CN116694139A - High-concentration large-lamellar intrinsic graphene water-based ink for droplet printing and preparation method thereof - Google Patents
High-concentration large-lamellar intrinsic graphene water-based ink for droplet printing 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 161
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 110
- 238000007639 printing Methods 0.000 title claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 50
- 239000010439 graphite Substances 0.000 claims abstract description 50
- 239000004094 surface-active agent Substances 0.000 claims abstract description 24
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 21
- 239000007864 aqueous solution Substances 0.000 claims abstract description 19
- 239000006185 dispersion Substances 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 238000010008 shearing Methods 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000006228 supernatant Substances 0.000 claims abstract description 7
- FVTCRASFADXXNN-SCRDCRAPSA-N flavin mononucleotide Chemical group 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 10
- 238000000034 method Methods 0.000 claims description 10
- 229950001574 riboflavin phosphate Drugs 0.000 claims description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 abstract description 5
- 239000002608 ionic liquid Substances 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 230000007847 structural defect Effects 0.000 abstract description 4
- 239000000976 ink Substances 0.000 description 67
- 239000010410 layer Substances 0.000 description 16
- 230000007547 defect Effects 0.000 description 9
- 239000011229 interlayer Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 230000002687 intercalation Effects 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
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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
Abstract
The invention provides high-concentration large-lamellar intrinsic graphene water-based ink for droplet printing and a preparation method thereof, and solves the problems that the existing graphene ink for droplet printing is graphene oxide ink, and most of the graphene ink adopts an organic solvent or ionic liquid as a solvent, and has more structural defects, organic residues, lower conductivity and other application limitations even though the graphene ink is subjected to reduction treatment. The invention comprises the following steps: 1) Adding a surfactant into deionized water, and performing ultrasonic treatment to obtain a surfactant aqueous solution; 2) Adding flake graphite into the surfactant aqueous solution obtained in the step 1), and performing ultrasonic treatment to obtain a graphite mixed solution; 3) Carrying out low-power ultrasonic treatment or shearing treatment on the graphite mixed solution obtained in the step 2) to obtain graphene dispersion liquid; 4) And (3) standing the graphene dispersion liquid obtained in the step (3) for 30-72h at 15-40 ℃, filtering, centrifuging, and removing the supernatant to obtain the high-concentration large-lamellar intrinsic graphene water-based ink for droplet printing.
Description
Technical Field
The invention belongs to the technical field of droplet printing and graphene preparation, and particularly relates to high-concentration large lamellar intrinsic graphene water-based ink for droplet printing and a preparation method thereof.
Background
The graphene ink is used as the basis of flexible electronic components, is applied to printing technologies such as droplet printing, ink-jet printing, aerosol printing, direct writing, screen printing and the like, and has wide application prospects. The droplet printing technology can realize efficient preparation of the three-dimensional graphene device, and has the advantages of low cost, simple process flow, high forming efficiency and the like. The three-dimensional graphene device for droplet printing requires that graphene ink has the characteristics of high concentration and large sheets so as to ensure effective lap joint between three-dimensional graphene sheets after droplet printing and ensure the mechanical strength, electrothermal and other functionalities of a macroscopic body of the three-dimensional graphene device.
Currently, there are scholars to prepare graphene inks for droplet printing, such as: chinese patent application CN112661144A oxidizes natural crystalline flake graphite into graphene oxide, and hydrothermally mixes nitrogen to prepare nitrogen-doped graphene oxide ink suitable for uniform droplet injection, and the ink has the advantages of stable dispersion, micron-sized sheet spreading and the like. Chinese patent application CN108545732A, suspension of graphene oxide and cross-linking agent solution prepared by Hummers method is subjected to chemical cross-linking reaction to prepare graphene oxide ink for 3D printing, and the graphene oxide ink can be directly printed into a graphene oxide flexible bracket with higher precision under the conditions of no high polymer binder and no additive. However, the inks for droplet printing prepared at present are graphene oxide inks, and mostly organic solvents or ionic liquids are used as solvents thereof; the ink needs high temperature or chemical reduction treatment after printing, and the post-treatment process is complex; even if post-treatment is performed, oxygen-containing functional groups, defects and organic matters of the graphene cannot be completely removed, which can deteriorate the intrinsic structure and conductivity of the graphene, and is unfavorable for the three-dimensional graphene device to exert the advantage of high conductivity, so that the application of the three-dimensional graphene device in the field of droplet printing is limited.
