CN111423768A

CN111423768A - Titanium quantum dot doped graphene-based conductive ink and preparation method and application thereof

Info

Publication number: CN111423768A
Application number: CN202010296753.7A
Authority: CN
Inventors: 吴立刚; 叶德林; 胡柱东; 彭令; 曾垂彬; 孔金波; 刘秋明; 马宇飞
Original assignee: Guangdong Kangxi Technology Co Ltd
Current assignee: Guangdong Kangxi Technology Co Ltd
Priority date: 2020-04-15
Filing date: 2020-04-15
Publication date: 2020-07-17
Anticipated expiration: 2040-04-15
Also published as: CN111423768B

Abstract

The invention provides titanium quantum dot doped graphene-based conductive ink which comprises, by weight, 15-40 parts of 5-150 mg/m L graphene dispersion liquid, 40-120 parts of 5-80 mg/m L titanium quantum dot dispersion liquid, 5-25 parts of conductive carbon black, 0.5-2.5 parts of polyacrylonitrile-maleic anhydride copolymer, 0.5-2.5 parts of a structure stabilizer, 100-500 parts of a first dispersing agent, 50-200 parts of a second dispersing agent, 5-20 parts of a stripping resin and 5-10 parts of a flatting agent.

Description

Titanium quantum dot doped graphene-based conductive ink and preparation method and application thereof

Technical Field

The invention relates to the technical field of nano materials, in particular to titanium quantum dot doped graphene-based conductive ink, and further relates to a preparation method of the titanium quantum dot doped graphene-based conductive ink and application of the titanium quantum dot doped graphene-based conductive ink in preparation of a graphene conductive film.

Background

Graphene is a two-dimensional nanomaterial with a hexagonal honeycomb lattice structure formed by carbon atoms through sp2 hybrid orbitals and only one layer of carbon atoms thick. The unique structure of graphene gives it a number of excellent properties, such as a high theoretical specific surface area (2630 m)²G) and ultrahigh electron mobility (200000 cm)²/v.s), high thermal conductivity (5000W/m.K), high Young's modulus (1.0TPa), and high light transmittance (97.7%), among others. By virtue of the advantages of the structure and the performance of the graphene, the graphene has a huge application prospect in the fields of energy storage and conversion devices, nano-electronic devices, multifunctional sensors, flexible wearable electronics, electromagnetic shielding, corrosion prevention and the like. In view of the flexibility and the conductive characteristic of graphene, the graphene slurry is added into the printing ink to prepare the conductive printing ink, and the graphene heating layer is further prepared by spraying and drying the printing ink to prepare the graphene heating body.

Along with the trend of people to good and healthy life, the traditional heating system is improved, more economic and clean alternative energy is searched, and the development of a novel green low-carbon heating system is reluctant. An electric heating technology based on graphene infrared emission performance, namely graphene-based infrared heating ink and an infrared heating body technology thereof, provides an effective solution for solving the problems. Compared with the traditional heating methods such as coal burning, steam, hot air and resistance, the graphene heating method has the advantages of high heating speed, high electricity-heat conversion rate, automatic temperature control, zone control, stable heating, no noise in the heating process, low operation cost, relatively uniform heating, small occupied area, low investment and production cost, long service life, high working efficiency and the like, and is more beneficial to popularization and application. The energy-saving heating device replaces the traditional heating, has particularly remarkable electricity-saving effect, can generally save electricity by about 30 percent, and even can achieve 60 to 70 percent in individual occasions.

The most central part of devices such as graphene infrared heating murals, wallpaper, floors and the like is the graphene heating plate/functional layer. In the prior art, graphene is generally prepared into graphene slurry, ink or paint, and then prepared into a graphene heating coating layer by a printing method. However, the graphene heating plate/functional layer prepared by the methods has the problems of poor thickness controllability, unstable structure of the graphene heating layer, too large sheet resistance, difficulty in practical application, easiness in brittle fracture after long-term use, single selectable printing base material, uneven heat generation and the like, so that the conventional graphene-based conductive ink heating layer is short in service life and not suitable for long-term use.

Disclosure of Invention

In view of the above, the invention provides a titanium quantum dot doped graphene-based conductive ink, which is used for solving the common problems in the prior art that the graphene ink is poor in stability, the thickness of a printed image layer of the graphene ink is difficult to control, the conductivity is poor, a conductive film formed after printing is easy to crack and age, and the heating is not uniform after long-time use.

