CN114276713A - High-conductivity water-based graphene ink and preparation method thereof - Google Patents
High-conductivity water-based graphene ink and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high-conductivity graphene ink and a preparation method thereof, and belongs to the technical field of coatings. The invention provides high-conductivity water-based graphene filler ink and a preparation method thereof. The invention adopts a mixed acid method to modify microcrystalline cellulose, regulates and controls the surface carboxylation degree of the cellulose through different reaction temperatures, further improves the water dispersibility and stability of the cellulose, simultaneously the carboxylated microcrystalline cellulose is used as a green dispersant, the higher carboxyl concentration on the surface of the carboxylated microcrystalline cellulose can improve the dispersion concentration of graphene filler in a water phase, the lower dispersion particle size is lower, and the prepared high-conductivity water-based graphene ink has good compatibility with binders such as water-based resin and the like, and has good application prospects in the fields of electronic tags, new energy sources, coatings, ink, batteries, artificial intelligence, aerospace, communication and the like.
Description
Technical Field
The invention relates to a high-conductivity graphene ink and a preparation method thereof, and belongs to the technical field of coatings.
Background
The conductive ink is a paste ink formed by uniformly dispersing a conductive filler having conductivity in a resin system. After the surface of the base material is coated with the film, the resin is solidified along with the volatilization of the solvent, and the space of the conductive particles in the system is continuously reduced, so that a complete conductive path is formed, and the surface of the material has certain conductivity. The conductive ink can be used for preparing products such as electronic labels, electromagnetic shielding films, antistatic films, battery electrodes and the like due to the special functionality of the conductive ink, and is widely applied to the fields of electronic industry, aerospace, new energy, industrial packaging, communication and the like.
The components of the conductive ink generally include: conductive filler, dispersant, solvent, resin matrix and auxiliary agent. The common conductive carbon filler comprises graphite, carbon black, graphene and the like, and has the advantages of multiple types, lower cost, relatively stable performance, strong acid and alkali resistance and the like compared with a metal conductive filler and an organic macromolecular conductive agent. However, graphene filler molecules have no polar groups, and the graphene filler molecules are easy to agglomerate and settle due to extremely strong van der waals force between the molecules, and are difficult to uniformly disperse in a water solvent. To improve the water dispersibility of the graphene filler, the addition of a dispersant is a common way. The main principle is that the dispersant is adsorbed on the surface of filler particles, so that the hydrophilic and hydrophobic properties of the filler particles are both considered, a stable uniform system is formed in an aqueous medium, and meanwhile, the dispersant has good compatibility with an aqueous resin adhesive, and further the conductive ink is prepared. At present, commonly used dispersing agents such as aromatic compounds, various surfactants, organic salts and the like are used in organic systems, so that the organic systems are under great environmental pressure, problems exist in sustainable development and safe operability, and the dispersion concentration of graphene in some high-conductivity material application fields is also a great challenge.
Microcrystalline cellulose is a straight-chain polysaccharide substance extracted from natural high-molecular cellulose, has high strength, low density, no toxicity, biodegradability, large specific surface area and certain surface activity, and is widely applied to the fields of biomedicine, packaging, adhesives, catalysis, supercapacitors and the like. The polar group hydroxyl and the carbon chain on the molecular chain of the microcrystalline cellulose are respectively endowed with the hydrophilicity and the hydrophobicity of the cellulose, and researches show that the microcrystalline cellulose can be used as a green dispersing agent to disperse various inorganic particle suspensions such as clay, graphene filler and the like in a water phase. However, the water dispersibility of the common microcrystalline cellulose is poor, and the common microcrystalline cellulose has some defects for the dispersion of some high-concentration fillers in the water phase, so that the common microcrystalline cellulose also limits the application of the common microcrystalline cellulose in the field of ink coatings. In an ink system, carboxylated cellulose is used as a dispersing agent, and the high surface carboxyl degree of the carboxylated cellulose can obviously improve the dispersion concentration of the filler and can also improve the interface compatibility with a binder such as an aqueous resin. The prior TEMPO oxidation method which is widely applied can selectively oxidize the alcoholic hydroxyl on the cellulose to generate carboxyl, but the reaction steps are complicated and long in time, and the TEMPO reagent has toxicity and can cause pollution to the environment. Similar ammonium persulfate oxidation reaction has the problems of too long reaction time, low efficiency and the like.