Therefore, it is necessary to explore a novel graphene ink for droplet printing.
Disclosure of Invention
The invention aims to solve the problems that the existing graphene ink for droplet printing is graphene oxide ink, and organic solvents or ionic liquids are mostly adopted as solvents of the graphene ink, and the graphene ink still has more structural defects, organic residues, lower conductivity and other application limitations even though the graphene ink is subjected to reduction treatment, and provides high-concentration large-lamellar intrinsic graphene water-based ink for droplet printing and a preparation method thereof.
In order to achieve the above purpose, the technical solution provided by the present invention is:
the preparation method of the high-concentration large-lamellar intrinsic graphene water-based ink for droplet printing is characterized by comprising the following steps of:
1) Adding a surfactant into deionized water, and performing ultrasonic treatment to obtain a surfactant aqueous solution;
the surfactant is riboflavin sodium phosphate or polyvinylpyrrolidone, the concentration is 0.2-2mg/ml, and a small amount of surfactant compared with flake graphite is added, so that the surface tension of an aqueous solution can be effectively reduced, and the conductivity of the intrinsic graphene ink can not be influenced under the condition of no post-treatment;
the ultrasonic power is 60-240W, the ultrasonic time is 2-20min, the ultrasonic within the power range enables the surfactant to be fully dissolved in water, the surface tension of the aqueous solution is effectively reduced, the aim is that the surfactant in the subsequent step 2) can be uniformly intercalated into the flake graphite, the stripping efficiency of graphite powder is improved, and the long-term stability of the prepared intrinsic graphene ink is effectively maintained;
2) Adding flake graphite into the surfactant aqueous solution obtained in the step 1), and performing ultrasonic treatment to obtain a graphite mixed solution;
the mesh number of the crystalline flake graphite is 80-500 meshes, and the concentration is 15-45mg/ml;
the ultrasonic power is 180-860W, the ultrasonic time is 1-9h, the ultrasonic not only ensures that the flake graphite is fully mixed with the aqueous solution of the surfactant, but also can promote the surfactant to smoothly enter the gaps of the graphite layers and conduct intercalation treatment on the gaps, is favorable for expanding the graphite and primarily stripping the blocky flake graphite,
3) Carrying out low-power ultrasonic treatment or shearing treatment on the graphite mixed solution obtained in the step 2) to obtain graphene dispersion liquid; the low-power ultrasonic or shearing treatment can lead the exfoliated lamellar graphite to only conduct interlayer exfoliation without breaking perpendicular to the interlayer direction;
the power of the ultrasonic wave is 30-540W, and the ultrasonic wave time is 0.5-3h;
the shearing rotating speed is 800-2500rpm, and the shearing time is 0.5-3h;
4) And (3) standing the graphene dispersion liquid obtained in the step (3) for 30-72h at 15-40 ℃ for removing graphite precipitates which are not peeled off, centrifuging filtrate after filtering, and removing supernatant to obtain the high-concentration large-lamellar intrinsic graphene water-based ink for droplet printing.
Further, in the step 2), the ultrasonic power is 580-860W, the ultrasonic time is 3-7h, and the optimized ultrasonic power and time can enable the surfactant to be rapidly and effectively intercalated into the gaps of the graphite layers and perform preliminary interlayer stripping and crushing in the direction perpendicular to the interlayer to form lamellar graphite;
further, in the step 4), the rotation speed of the centrifugation is 1500-4500rpm, and the centrifugation time is 5-20min.