In a first aspect, the invention provides a titanium quantum dot doped graphene-based conductive ink, which comprises the following components in parts by weight:

15-40 parts of 5-150 mg/m L graphene dispersion liquid, 40-120 parts of 5-80 mg/m L titanium quantum dot dispersion liquid, 5-25 parts of conductive carbon black, 0.5-2.5 parts of polyacrylonitrile-maleic anhydride copolymer, 0.5-2.5 parts of structure stabilizer, 100-500 parts of first dispersing agent, 50-200 parts of second dispersing agent, 5-20 parts of stripping resin and 5-10 parts of flatting agent;

the thickness of graphene in the graphene dispersing agent is 1-20 layers, the transverse size of the graphene in the graphene dispersing agent is 300-1000 nm, the size of titanium quantum dots in the titanium quantum dot dispersing liquid is less than 20nm, and the polymerization degree of the polyacrylonitrile-maleic anhydride copolymer is 50-500.

Preferably, the titanium quantum dot doped graphene-based conductive ink is characterized by comprising the following components in parts by weight:

20-30 parts of 30-60 mg/m L graphene dispersion liquid, 80-100 parts of 15-45 mg/m L titanium quantum dot dispersion liquid, 10-15 parts of conductive carbon black, 1.0-1.6 parts of polyacrylonitrile-maleic anhydride copolymer, 0.8-1.5 parts of structure stabilizer, 200-400 parts of first dispersing agent, 80-160 parts of second dispersing agent, 8-15 parts of stripping resin and 6-8 parts of flatting agent;

the thickness of graphene in the graphene dispersing agent is 5-12 layers, the transverse size of the graphene in the graphene dispersing agent is 500-800 nm, the size of titanium quantum dots in the titanium quantum dot dispersing liquid is 1-10 nm, and the polymerization degree of the polyacrylonitrile-maleic anhydride copolymer is 100-200.

Preferably, the first dispersing agent comprises 1-10 mol/L of strong acid solution, ethanol and cellulose derivatives, wherein the weight ratio of the strong acid solution to the ethanol to the cellulose derivatives is 10: 50-300: 5-20;

the strong acid solution is hydrochloric acid solution or sulfuric acid solution, and the cellulose derivative is one or more of methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, cellulose acetate and cellulose nitrate.

Preferably, the second dispersant comprises a combination of one or more of propylene glycol, cyclohexanol, terpineol, ethanol, ethylene glycol, isopropanol, and ethyl acetate.

Preferably, the release resin is one or more of epoxy resin, polydimethylsiloxane resin, polycarbonate resin, polyurethane resin, acrylic resin, water-based alkyd resin, phenolic resin and silicone-acrylate resin.

Preferably, the leveling agent comprises polypyrrole and also comprises polyvinyl alcohol or polyethylene glycol, wherein the mass ratio of the polypyrrole to the polyvinyl alcohol or the polyethylene glycol is 8: 1-5;

the structure stabilizer comprises ethylenediamine and p-methyl phenol, and the mass ratio of the ethylenediamine to the p-methyl phenol is 10: 1-15.

The titanium quantum dot doped graphene-based conductive ink comprises a graphene dispersion liquid, a titanium quantum dot dispersion liquid, conductive carbon black, a polyacrylonitrile-maleic anhydride copolymer, a structural stabilizer, a first dispersing agent, a second dispersing agent, stripping resin and a leveling agent. The reason for selecting the platinum quantum dots for doping is as follows: the platinum quantum dots have good physical stability, can be well dispersed in the ink and keep the excellent conductivity of the conductive ink, and moreover, the platinum quantum dots have stable chemical properties, are not easy to react with other chemical substances in the environment, keep the quantum dot effect of the platinum quantum dots for a long time and avoid annihilation of the quantum effect caused by environmental change; for the applicant, the preparation process of the platinum quantum dot doped graphene-based conductive ink is relatively mature, and the product quality is easy to control. Most importantly, the platinum quantum dot doped graphene-based conductive ink achieves unexpected technical effects: the platinum quantum dots are uniformly doped into the graphene sheet layer, so that the dispersion of the graphene sheet layer is effectively promoted, meanwhile, by means of factors such as quantum filling effect and surface steric hindrance effect of the platinum quantum dots, the structural stability and chemical stability of the graphene are improved, and the structure, sheet resistance stability and the like of the conductive ink and a heating device using the conductive ink are improved. The titanium quantum dots are loaded through the graphene sheet layer structure, so that on one hand, the titanium quantum dots can be fully doped between the graphene sheet layer structures, the effect of assisting a plurality of graphene sheet layers to form few graphene sheet layers is achieved, and the titanium quantum dots can be prevented from being agglomerated; on the other hand, the dispersed few-layer graphene sheet layer has a larger specific surface area, can realize more thorough doping with the titanium quantum dots, can also strengthen the reaction with other components in the ink, and strengthens the overall stability of the ink. The conductive carbon black can further enhance the conductivity and flexibility of the ink and the corresponding conductive film, and the conductive ink is conveniently printed on a flexible substrate to prepare a flexible heating plate. The first dispersing agent, the second dispersing agent and the stripping resin play a role in stabilizing the surface active functional groups of the graphene oxide, and have functions of protecting the graphene oxide and enhancing the conductivity. The polyacrylonitrile-maleic anhydride copolymer and the flatting agent play a role in blending the ink, can enhance the uniformity and the fluidity of the ink, reduce the viscosity of the ink and facilitate the printing or spraying of the ink. The structural stabilizer can maintain the stable structure of the printing ink for a long time, and particularly, through constructing a reductive environment, part of active graphene oxide forms reduced graphene oxide with stable structure, so that the structural stability of the printing ink and the corresponding conductive thin film is enhanced.