Disclosure of Invention
In order to solve at least one problem, the invention provides an aqueous high-conductivity graphene filler ink and a preparation method thereof. According to the invention, microcrystalline cellulose is modified by adopting a mixed acid method, carboxylated cellulose nanocrystals CCNC with different carboxyl contents are prepared at different reaction temperatures, the water dispersibility and stability of cellulose are improved, the optimum temperature for preparing CCNC with the highest carboxylation degree is selected, the carboxylated cellulose nanocrystals are used as a green dispersing agent, the dispersibility of graphene filler is improved in a water phase, and the graphene filler has good compatibility with adhesives such as water-based resin, and the prepared water-based high-conductivity graphene ink has good application prospects in the fields of electronic tags, new energy sources, coatings, printing ink, batteries, artificial intelligence, aerospace, communication and the like
The first purpose of the invention is to provide a preparation method of water-based high-conductivity graphene ink, which specifically comprises the following steps:
adding conductive graphite into a carboxylated cellulose nanocrystalline water dispersion, grinding, and filtering with a filter cloth after ultrasonic treatment to obtain aqueous conductive slurry;
and (3) mixing the aqueous conductive slurry with the aqueous resin dispersion liquid, adding an auxiliary agent, and uniformly mixing to obtain the aqueous carboxylated cellulose nanocrystalline dispersed graphene ink.
In one embodiment, the preparation method of the carboxylated cellulose nanocrystal water dispersion comprises the following steps:
step1, uniformly mixing sulfuric acid and nitric acid to obtain a mixed acid aqueous solution;
step2, mechanically stirring the cellulose and the mixed acid aqueous solution, standing, separating out an upper layer mixed acid clear solution, and diluting a lower layer dispersion solution with deionized water;
and Step3, centrifuging until the supernatant is neutral, re-dispersing in water and performing ultrasonic treatment to prepare the carboxylated cellulose nanocrystalline water dispersion liquid.
In one embodiment, the concentration of the mixed acid in Step1 is as follows: the concentration of the sulfuric acid is 1-6 mol/L; the concentration of the nitric acid is 1-4 mol/L.
In one embodiment, the stirring temperature in Step2 is 60-120 ℃.
In one embodiment, the mass ratio of the cellulose to the mixed acid in Step3 is as follows: cellulose: concentrated sulfuric acid: concentrated nitric acid 1: (2-6): (1-4).
In one embodiment, the centrifugation mode of Step3 is specifically as follows: the centrifugation speed is 8000-.
In one embodiment, Step3 shows that the concentration of the re-dispersed carboxylated cellulose nanocrystals in water is 1-15 mg/ml.
In one embodiment, the sonication time is between 4 and 10 hours.
In one embodiment, the water-based resin is one or more of polyurethane resin, acrylic resin, polyvinyl alcohol, phenolic resin, alkyd resin, silicone resin, epoxy resin, amino resin, polyester resin, and the like.
In one embodiment, the method specifically comprises the following steps:
adding conductive graphite into a carboxylated cellulose nanocrystalline water dispersion, grinding for 24 hours, and filtering with a filter cloth after ultrasonic treatment to obtain aqueous conductive slurry;
and (3) mixing the aqueous conductive slurry and the aqueous resin dispersion liquid at 300rpm, stirring for 1h, adding the auxiliary agent, and uniformly mixing to obtain the aqueous carboxylated cellulose nanocrystalline dispersed graphene ink.
In one embodiment, the aqueous carboxylated cellulose nanocrystal dispersed graphene ink comprises the following components in percentage by weight: 0.1-10 wt% of carboxylated cellulose nanocrystal, 0.01-15 wt% of carbon filler, 30-99 wt% of water-based dispersion medium, 10-50 wt% of resin adhesive and 0.01-1 wt% of auxiliary agent.
In one embodiment, the filter cloth has a pore size of 400-800 mesh.