Meanwhile, the invention also provides the high-concentration large-sheet-layer intrinsic graphene water-based ink for droplet printing, which is prepared by the preparation method, wherein the concentration of the high-concentration large-sheet-layer intrinsic graphene water-based ink is 8-20mg/ml, the transverse dimension of the intrinsic graphene sheet layer is 5-11 mu m, and the thickness of the intrinsic graphene sheet layer is 1-2nm.
Further, it I D /I G The value is 0.1-0.3.
Further, the conductivity of the intrinsic graphene is 3500-50000S/m.
In addition, the invention also provides a three-dimensional graphene device, which is characterized in that the high-concentration large-sheet-layer intrinsic graphene water-based ink microdroplet for microdroplet printing is prepared by adopting the preparation method.
The principle of the invention is as follows:
the method for preparing the ink is different from the existing preparation method, breaks through the conventional thinking, firstly, the surfactant is added into deionized water for ultrasonic treatment to obtain a surfactant aqueous solution, so that the surface tension of the aqueous solution is effectively reduced, and the stripping efficiency of graphite is improved; adding the flake graphite into a surfactant aqueous solution, mixing and carrying out ultrasonic treatment for a period of time, enabling the surfactant to enter a graphite layer gap to carry out intercalation treatment while uniformly mixing the surfactant, the flake graphite and deionized water by utilizing ultrasonic treatment, facilitating graphite expansion, carrying out primary interlayer stripping on the block-shaped flake graphite and crushing the block-shaped flake graphite into lamellar graphite in a direction perpendicular to an interlayer direction, and improving the concentration of graphene ink; and then, carrying out low-power ultrasonic or shearing treatment to implode larger cavitation bubbles to generate smaller cavitation bubbles, and further stripping the intercalated expanded graphite by the smaller cavitation bubbles, wherein the force only enables the stripped lamellar graphite to be only subjected to interlayer stripping without crushing perpendicular to the interlayer direction, so that the stripped graphene is not broken, large-size lamellar layers can be effectively maintained, finally, further standing, filtering and centrifuging are carried out to remove supernatant liquid to prepare the intrinsic graphene ink with high concentration and large lamellar layers for droplet printing, and further, effective lap joint between the three-dimensional graphene lamellar layers after droplet printing is ensured, and the mechanical strength, electrothermal functionality and the like of a macroscopic body of the three-dimensional graphene device are ensured.
The invention has the advantages that:
1. the intrinsic graphene ink for droplet printing prepared by the invention is water-based ink, and has lower structural defect and I D /I G The value is 0.1-0.3, the intrinsic graphene has the characteristics of high concentration and large lamellar, the conductivity of the intrinsic graphene is 3500-50000S/m, and the intrinsic graphene can be used in the field of droplet printing. The whole preparation method is simple, friendly and easy to operate, uses environment-friendly and nontoxic water as a solvent thereof, does not need subsequent treatment, and has no problems of organic matter residue, lower conductivity and limited application caused by the subsequent treatment.
2. According to the invention, the surfactant is fully dissolved in water, so that the surface tension of an aqueous solution is reduced from 72mN/m to 45-60mN/m, and the surfactant is enabled to enter a graphite layer gap for intercalation treatment in the subsequent ultrasonic treatment, thereby being beneficial to expanding graphite and effectively improving the intrinsic graphene ink concentration; therefore, the intrinsic graphene ink prepared by the method has higher concentration of 8-20mg/ml.
3. The invention uses the phenomenon that the high-speed flowing deionized water and cavitation bubbles pull the graphite sheet layer open in the whole preparation process, and uses the soft acting force of low-power ultrasonic or shearing to process the graphite mixed solution, so that larger cavitation bubbles implode to generate smaller cavitation bubbles, the smaller cavitation bubbles can further peel the intercalated expanded graphite, the force only enables the peeled lamellar graphite to peel only from layers without breaking perpendicular to the interlayer direction, the peeled graphene is not broken, the large-size sheet layer can be effectively maintained, the lateral dimension of the prepared intrinsic graphene sheet layer is 5-11 mu m, the thickness is 1-2nm, and the use requirement of droplet printing is met.