In a second aspect, the invention provides a preparation method of titanium quantum dot doped graphene-based conductive ink, which is used for solving the problems that the preparation process of the ink is complex and difficult to control, the prepared ink is poor in stability, a printed conductive ink printing layer is easy to age and deteriorate, and the printed conductive ink printing layer is fragile and uneven in heating caused by long-term use and the like in the existing ink preparation technology.

A preparation method of titanium quantum dot doped graphene-based conductive ink comprises the following steps of:

preparing graphene dispersion liquid, namely providing graphite powder, preparing graphene oxide by adopting a modified Hummers method, and centrifuging and resuspending to obtain 5-150 mg/m L graphene dispersion liquid;

preparing titanium quantum dot dispersion liquid, namely providing a titanium raw material, stripping the titanium raw material by adopting a liquid phase stripping method, and centrifuging and resuspending to prepare 5-80 mg/m L titanium quantum dot dispersion liquid;

preparing graphene-carbon black color paste: taking and stirring 50-250 parts of first dispersing agent, and slowly adding 15-40 parts of graphene dispersion liquid and 5-25 parts of conductive carbon black into the first dispersing agent to obtain graphene-carbon black color paste;

preparing titanium quantum dot slurry: taking and stirring 50-250 parts of first dispersing agent, and slowly adding 40-120 parts of titanium quantum dot dispersion liquid and 5-20 parts of stripping resin into the first dispersing agent to prepare titanium quantum dot slurry;

preparing a titanium quantum dot doped graphene-based mixed solution: respectively slowly dropwise adding the titanium quantum dot slurry and 50-200 parts of second dispersing agent into the stirred graphene carbon black color paste, transferring the mixed solution into a high-pressure reaction kettle at 70-100 ℃ after dropwise adding is finished, naturally cooling after reacting for 0.5-2 h, and continuously stirring in the reaction process to obtain the titanium quantum dot doped graphene-based mixed solution;

preparing titanium quantum dot doped graphene-based conductive ink: adding 0.5-2.5 parts of a structure stabilizer, 0.5-2.5 parts of a polyacrylonitrile-maleic anhydride copolymer and 5-10 parts of a flatting agent into the titanium quantum dot doped graphene base mixed solution while stirring the titanium quantum dot doped graphene base mixed solution, and continuously stirring for 0.5-6 hours after the addition is finished to prepare the titanium quantum dot doped graphene base conductive ink;

the stirring speed is 100-5000 rpm.

Preferably, in the process of preparing the graphene dispersion liquid, the prepared graphene oxide is transferred to a high-temperature carbonization furnace for high-temperature carbonization for 30-90 s, inert gas is filled in the high-temperature carbonization furnace, the temperature of the high-temperature carbonization furnace is 500-1200 ℃, and the graphene oxide expanded at high temperature is prepared into 5-150 mg/m L graphene dispersion liquid.

More preferably, the inert gas is nitrogen or argon.

Preferably, in the graphene dispersion liquid preparation process, the prepared graphene oxide is transferred into a microfluidic reactor, the pressure of a feed pump of the microfluidic reactor is 100Mpa, and the strong pressure shearing time is 15 s.

Preferably, in the process of preparing the titanium quantum dot dispersion liquid, the titanium raw material is added into a polar solvent, and ultrasonic treatment is carried out for 10-15h by adopting a probe under an ice bath environment;

after the probe finishes ultrasonic treatment, performing ultrasonic treatment in a water bath for 6-15h, and keeping the temperature of the water bath at 5-15 ℃;

and after the water bath ultrasound is finished, centrifuging and resuspending to obtain the titanium quantum dot dispersion liquid.