In one embodiment, the adjuvant comprises a wetting agent and a defoamer: the wetting agent is selected from one of alkyl sulfate, sulfonate, fatty acid or fatty acid ester sulfate, carboxylic acid soap, phosphate, polyether modified polysiloxane, polyoxyethylene alkyl phenol ether, polyoxyethylene fatty alcohol ether and polyoxyethylene polyoxypropylene segmented copolymer; the defoaming agent is one or more of mineral oil, alcohol, fatty acid and fatty acid ester, amide, phosphate, organosilicon, polyether and polyether modified polysiloxane.
The second purpose of the invention is to provide the water-based high-conductivity graphene ink by using the method.
The third purpose of the invention is to provide the application of the water-based high-conductivity graphene ink in the fields of electronic tags, new energy, coatings, printing ink, batteries, artificial intelligence, aerospace and communication.
In one embodiment, the aqueous highly conductive graphene ink produces a conductive coating.
In one embodiment, the aqueous highly conductive graphene ink is coated on a PET (thickness 40 μm) film using a 30 μm doctor blade and dried in an oven at 60 ℃ for 3min to prepare a conductive coating.
The invention has the beneficial effects that:
(1) the water-based high-conductivity graphene ink prepared by the invention adopts the bio-based dispersing agent, and the dispersing medium is deionized water, so that the pollution to the environment is reduced.
(2) The invention carries out carboxylation modification on microcrystalline cellulose, introduces hydrophilic carboxyl polar groups on a cellulose molecular chain, and the prepared carboxylated cellulose nanocrystalline has good water dispersibility and stability, simple preparation process, controlled reaction and easy repetition.
(3) The invention prepares the carboxylated cellulose nanocrystalline CCNC with different carboxyl contents through different reaction temperatures, reduces the microscopic size (grain diameter) of the cellulose, obviously improves the dispersibility and stability of the cellulose in a water phase, and determines the optimal temperature for preparing the CCNC with high carboxyl content.
(4) The carboxylated cellulose nanocrystal prepared by the invention has good water dispersibility, and simultaneously has good compatibility with water-based resin, and can be compounded with the water-based resin to prepare stable water-based ink.
(5) The invention utilizes the carboxylated cellulose nanocrystals to disperse the graphene filler in the water phase, and has good dispersion effect under higher filler content.
(6) The aqueous carboxylated cellulose nanocrystalline dispersed graphene ink prepared by the invention has excellent conductivity and adhesive force on a coating, good stripping effect on graphite filler, good stability, and stable storage for more than 2 months, and has good application prospect in the fields of electronic tags, new energy, coatings, inks, batteries, artificial intelligence, aerospace, communication and the like.
Drawings
FIG. 1 is a digital photograph of carboxylated cellulose nanocrystal water dispersions of example 1 and comparative example 3.
FIG. 2 is a digital photograph of an aqueous highly conductive graphene ink prepared in example 4, wherein a is an aqueous conductive ink prepared at 80 ℃; b is the state of the aqueous conductive ink prepared at 80 ℃ on PET.
Fig. 3 is a graph of the conductivity of the coating for each of the samples in example 2, example 3, example 4, example 5, and example 6.
Detailed Description
Example 1
The preparation method of the carboxylated cellulose nanocrystalline water dispersion liquid at different reaction temperatures specifically comprises the following steps:
58.8g of sulfuric acid and 25.2g of nitric acid are respectively added into 100ml of deionized water, slowly stirred and diluted to a specific concentration, and then uniformly mixed and stirred according to a mass ratio (concentrated sulfuric acid: concentrated nitric acid is 6: 4) to prepare a mixed acid aqueous solution. Cellulose and a mixed acid aqueous solution were added to a 100ml three-necked flask in a mass ratio (cellulose: concentrated sulfuric acid: concentrated nitric acid: 1: 6: 4), and the mixture was stirred at 60 ℃, 70 ℃, 80 ℃, 90 ℃ and 100 ℃ for 3 hours, respectively. Standing for 30min, separating out upper mixed acid clear liquid, diluting lower dispersion liquid with deionized water, repeatedly centrifuging until the clear liquid is neutral, re-dispersing in deionized water at a concentration of 10mg/ml, and performing ultrasonic treatment in a cell crusher for 1h to prepare the carboxylated cellulose nanocrystal water dispersion liquid. The carboxylated cellulose nanocrystal water dispersion is designated as CCNCX according to the reaction temperature, wherein X ℃ is 60, 70, 80, 90, 100 according to the temperature.