Drawings
FIG. 1 is a flow chart of a process for preparing a high-concentration large lamellar intrinsic graphene water-based ink for droplet printing according to the invention;
FIG. 2 is an optical photograph of the intrinsic graphene ink prepared in example 1 without precipitation after standing for 300 hours;
FIG. 3 is a scanning electron microscope image of an intrinsic graphene sheet in the ink prepared in example 3;
fig. 4 is a raman spectrum of the intrinsic graphene ink prepared in examples 1-6.
Detailed Description
The invention is described in further detail below with reference to the attached drawings and specific examples:
example 1
As shown in fig. 1, the preparation method of the high-concentration large lamellar intrinsic graphene water-based ink for droplet printing comprises the following steps:
step 1: adding riboflavin sodium phosphate into deionized water according to the requirement of 0.2mg/ml of the target concentration of the riboflavin sodium phosphate, mixing, and carrying out ultrasonic treatment at 60W for 2min to obtain a riboflavin sodium phosphate aqueous solution;
step 2: adding 500-mesh flake graphite into the riboflavin sodium phosphate aqueous solution obtained in the step 1 according to the requirement of 15mg/ml of the target concentration of the flake graphite, mixing, and carrying out ultrasonic treatment for 1h at 860W to obtain a graphite mixed solution;
step 3: ultrasonically dispersing the graphite mixed solution for 3 hours at the power of 30W to obtain graphene dispersion liquid;
step 4: standing graphene dispersion at 15deg.C for 30 hr, filtering, centrifuging at 1500rpm for 20min, and removing supernatant to obtain intrinsic graphene ink for droplet printing with graphene ink concentration of 8mg/ml and lamellar lateral dimension of 5 μm, which has low defect, and has a particle size of I D /I G The value was 0.28 as shown in fig. 4.
The optical photograph of the large-sheet high-concentration intrinsic graphene water-based ink for droplet printing prepared in the embodiment 1 after standing for 300 hours is shown in fig. 2, and no precipitation is generated in the ink after standing for 300 hours, which proves that the prepared intrinsic graphene water-based ink can be kept uniform and stable for a long time. The ink droplets prepared in example 1 were printed into graphene devices having a resistance of 171.2 Ω, a length of 7.2mm, a width of 150 μm, and a height of 80 μm, and a conductivity of 3500S/m.
Example 2
The difference from example 1 is that: in step 3, the mixture was sheared at a high speed of 800rpm for 3 hours. The ink with the concentration of 8mg/ml and the transverse dimension of the lamellar is 5 mu m, the defect is low, I D /I G The value was 0.26 as shown in fig. 4.
The ink droplets prepared in example 2 were printed into graphene devices having a resistance of 181.2 Ω, a length of 6.0mm, a width of 134 μm, and a height of 65 μm, and a conductivity of 3800S/m.
Example 3
The preparation method of the high-concentration large-lamellar intrinsic graphene water-based ink for droplet printing comprises the following steps of:
step 1: adding riboflavin sodium phosphate into deionized water according to the requirement of the riboflavin sodium phosphate target concentration of 1.1mg/ml, mixing, and carrying out ultrasonic treatment at 150W for 10min to obtain a riboflavin sodium phosphate aqueous solution;
step 2: adding 325 mesh flake graphite into riboflavin sodium phosphate aqueous solution for mixing according to the requirement of 30mg/ml of flake graphite target concentration, and performing ultrasonic treatment for 5h at 720W to obtain graphite mixed solution;
step 3: ultrasonically dispersing the graphite mixed solution for 2 hours at the power of 300W to obtain graphene dispersion liquid;
step 4: standing graphene dispersion at 25deg.C for 50 hr, filtering, centrifuging at 3000rpm for 15min, and removing supernatant to obtain intrinsic graphene ink for droplet printing, wherein graphene ink concentration is 14mg/ml, lamellar lateral dimension is 11 μm, its scanning electron microscope image is shown in FIG. 3, its defect is low, and I is D /I G The value was 0.18 as shown in fig. 4.
The ink droplets prepared in example 3 were printed into graphene devices having a resistance of 21.9 Ω, a length of 5.7mm, a width of 121 μm, and a height of 43 μm, and a conductivity of 50000S/m.