More preferably, the polar solvent is one or more of isopropanol, ethanol, water and N-methylpyrrolidone.

Preferably, in the process of preparing the titanium quantum dot doped graphene-based mixed solution, the titanium quantum dot slurry and 50-200 parts of second dispersing agent are respectively and slowly dripped into the stirred graphene carbon black color paste, after the dripping is finished, the mixed solution is firstly transferred into a microwave digestion instrument for microwave digestion for 5-15 min, the temperature of the microwave digestion is 65-70 ℃, and the power is 280-330W.

The preparation method of the titanium quantum dot doped graphene-based conductive ink comprises the six steps of preparing a graphene dispersion liquid, preparing a titanium quantum dot dispersion liquid, preparing graphene-carbon black color paste, preparing titanium quantum dot slurry, preparing a titanium quantum dot doped graphene-based mixed solution, preparing the titanium quantum dot doped graphene-based conductive ink and the like, and the conductive ink with a stable structure and complete functions and the corresponding conductive film can be prepared through the six steps. The preparation method comprises the steps of firstly preparing the graphene-carbon black color paste and the titanium quantum dot slurry, ensuring that all components are fully mixed and dissolved, and then mixing and stirring the graphene-carbon black color paste and the titanium quantum dot slurry, so that on one hand, all the components can be further and completely mixed, on the other hand, the titanium quantum dots can be promoted to be fully doped with graphene, the further dispersion of the graphene and the carbon black is promoted, and preparation conditions are provided for the reaction in a high-pressure reaction kettle in the next step. And finally, the structural stabilizer, the polyacrylonitrile-maleic anhydride copolymer and the leveling agent are added to mainly blend the uniformity of the ink and reduce the viscosity of the ink, and meanwhile, the long-term stability of the ink structure can be maintained, and the effective storage period is prolonged.

In a third aspect, the invention provides application of a titanium quantum dot doped graphene-based conductive ink in preparation of a graphene conductive film, and the graphene conductive film is applied to electric heating equipment to overcome the defects of low heating speed, difficulty in accurate temperature control, non-uniform heating, high energy consumption, high production cost, waste gas pollutant generation and the like of the conventional heating devices such as coal-fired heating, electric heating and solar heating.

The invention provides application of the titanium quantum dot doped graphene-based conductive ink in preparation of a graphene conductive film.

Specifically, the titanium quantum dot doped graphene-based conductive ink is arranged on a substrate material in a blade coating, spin coating, direct writing, screen printing, silk printing, ink-jet printing or electrostatic spinning mode, and a graphene conductive film is obtained after curing.

The titanium quantum dot doped graphene-based conductive ink is applied to preparation of a graphene conductive film, the obtained graphene conductive film has considerable flexibility, toughness, hardness and adhesion, and can be printed on various substrates to prepare heating plates or other heating equipment.

Advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of embodiments of the invention.

Drawings

In order to more clearly illustrate the contents of the present invention, a detailed description thereof will be given below with reference to the accompanying drawings and specific embodiments.

Fig. 1 is a schematic structural view of a PI board on which a temperature sensor is disposed.

Detailed Description

While the following is a description of the preferred embodiments of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.

The following describes in detail the preparation method of the titanium quantum dot doped graphene-based conductive ink of the present invention and the titanium quantum dot doped graphene-based conductive ink prepared in each example.

Example 1

The preparation method of the Graphene dispersion liquid comprises the steps of providing 500mg of graphite powder, preparing Graphene Oxide (GO) by adopting a modified Hummers method, placing Graphene Oxide in an ice water bath, carrying out ultrasonic treatment for 10 minutes under 250W power by using an ultrasonic dispersion instrument, repeating the steps once, taking supernate, centrifuging and re-suspending to obtain the Graphene Oxide dispersion liquid with the thickness of 12-20 layers and the transverse dimension of 700-1000 nm, and carrying out centrifugal concentration according to requirements to adjust the concentration of the Graphene Oxide dispersion liquid to 150mg/m L.