Example 2
The preparation method (60 ℃) based on the carboxylated cellulose nanocrystalline dispersed graphite/aqueous polyurethane ink and the conductive coating thereof comprises the following specific steps:
50g of carboxylated cellulose nanocrystalline water dispersion (CCNC60) is taken in a 200ml beaker, 5g of conductive graphite is taken and added into the beaker, the mixture is stirred for 30min at room temperature by magnetic stirring, the mixture is taken out after being ground for 24h by a ball mill, the mixture is subjected to ultrasonic treatment for 6h in a 120W cell crusher, and residues are filtered by 400-mesh filter cloth to prepare the aqueous conductive slurry. Then 28.5g (35% of solid content) of the aqueous polyurethane dispersion liquid is added, magnetic stirring is carried out for 1 hour, 0.5 wt% of polyether modified polysiloxane wetting agent WE 3221 and 0.5 wt% of mineral oil defoaming agent ST 2437 are added, and uniform mixing is carried out, so that the graphene/aqueous polyurethane ink is prepared. The ink was coated on a PET (thickness 40 μm) film using a 30 μm doctor blade and dried in an oven at 60 ℃ for 3min to prepare a conductive coating. The aqueous ink was designated as X% CG60/WPU according to the amount of the conductive graphite added, wherein X% was 6%, 7%, 8%, 9%, 10% depending on the content.
Example 3
The preparation method (70 ℃) based on the carboxylated cellulose nanocrystal dispersed graphene/waterborne polyurethane ink and the conductive coating thereof comprises the following specific steps:
taking 50g of carboxylated cellulose nanocrystalline water dispersion (CCNC100) into a 200ml beaker, taking 5g of conductive graphite, adding the conductive graphite into the beaker, pre-stirring for 30min at room temperature by using magnetic stirring, grinding for 24h by using a ball mill, taking out, carrying out ultrasonic treatment for 6h in a 120W cell crushing instrument, and filtering residues by using 400-mesh filter cloth to prepare the aqueous conductive slurry. Then 28.5g (35% of solid content) of the aqueous polyurethane dispersion liquid is added and stirred for 1 hour by magnetic force, and 0.5 wt% of polyether modified polysiloxane wetting agent WE 3221 and 0.5 wt% of mineral oil defoaming agent ST 2437 are added and mixed uniformly to obtain the graphene/aqueous polyurethane ink. The ink was coated on a PET (thickness 40 μm) film using a 30 μm doctor blade and dried in an oven at 60 ℃ for 3min to prepare a conductive coating. According to the addition amount of the conductive graphite, the water-based ink is marked as X% CG70/WPU, wherein the X% is 6%, 7%, 8%, 9% and 10% respectively according to different contents.
Example 4
The preparation method (80 ℃) based on the carboxylated cellulose nanocrystal dispersed graphene/waterborne polyurethane ink and the conductive coating thereof comprises the following specific steps:
50g of carboxylated cellulose nanocrystalline water dispersion (CCNC80) is taken in a 200ml beaker, 5g of conductive graphite is taken and added into the beaker, the mixture is stirred for 30min at room temperature by magnetic stirring, the mixture is taken out after being ground for 24h by a ball mill, the mixture is subjected to ultrasonic treatment for 6h in a 120W cell crusher, and residues are filtered by 400-mesh filter cloth to prepare the aqueous conductive slurry. Then 28.5g (35% of solid content) of the aqueous polyurethane dispersion liquid is added, magnetic stirring is carried out for 1 hour, 0.5 wt% of polyether modified polysiloxane wetting agent WE 3221 and 0.5 wt% of mineral oil defoaming agent ST 2437 are added, and uniform mixing is carried out, so that the graphene/aqueous polyurethane ink is prepared. The ink was coated on a PET (thickness 40 μm) film using a 30 μm doctor blade and dried in an oven at 60 ℃ for 3min to prepare a conductive coating. The aqueous ink was designated as X% CG80/WPU according to the amount of the conductive graphite added, wherein X% was 6%, 7%, 8%, 9%, 10% depending on the content.