Example 4
The difference from example 3 is that: in step 3, the shear was carried out at a high speed of 1600rpm for 2 hours. The ink with the density of 14mg/ml and the transverse dimension of the lamellar is 11 mu m, the defect is low, I D /I G The value was 0.18 as shown in fig. 4.
The ink droplets prepared in example 4 were printed into graphene devices having a resistance of 15.2 Ω, a length of 5.4mm, a width of 132 μm, and a height of 56 μm, and a conductivity of 48000S/m.
Example 5
The preparation method of the high-concentration large-lamellar intrinsic graphene water-based ink for droplet printing comprises the following steps of:
step 1: adding polyvinylpyrrolidone into deionized water according to the requirement of polyvinylpyrrolidone target concentration of 2mg/ml, mixing, and performing ultrasonic treatment at 240W for 20min to obtain polyvinylpyrrolidone aqueous solution;
step 2: adding 80-mesh flake graphite into polyvinylpyrrolidone aqueous solution according to the requirement of 45mg/ml of the target concentration of the flake graphite, mixing, and performing ultrasonic treatment for 9 hours at 180W to obtain a graphite mixed solution;
step 3: ultrasonically dispersing the graphite mixed solution for 0.5h at the power of 540W to obtain graphene dispersion liquid;
step 4: standing graphene dispersion at 40deg.C for 72 hr, filtering, centrifuging at 4500rpm for 5min, and removing supernatant to obtain intrinsic graphene ink for droplet printing with graphene ink concentration of 18mg/ml and lamellar lateral dimension of 8 μm, which has low defect, and has a size of I D /I G The value was 0.10 as shown in fig. 4.
The ink droplets prepared in example 5 were printed into graphene devices having a resistance of 11.0 Ω, a length of 4.3mm, a width of 178 μm, and a height of 82 μm, and a conductivity of 26750S/m.
Example 6
The difference from example 5 is that: in step 3, the mixture was sheared at a high speed of 2500rpm for 0.5h. The ink with the concentration of 18mg/ml and the transverse dimension of the lamellar is 8 mu m, the defect is low, I D /I G The value was 0.12 as shown in fig. 4.
The ink droplets prepared in example 6 were printed into graphene devices having a resistance of 17.3 Ω, a length of 4.8mm, a width of 168 μm, and a height of 74 μm, and a conductivity of 22300S/m.
Example 7
The difference from example 5 is that: in step 2, the ultrasonic treatment was performed at 580W for 7 hours. The ink with 20mg/ml concentration and 9 mu m transverse dimension of the lamellar is prepared in the same way, the defect is low, I D /I G The value was 0.15.
The ink droplets prepared in example 7 were printed into graphene devices having a resistance of 17.9 Ω, a length of 4.2mm, a width of 135 μm, and a height of 56 μm, and a conductivity of 31000S/m.
Example 8
The difference from example 5 is that: in step 2, the ultrasonic treatment was performed at 860W for 3 hours. The ink with 20mg/ml concentration and 8 mu m transverse dimension of the lamellar is prepared in the same way, the defect is low, I D /I G The value was 0.14.
The ink droplets prepared in example 8 were printed into graphene devices having a resistance of 17.4 Ω, a length of 4.0mm, a width of 123 μm, and a height of 62 μm, and a conductivity of 30200S/m.
In summary, the method can prepare the high-concentration large-lamellar intrinsic graphene water-based ink, and solves the problems that the existing graphene ink for droplet printing is graphene oxide ink, and most of the graphene ink adopts an organic solvent or ionic liquid as a solvent, and has more structural defects, organic residues, lower conductivity and other application limitations even though the graphene ink is subjected to reduction treatment.
While the invention has been described with reference to certain preferred embodiments, it will be understood by those skilled in the art that various changes and substitutions of equivalents may be made without departing from the spirit and scope of the invention.