The preparation method of the titanium quantum dot dispersion liquid comprises the steps of providing 500mg of titanium powder, peeling the titanium raw material by a liquid phase peeling method, centrifuging and resuspending to obtain 5-80 mg/m L titanium quantum dot dispersion liquid, adding 500mg of titanium powder into 100m L isopropanol, then selecting probe ultrasonic for 250W, carrying out ultrasonic for 10h, selecting ultrasonic on/off time to be 2/4s, carrying out ultrasonic in an ice bath environment, then adopting water bath ultrasonic, carrying out water bath ultrasonic power to be 360W, carrying out ultrasonic time to be 8h, keeping the water bath temperature to be 10 ℃, carrying out centrifugation to obtain the required metal elementary substance titanium quantum dot after ultrasonic treatment, carrying out size range to be less than 20nm, carrying out centrifugation for 35min to prepare the 80mg/m L titanium quantum dot dispersion liquid, collecting precipitate, continuing centrifugation for 12,000g for 20min, collecting precipitate, and obtaining centrifugal force of the titanium quantum dot dispersion liquid with the concentration of 80mg/m L by centrifugal force.

Preparing graphene-carbon black color paste, namely taking 200m L of 2 mol/L sulfuric acid solution and 0.4Kg of methyl cellulose, respectively adding the sulfuric acid solution and the methyl cellulose into ethanol, stirring and complementing the ethanol to 5000m L to obtain a first dispersing agent, taking 2500m L first dispersing agent and stirring the first dispersing agent, slowly adding 400m L graphene dispersion liquid and 50g of conductive carbon black into the first dispersing agent, and continuously stirring at 1500rpm for 30min to obtain the graphene-carbon black color paste.

And (3) preparing titanium quantum dot slurry, namely taking the residual 2500m L first dispersing agent and stirring the first dispersing agent, respectively slowly adding 1200m L titanium quantum dot dispersion liquid and 200g of acrylic resin into the first dispersing agent, and continuously stirring for 30min at 5000rpm to obtain the titanium quantum dot slurry.

And (2) preparing a titanium quantum dot doped graphene-based mixed solution, namely respectively slowly dropwise adding the prepared titanium quantum dot slurry and 2000m L terpineol into the graphene carbon black color paste while stirring, wherein the stirring speed is 500rpm, after dropwise addition is completed, transferring the stirred mixed solution into a stainless steel high-pressure reaction kettle at 100 ℃, reacting for 0.5h, naturally cooling after the reaction is completed, and stirring at 500rpm continuously in the reaction process to obtain the titanium quantum dot doped graphene-based mixed solution.

Preparing titanium quantum dot doped graphene-based conductive ink: while stirring the titanium quantum dot doped graphene-based mixed solution at 500rpm, 25g of the structural stabilizer, 25g of the polyacrylonitrile-maleic anhydride copolymer and 100g of the leveling agent are added to the titanium quantum dot doped graphene-based mixed solution. Wherein, 25g of the structure stabilizer comprises 10g of ethylenediamine and 15g of p-methylphenol, the polymerization degree of the polyacrylonitrile-maleic anhydride copolymer is 50, and 100g of the flatting agent comprises 83.5g of polypyrrole and 16.3g of polyvinyl alcohol. And after the addition is finished, stirring at 1500rpm for 6 hours to obtain the titanium quantum dot doped graphene-based conductive ink.

Example 2

The preparation method of the Graphene dispersion liquid comprises the steps of providing 500mg of graphite powder, preparing Graphene Oxide (GO) by a modified Hummers method, further transferring the prepared Graphene Oxide to a high-temperature carbonization furnace for high-temperature carbonization for 30s, filling nitrogen into the high-temperature carbonization furnace, wherein the temperature of the high-temperature carbonization furnace is 1200 ℃, placing the Graphene Oxide subjected to high-temperature expansion in an ice water bath, carrying out ultrasonic treatment for 20 minutes under 250W power by using an ultrasonic dispersion instrument, repeating the ultrasonic treatment once, taking supernate, centrifuging and re-suspending to prepare the Graphene Oxide dispersion liquid with the thickness ranging from 8 to 15 layers and the transverse dimension ranging from 700 nm to 1000nm, and centrifuging and concentrating according to requirements to adjust the concentration of the Graphene Oxide dispersion liquid to 120mg/m L.

The preparation method of the titanium quantum dot dispersion liquid comprises the steps of providing 500mg of titanium powder, peeling the titanium raw material by a liquid phase peeling method, centrifuging and resuspending to obtain 5-80 mg/m L of the titanium quantum dot dispersion liquid, in the embodiment, adding 500mg of titanium powder into 100m L of ethanol, selecting probe ultrasound for 250W, performing ultrasound for 15h, selecting ultrasound on/off time as 2/4s, performing ultrasound in an ice bath environment, then performing water bath ultrasound, wherein the water bath ultrasound power is 360W, the ultrasound time is 12h, the water bath temperature is kept at 10 ℃, performing centrifugation to obtain the required metal simple substance titanium quantum dot after the ultrasound, the size range is less than 10nm, in order to prepare the 60mg/m L of the titanium quantum dot dispersion liquid, firstly performing centrifugal force of 5000g for 35min, collecting precipitate for continuing centrifugation for 12,000g for 20min, collecting precipitate to prepare the titanium quantum dot dispersion liquid with the concentration of 60mg/m L.