Example 5
The preparation method (90 ℃) of the carboxylated cellulose nanocrystal based dispersed graphene/waterborne polyurethane ink and the conductive coating thereof comprises the following specific steps:
taking 50g of carboxylated cellulose nanocrystalline water dispersion (CCNC90) into a 200ml beaker, taking 5g of conductive graphite, adding the conductive graphite into the beaker, pre-stirring for 30min at room temperature by using magnetic stirring, grinding for 24h by using a ball mill, taking out, carrying out ultrasonic treatment for 6h in a 120W cell crushing instrument, and filtering residues by using 400-mesh filter cloth to prepare the aqueous conductive slurry. Then 28.5g (35% of solid content) of the aqueous polyurethane dispersion liquid is added and stirred for 1 hour by magnetic force, and 0.5 wt% of polyether modified polysiloxane wetting agent WE 3221 and 0.5 wt% of mineral oil defoaming agent ST 2437 are added and mixed uniformly to obtain the graphene/aqueous polyurethane ink. The ink was coated on a PET (thickness 40 μm) film using a 30 μm doctor blade and dried in an oven at 60 ℃ for 3min to prepare a conductive coating. According to the addition amount of the conductive graphite, the water-based ink is marked as X% CG90/WPU, wherein the X% is 6%, 7%, 8%, 9% and 10% respectively according to different contents.
Example 6
The preparation method (100 ℃) of the carboxylated cellulose nanocrystal based dispersed graphene/waterborne polyurethane ink and the conductive coating thereof comprises the following specific steps:
taking 50g of carboxylated cellulose nanocrystalline water dispersion (CCNC100) into a 200ml beaker, taking 5g of conductive graphite, adding the conductive graphite into the beaker, pre-stirring for 30min at room temperature by using magnetic stirring, grinding for 24h by using a ball mill, taking out, carrying out ultrasonic treatment for 6h in a 120W cell crushing instrument, and filtering residues by using 400-mesh filter cloth to prepare the aqueous conductive slurry. Then 28.5g (35% of solid content) of the aqueous polyurethane dispersion liquid is added and stirred for 1 hour by magnetic force, and 0.5 wt% of polyether modified polysiloxane wetting agent WE 3221 and 0.5 wt% of mineral oil defoaming agent ST 2437 are added and mixed uniformly to obtain the graphene/aqueous polyurethane ink. The ink was coated on a PET (thickness 40 μm) film using a 30 μm doctor blade and dried in an oven at 60 ℃ for 3min to prepare a conductive coating. According to the addition amount of the conductive graphite, the water-based ink is marked as X% CG100/WPU, wherein the X% is 6%, 7%, 8%, 9% and 10% according to different contents.
Comparative example 1 comparison at Normal temperature
The preparation method of the carboxylated cellulose nanocrystalline water dispersion liquid specifically comprises the following steps:
58.8g of sulfuric acid and 25.2g of nitric acid are respectively added into 100ml of deionized water, slowly stirred and diluted to a specific concentration, and then uniformly mixed and stirred according to a mass ratio (concentrated sulfuric acid: concentrated nitric acid is 6: 4) to prepare a mixed acid aqueous solution. Cellulose and a mixed acid aqueous solution were added to a 100ml three-necked flask in a mass ratio (cellulose: concentrated sulfuric acid: concentrated nitric acid: 1: 6: 4), and the mixture was stirred at room temperature for 3 hours. Standing for 30min, separating out upper mixed acid clear liquid, diluting lower dispersion liquid with deionized water, repeatedly centrifuging 55 times, making the supernatant liquid neutral, re-dispersing in deionized water at a concentration of 10mg/ml, and performing ultrasonic treatment in a cell crusher for 1h to prepare carboxylated cellulose nanocrystalline water dispersion liquid, which is recorded as CCNC normal temperature.