Claims (7)
1. The preparation method of the high-concentration large-lamellar intrinsic graphene water-based ink for droplet printing is characterized by comprising the following steps of:
1) Adding a surfactant into deionized water, and performing ultrasonic treatment to obtain a surfactant aqueous solution;
the surfactant is riboflavin sodium phosphate or polyvinylpyrrolidone, and the concentration is 0.2-2mg/ml;
the power of the ultrasonic wave is 60-240W, and the ultrasonic wave time is 2-20min;
2) Adding flake graphite into the surfactant aqueous solution obtained in the step 1), and performing ultrasonic treatment to obtain a graphite mixed solution;
the mesh number of the crystalline flake graphite is 80-500 meshes, and the concentration is 15-45mg/ml;
the power of the ultrasonic wave is 180-860W, and the ultrasonic wave time is 1-9h;
3) Carrying out low-power ultrasonic treatment or shearing treatment on the graphite mixed solution obtained in the step 2) to obtain graphene dispersion liquid;
the power of the ultrasonic wave is 30-540W, and the ultrasonic wave time is 0.5-3h;
the shearing rotating speed is 800-2500rpm, and the shearing time is 0.5-3h;
4) And (3) standing the graphene dispersion liquid obtained in the step (3) for 30-72h at 15-40 ℃, filtering, centrifuging, and removing the supernatant to obtain the high-concentration large-lamellar intrinsic graphene water-based ink for droplet printing.
2. The method of manufacture of claim 1, wherein:
in the step 2), the power of the ultrasonic wave is 580-860W, and the ultrasonic wave time is 3-7h.
3. The method of manufacture of claim 1, wherein:
in the step 4), the rotating speed of the centrifugation is 1500-4500rpm, and the centrifugation time is 5-20min.
4. The high-concentration large-lamellar intrinsic graphene water-based ink for droplet printing is characterized in that: a method according to any one of claims 1 to 3; the concentration of the graphene is 8-20mg/ml, the transverse dimension of the intrinsic graphene sheet layer is 5-11 mu m, and the thickness of the intrinsic graphene sheet layer is 1-2nm.
5. The high concentration large lamellar intrinsic graphene water based ink for droplet printing in accordance with claim 4, characterized in that: its I D /I G The value is 0.1-0.3.
6. The high concentration large lamellar intrinsic graphene water based ink for droplet printing in accordance with claim 5, characterized in that: the conductivity of the intrinsic graphene is 3500-50000S/m.
7. A three-dimensional graphene device, characterized in that: a droplet printing high concentration large lamellar intrinsic graphene water-based ink droplet obtained by the preparation method of any one of claims 1 to 3.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104058396A (en) * | 2014-07-14 | 2014-09-24 | 复旦大学 | Method for preparing large-size high-quality graphene with controllable number of layers |
| CN105217612A (en) * | 2015-09-29 | 2016-01-06 | 北京航空航天大学 | A kind of ultrasonic assistant sand mill peels off the method preparing Graphene and the device peeling off Graphene processed |
| CN114314574A (en) * | 2022-01-04 | 2022-04-12 | 复旦大学 | Riboflavin sodium phosphate-assisted large-size graphene water-phase preparation method |
| CN114891399A (en) * | 2022-02-28 | 2022-08-12 | 西北工业大学 | Graphene ink used for printing flexible devices and free of high-temperature post-treatment and preparation method thereof |
-
2023
- 2023-05-23 CN CN202310585880.2A patent/CN116694139A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104058396A (en) * | 2014-07-14 | 2014-09-24 | 复旦大学 | Method for preparing large-size high-quality graphene with controllable number of layers |
| CN105217612A (en) * | 2015-09-29 | 2016-01-06 | 北京航空航天大学 | A kind of ultrasonic assistant sand mill peels off the method preparing Graphene and the device peeling off Graphene processed |
| CN114314574A (en) * | 2022-01-04 | 2022-04-12 | 复旦大学 | Riboflavin sodium phosphate-assisted large-size graphene water-phase preparation method |
| CN114891399A (en) * | 2022-02-28 | 2022-08-12 | 西北工业大学 | Graphene ink used for printing flexible devices and free of high-temperature post-treatment and preparation method thereof |
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