Preparing graphene-carbon black color paste, namely taking 100m L and 0.05Kg of methylcellulose and 0.15Kg of cellulose nitrate from 10 mol/L hydrochloric acid solution, adding the hydrochloric acid solution, the methylcellulose and the cellulose nitrate into ethanol respectively, stirring and complementing the ethanol to 4000m L to obtain first dispersing agent, taking 2000m L of the first dispersing agent and stirring the first dispersing agent, slowly adding 200m L of graphene dispersion liquid and 100g of conductive carbon black into the first dispersing agent, and continuously stirring at 500rpm for 120min to obtain the graphene carbon black color paste.

And (3) preparing titanium quantum dot slurry, namely taking the residual 2000m L first dispersing agent and stirring the first dispersing agent, slowly adding 1000m L titanium quantum dot dispersion liquid and 180g of epoxy resin into the first dispersing agent respectively, and continuously stirring at 4000rpm for 60min to obtain the titanium quantum dot slurry.

And (2) preparing a titanium quantum dot doped graphene-based mixed solution, namely, respectively slowly dropwise adding the prepared titanium quantum dot slurry and 800m L propylene glycol into graphene carbon black color paste while stirring, wherein the stirring speed is 400rpm, after dropwise addition is completed, transferring the stirred mixed solution into a stainless steel high-pressure reaction kettle at the temperature of 95 ℃, reacting for 0.5h, naturally cooling after the reaction is completed, and stirring at 4000rpm continuously in the reaction process to prepare the titanium quantum dot doped graphene-based mixed solution.

Preparing titanium quantum dot doped graphene-based conductive ink: 20g of structure stabilizer, 20g of polyacrylonitrile-maleic anhydride copolymer and 85g of flatting agent are added into the titanium quantum dot doped graphene base mixed solution while stirring the titanium quantum dot doped graphene base mixed solution at 500rpm, wherein 20g of structure stabilizer comprises 10g of ethylenediamine and 10g of p-methylphenol, the polymerization degree of the polyacrylonitrile-maleic anhydride copolymer is 400, and 85g of flatting agent comprises 60g of polypyrrole and 25g of polyvinyl alcohol. And after the addition is finished, stirring at 2500rpm for 6 hours to obtain the titanium quantum dot doped graphene-based conductive ink.

Example 3

The preparation method of the Graphene dispersion liquid comprises the steps of providing 500mg of graphite powder, preparing Graphene Oxide (GO) by a modified Hummers method, further transferring the prepared Graphene Oxide to a high-temperature carbonization furnace for high-temperature carbonization for 60s, filling argon into the high-temperature carbonization furnace, wherein the temperature of the high-temperature carbonization furnace is 1000 ℃, placing the Graphene Oxide subjected to high-temperature expansion in an ice water bath, carrying out ultrasonic treatment on the Graphene Oxide for 30 minutes under the power of 250W by using an ultrasonic dispersion instrument, repeating the ultrasonic treatment once, taking supernatant, centrifuging and re-suspending to prepare the Graphene Oxide dispersion liquid with the thickness ranging from 1 layer to 8 layers and the transverse dimension ranging from 700 nm to 1000nm, and centrifuging and concentrating according to requirements to adjust the concentration of the Graphene Oxide dispersion liquid to 100mg/m L.

The preparation method of the titanium quantum dot dispersion liquid comprises the steps of providing 500mg of titanium powder, peeling the titanium raw material by a liquid phase peeling method, centrifuging and resuspending to obtain the titanium quantum dot dispersion liquid with the concentration of 5-80 mg/m L, in the embodiment, adding 500mg of titanium powder into 100m L of water, selecting probe ultrasound for 250W, performing ultrasound for 15h, selecting ultrasound on/off time to be 2/4s, performing ultrasound in an ice bath environment, performing water bath ultrasound, wherein the water bath ultrasound power is 360W, the ultrasound time is 12h, keeping the water bath temperature at 10 ℃, performing centrifugation to obtain the required metal simple substance titanium quantum dot after ultrasound, and obtaining the titanium quantum dot dispersion liquid with the size range smaller than 10nm, in order to prepare the titanium quantum dot dispersion liquid with the concentration of 50mg/m L, firstly using the centrifugal force of 5000g, centrifuging for 35min, and collecting and precipitating to obtain the titanium quantum dot dispersion liquid with the concentration of 50mg/m L.

