol, wherein the ratio of the ethanol to the graphene dispersion liquid is 1:0.1-50, and obtaining the graphene ink for droplet jetting.
2. The graphene ink for printing towards the flexible device without high-temperature post-treatment according to claim 1, wherein: the ink surfactant content of the graphene ink is 0.05mg/mL at the lowest, the ratio of the ink surfactant to graphene is 1:20, the Zeta potential absolute value is 50-70mV, the transverse size of a graphene sheet layer in dispersion liquid is 3-10 micrometers, and the thickness of the graphene sheet layer is 1-1.5nm, so that the trace amount of surfactant does not influence the lap joint between two-dimensional graphene sheet layers, does not influence the conductivity of a graphene pattern, and does not need high-temperature post-treatment.
3. A method for preparing the graphene ink for printing facing flexible devices according to claim 1 without high-temperature post-treatment, which is characterized by comprising the following steps:
step 1, preparing a graphene dispersion liquid:
adding the graphene powder into deionized water, carrying out ultrasonic treatment for 0.5-20h, and keeping the temperature of the mixed liquid to be less than 30 ℃ in the ultrasonic process;
during ultrasonic treatment, the ultrasonic power is gradient power from high to low, and the power range is 30-700W;
adding a riboflavin sodium phosphate aqueous solution for multiple times in the graphene ultrasonic process to prepare a graphene dispersion solution with the concentration of 1-10mg/mL, and storing the graphene dispersion solution in a brown reagent bottle;
the final concentration of the riboflavin sodium phosphate in the graphene dispersion liquid is 0.05-0.5 mg/mL;
the concentration of the riboflavin sodium phosphate aqueous solution is 0.1-1 mg/mL;
step 2: adding ethanol into the graphene dispersion liquid, wherein the ratio of the ethanol to the graphene dispersion liquid is 1:0.1-50, and obtaining the graphene ink for micro-droplet jetting.
4. The method of claim 3, wherein: the ultrasonic power is set to be 1-5 in power gradient from high to low.
5. The method of claim 3, wherein: the riboflavin sodium phosphate aqueous solution is added for 1-20 times.
6. The method of claim 3, wherein: the preparation of the graphene powder comprises the following steps: mixing 1g of crystalline flake graphite with a strong oxidant, reacting at a gradient temperature, and freeze-drying to obtain graphene oxide powder; mixing graphene oxide and a reducing agent in a ratio of 1:10-100, placing the mixed solution into a reaction kettle, carrying out hydrothermal reaction at the temperature of 100 ℃ and 250 ℃ for 6-12h, and carrying out freeze drying to obtain primary reduced graphene powder; and (3) putting the primary reduced graphene into a tubular furnace, introducing argon for protection, setting the temperature programming of the tubular furnace to 200-1500 ℃, and keeping the temperature for 0.5-10h to obtain secondary reduced graphene powder.
7. The method of claim 6, wherein: the gradient temperature reaction is set to be 1-3, the temperature range is 0-200 ℃, and the reaction time is 1-30 h.
8. The method of claim 6, wherein: the strong oxidant can be a mixed oxidant of 20-50mL of concentrated sulfuric acid and 6-10g of potassium permanganate.
9. The method of claim 6, wherein: the reducing agent may be ammonium carbonate, hydrazine hydrate or melamine.
10. The method of claim 6, wherein: the flow rate of the argon gas is 10-20 mL/min.
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| CN202210206028.5A CN114891399A (en) | 2022-02-28 | 2022-02-28 | Graphene ink used for printing flexible devices and free of high-temperature post-treatment and preparation method thereof |
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| CN116694139A (en) * | 2023-05-23 | 2023-09-05 | 西北工业大学 | High-concentration large-lamellar intrinsic graphene water-based ink for droplet printing and preparation method thereof |
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| KR20160083673A (en) * | 2015-01-02 | 2016-07-12 | 연세대학교 산학협력단 | Method for forming graphene nanoribbon using flavin derivative |
| CN110511618A (en) * | 2018-09-21 | 2019-11-29 | 西安交通大学 | A kind of preparation method and its film, composite material film of Graphene conductive ink |
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| KR20160083673A (en) * | 2015-01-02 | 2016-07-12 | 연세대학교 산학협력단 | Method for forming graphene nanoribbon using flavin derivative |
| CN110511618A (en) * | 2018-09-21 | 2019-11-29 | 西安交通大学 | A kind of preparation method and its film, composite material film of Graphene conductive ink |
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| CN116694139A (en) * | 2023-05-23 | 2023-09-05 | 西北工业大学 | High-concentration large-lamellar intrinsic graphene water-based ink for droplet printing and preparation method thereof |
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