Comparative example 2
The preparation method of the carboxylated cellulose nanocrystal based dispersed graphene/waterborne polyurethane ink and the conductive coating thereof comprises the following steps:
50g of the carboxylated cellulose nanocrystal water dispersion (CCNC normal temperature) in the comparative example 1 was put in a 200ml beaker, 5g of conductive graphite was taken, the conductive graphite was added to the beaker, the mixture was stirred magnetically for 30min at room temperature, the mixture was ground in a ball mill for 24 hours and then taken out, the mixture was subjected to ultrasonic treatment in a 120W cell crusher for 6 hours, and the residue was filtered through 400 mesh filter cloth to prepare an aqueous conductive slurry. And then adding 28.5g (35% of solid content) of aqueous polyurethane dispersion liquid, magnetically stirring for 1h, adding 0.5 wt% of polyether modified polysiloxane wetting agent WE 3221 and 0.5 wt% of mineral oil defoaming agent ST 2437, and uniformly mixing to obtain the graphene/aqueous polyurethane ink. The ink was coated on a PET (thickness 40 μm) film using a 30 μm doctor blade and dried in an oven at 60 ℃ for 3min to prepare a conductive coating.
Comparative example 3
The preparation method of the microcrystalline cellulose (MCC) water dispersion comprises the following steps:
taking 1g of microcrystalline cellulose powder and 100g of deionized water, adding into a 200ml beaker, carrying out water bath ultrasound for 30min, and preparing a cellulose water dispersion, which is marked as MCC.
Comparative example 4
The preparation method of the microcrystalline cellulose-based dispersed graphene/waterborne polyurethane ink and the conductive coating thereof comprises the following steps:
50g of microcrystalline cellulose aqueous dispersion (MCC) in comparative example 3 was placed in a 200ml beaker, 5g of conductive graphite was added to the beaker, and the mixture was stirred magnetically for 30min at room temperature, ground with a ball mill for 24 hours, taken out, sonicated in a 120W cell disruptor for 6 hours, and the residue was filtered through a 400 mesh filter cloth to prepare an aqueous conductive slurry. Then 28.5g (35% of solid content) of the aqueous polyurethane dispersion liquid is added, magnetic stirring is carried out for 1 hour, 0.5 wt% of polyether modified polysiloxane wetting agent WE 3221 and 0.5 wt% of mineral oil defoaming agent ST 2437 are added, and uniform mixing is carried out, so that the graphene/aqueous polyurethane ink is prepared. The ink was coated on a PET (thickness 40 μm) film using a 30 μm doctor blade and dried in an oven at 60 ℃ for 3min to prepare a conductive coating.
TABLE 1 comparison of carboxyl group content, zeta potential, particle size of aqueous dispersion, and particle size of ink before and after modification of cellulose
Table 1 shows comparison of the carboxyl group content of cellulose before and after modification, zeta potential, particle size of aqueous dispersion, and particle size of ink. The carboxyl content of the unmodified microcrystalline cellulose MCC is lower than a critical value of 0.005mmol/g, and after modification by a mixed acid method, the carboxyl content of the carboxylated cellulose nanocrystal CCNC after temperature rise is obviously higher than the carboxyl content modified at normal temperature, wherein the carboxyl content reaches 2.67 +/-0.3 mmol/g at the maximum at 80 ℃, which indicates that the degree of oxidation of hydroxyl in the MCC into carboxyl is the highest at 80 ℃. The Zeta potential of the aqueous dispersion of carboxylated cellulose nanocrystalline CCNC was measured and at 80 ℃ the CCNC reached a minimum value of-55 mV, indicating that the electrostatic repulsion force of the CCNC prepared at 80 ℃ in water is the greatest. Meanwhile, the particle size of the modified CCNC is obviously reduced compared with that of the MCC aqueous dispersion before modification, because the non-crystalline region of the cellulose is hydrolyzed at high temperature after the mixed acid is added, and the crystalline region is not hydrolyzed, so that the small-size CCNC is realized. In the aspect of ink dispersibility, the particle size of graphite particles dispersed by CCNC prepared at 80 ℃ as a dispersing agent is minimum and is not 21.4 microns, which shows that the high carboxyl content at 80 ℃ improves the dispersibility of CCNC in water, and simultaneously, the adsorption capacity to graphite particles is maximized, so that the graphite particles can be stably and uniformly dispersed in water, and the agglomeration of graphite sheets is maximally inhibited.