Preparing graphene-carbon black color paste, namely taking 150m L, 0.1Kg of ethyl cellulose, 0.1Kg of hydroxymethyl cellulose and 0.1Kg of cellulose acetate of 8 mol/L sulfuric acid solution, respectively adding the sulfuric acid solution, the ethyl cellulose, the hydroxymethyl cellulose and the cellulose acetate into ethanol, and complementing the ethanol to 3500m L while stirring to prepare first dispersing agent, taking 1750m L first dispersing agent and stirring the first dispersing agent, slowly adding 320m L graphene dispersion liquid and 120g of conductive carbon black into the first dispersing agent, and continuously stirring at 100rpm for 60min to obtain the graphene color paste carbon black.

And (3) preparing titanium quantum dot slurry, namely taking the remaining 1750m L first dispersing agent, stirring the first dispersing agent, slowly adding 1000m L titanium quantum dot dispersion liquid, 50g polydimethylsiloxane resin and 100g acrylic resin into the first dispersing agent respectively, and continuously stirring at 3500rpm for 100min to prepare the titanium quantum dot slurry.

And (2) preparing a titanium quantum dot doped graphene-based mixed solution, namely, respectively slowly dropwise adding the prepared titanium quantum dot slurry, 400m L cyclohexanol and 600m L ethyl acetate into graphene carbon black color paste while stirring, wherein the stirring speed is 300rpm, after dropwise addition is finished, transferring the stirred mixed solution into a stainless steel high-pressure reaction kettle at the temperature of 90 ℃, reacting for 1h, naturally cooling after the reaction is finished, and stirring at 3000rpm continuously in the reaction process to obtain the titanium quantum dot doped graphene-based mixed solution.

Preparing titanium quantum dot doped graphene-based conductive ink: while stirring the titanium quantum dot doped graphene-based mixed solution at 300rpm, 8g of a structural stabilizer, 16g of a polyacrylonitrile-maleic anhydride copolymer and 65g of a leveling agent were added to the titanium quantum dot doped graphene-based mixed solution. Wherein 8g of the structure stabilizer comprises 4g of ethylenediamine and 4g of p-methylphenol, the polymerization degree of the polyacrylonitrile-maleic anhydride copolymer is 100, and 65g of the flatting agent comprises 40g of polypyrrole and 25g of polyethylene glycol. And after the addition is finished, stirring at 3000rpm for 5 hours to obtain the titanium quantum dot doped graphene-based conductive ink.

Example 4

The preparation method of the Graphene dispersion liquid comprises the steps of providing 500mg of graphite powder, preparing Graphene Oxide (GO) by a modified Hummers method, further transferring the prepared Graphene Oxide to a high-temperature carbonization furnace for high-temperature carbonization for 60s, filling nitrogen into the high-temperature carbonization furnace, wherein the temperature of the high-temperature carbonization furnace is 900 ℃, in order to further obtain few-layer Graphene Oxide, placing the Graphene Oxide subjected to high-temperature expansion in an ice water bath, carrying out ultrasonic treatment for 20 minutes at 350W power by using an ultrasonic dispersion instrument, collecting the Graphene Oxide, transferring the primarily dispersed Graphene Oxide into a microfluidic reactor, wherein the pressure of a feeding pump of the microfluidic reactor is 100MPa, the strong-pressure shearing time is 15s, collecting the Graphene Oxide, carrying out ultrasonic treatment for 30 minutes at 250W power by using the ultrasonic dispersion instrument again, taking supernatant, centrifuging, and re-suspending to obtain the Graphene Oxide dispersion liquid with the thickness range of 1-5 layers and the transverse dimension of 700-1000 nm, and carrying out centrifugal concentration according to the requirement so as to adjust the concentration of the Graphene Oxide dispersion liquid to 80 mg/L.