FIG. 1 is a digital photograph of an aqueous MCC dispersion in comparative example 3 and a dispersion of a carboxylated cellulose nanocrystal solution in example 1 at 80 ℃. Before the modification (on the left side of figure 1), the microcrystalline cellulose with larger size and stronger hydrogen bond action among molecules under the same concentration (10mg/ml) is in an opaque and suspended state in water, after the carboxylation modification (on the right side of figure 1) at 80 ℃, the size of the formed carboxylated cellulose nanocrystal is obviously reduced, the oxidized carboxyl concentration on the surface of the molecule is increased, electrostatic repulsion is generated, excellent suspension stability is kept, the color of the molecule in water is gradually transparent and light blue, and the better dispersibility of the carboxylated cellulose nanocrystal in water is also shown. Fig. 2 shows that in the aqueous highly conductive graphene ink prepared in example 4, graphite particles can be uniformly dispersed in an aqueous phase, and no obvious particles or delamination occurs, which corresponds to the particle size of the ink.
Fig. 3 is a graph of the conductivity of the coating layer of each of examples 2, 3, and 4. The conductivity of the coating increases linearly with increasing graphite content at the same temperature. Under the condition of the same graphite addition amount, the electrical conductivity of the CCNC80/WPU is higher than that of the other two groups, the high carboxyl content in the carboxylated cellulose nanocrystals prepared at 80 ℃ improves the dispersibility of the CCNC serving as a dispersing agent in water, the adsorption effect on graphite is improved to the greatest extent, and a more uniform conductive network can be formed and the conductivity of the conductive coating is improved when the conductive coating is prepared.
Claims (10)
1. A preparation method of water-based high-conductivity graphene ink is characterized by comprising the following steps:
adding conductive graphite into a carboxylated cellulose nanocrystalline water dispersion, grinding, and filtering after ultrasonic treatment to prepare aqueous conductive slurry;
and (3) mixing the aqueous conductive slurry with the aqueous resin dispersion liquid, adding an auxiliary agent, and uniformly mixing to obtain the aqueous carboxylated cellulose nanocrystalline dispersed graphene ink.
2. The preparation method of the highly conductive graphene ink according to claim 1, wherein the preparation method of the carboxylated cellulose nanocrystalline water dispersion liquid is as follows:
step1, uniformly mixing sulfuric acid and nitric acid to obtain a mixed acid aqueous solution;
step2, mechanically stirring the cellulose and the mixed acid aqueous solution, standing, separating out an upper layer mixed acid clear solution, and diluting a lower layer dispersion solution with deionized water;
and Step3, centrifuging until the supernatant is neutral, re-dispersing in water and performing ultrasonic treatment to prepare the carboxylated cellulose nanocrystalline water dispersion liquid.
3. The method for preparing the aqueous highly conductive graphene ink according to claim 2, wherein in Step1, the concentration of the mixed acid is as follows: the concentration of the sulfuric acid is 1-6 mol/L; the concentration of nitric acid is 1-4 mol/L;
in Step2, the mass ratio of the cellulose to the mixed acid is as follows: cellulose: concentrated sulfuric acid: concentrated nitric acid 1: (2-6): (1-4);
in Step3, the concentration of the re-dispersed carboxylated cellulose nanocrystals in water is 1-15 mg/ml.
4. The method for preparing the aqueous highly conductive graphene ink according to claim 2, wherein the stirring temperature in Step2 is 60-120 ℃.
5. The method for preparing the aqueous highly conductive graphene ink according to claim 2 or 3, wherein the stirring temperature in Step2 is 80-100 ℃.
6. The method for preparing the aqueous highly conductive graphene ink according to claim 1, wherein in one embodiment, the ultrasonic time is 4-10 h.
7. The method for preparing the water-based highly conductive graphene ink according to claim 1, wherein the water-based resin is one or more of polyurethane resin, acrylic resin, polyvinyl alcohol, phenolic resin, alkyd resin, silicone resin, epoxy resin, amino resin, polyester resin and other water-based resins.
8. The aqueous high-conductivity graphene ink obtained by the preparation method of any one of claims 1 to 7.
9. The preparation method of the aqueous high-conductivity graphene ink according to claims 1 to 7 or the application of the aqueous high-conductivity graphene ink according to claim 8 in the fields of electronic tags, new energy sources, coatings, inks, batteries, artificial intelligence, aerospace and communication.
10. The use according to claim 9, wherein the conductive coating is prepared by the aqueous highly conductive graphene ink.
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