The preparation method of the titanium quantum dot dispersion liquid comprises the steps of providing 500mg of titanium powder, peeling the titanium raw material by a liquid phase peeling method, centrifuging and resuspending to obtain 5-80 mg/m L of the titanium quantum dot dispersion liquid, adding 500mg of the titanium powder into 100m L of N-methylpyrrolidone, selecting probe ultrasonic for 250W, carrying out ultrasonic for 15h, selecting ultrasonic on/off time to be 2/4s, carrying out ultrasonic in an ice bath environment, then adopting water bath ultrasonic, wherein the water bath ultrasonic power is 360W, the ultrasonic time is 12h, keeping the water bath temperature at 10 ℃, and then adopting a centrifugal method to obtain the required metal simple substance titanium quantum dot after ultrasonic treatment, wherein the size range is less than 10nm, in order to prepare 40mg/m L of the titanium quantum dot dispersion liquid, 5000g of the titanium quantum dot dispersion liquid is firstly adopted, centrifuged for 35min, and collected and precipitated to obtain 60mg/m L of the titanium quantum dot dispersion liquid.

Preparing graphene-carbon black color paste, namely taking 100m L of hydrochloric acid solution of 5 mol/L, 0.1Kg of hydroxymethyl cellulose and 0.1Kg of cellulose nitrate, respectively adding the hydrochloric acid solution, the hydroxymethyl cellulose and the cellulose nitrate into ethanol, stirring and complementing the ethanol to 3000m L to obtain first dispersing agent, taking 1500m L of the first dispersing agent and stirring the first dispersing agent, slowly adding 300m L of graphene dispersion liquid and 120g of conductive carbon black into the first dispersing agent, and continuously stirring at 3000rpm for 30min to obtain the graphene carbon black color paste.

And (3) preparing titanium quantum dot slurry, namely taking the rest 1500m L first dispersing agent and stirring the first dispersing agent, respectively and slowly adding 900m L titanium quantum dot dispersion liquid, 60g of polycarbonate resin, 30g of polyurethane resin and 30g of epoxy resin into the first dispersing agent, and continuously stirring at 3000rpm for 120min to obtain the titanium quantum dot slurry.

And (2) preparing a titanium quantum dot doped graphene-based mixed solution, namely, respectively slowly dropwise adding the prepared titanium quantum dot slurry, 800m L ethanol and 400m L terpineol into graphene carbon black color paste while stirring, wherein the stirring speed is 250rpm, after dropwise adding is completed, the mixed solution is transferred into a microwave digestion instrument to be subjected to microwave digestion for 15min, the microwave digestion temperature is 65 ℃, the power is 280W, the mixed solution subjected to microwave digestion is transferred into a stainless steel high-pressure reaction kettle at 85 ℃, the reaction is carried out for 1h, the mixed solution is naturally cooled after the reaction is completed, and the stirring is carried out at 250rpm in the reaction process, so that the titanium quantum dot doped graphene-based mixed solution is prepared.

Preparing titanium quantum dot doped graphene-based conductive ink: while stirring the titanium quantum dot doped graphene-based mixed solution at 300rpm, 12g of a structural stabilizer, 13g of a polyacrylonitrile-maleic anhydride copolymer and 75g of a leveling agent were added to the titanium quantum dot doped graphene-based mixed solution. Wherein, 12g of the structure stabilizer comprises 5g of ethylenediamine and 7g of p-methylphenol, the polymerization degree of the polyacrylonitrile-maleic anhydride copolymer is 150, and 75g of the flatting agent comprises 60g of polypyrrole and 15g of polyvinyl alcohol. And after the addition is finished, stirring is continuously carried out at 3500rpm for 4 hours, so that the titanium quantum dot doped graphene-based conductive ink is prepared.

Example 5

The preparation method of the Graphene dispersion liquid comprises the steps of providing 500mg of graphite powder, preparing Graphene Oxide (GO) by a modified Hummers method, further transferring the prepared Graphene Oxide to a high-temperature carbonization furnace for high-temperature carbonization for 90s, filling nitrogen into the high-temperature carbonization furnace, wherein the temperature of the high-temperature carbonization furnace is 700 ℃, in order to further obtain few-layer Graphene Oxide, placing the high-temperature expanded Graphene Oxide in an ice water bath, carrying out ultrasonic treatment for 20 minutes at 350W power by using an ultrasonic dispersion instrument, collecting the Graphene Oxide, transferring the primarily dispersed Graphene Oxide into a microfluidic reactor, wherein the pressure of a feeding pump of the microfluidic reactor is 100MPa, the strong-pressure shearing time is 15s, collecting the Graphene Oxide, carrying out ultrasonic treatment for 20 minutes at 250W power by using the ultrasonic dispersion instrument again, taking supernatant, centrifuging, and preparing the Graphene Oxide dispersion liquid with the thickness range of 1-5 layers and the transverse dimension of 700-1000 nm, and carrying out centrifugal concentration according to requirements so as to adjust the concentration of the Graphene Oxide dispersion liquid to 50 mg/L m.

The preparation method of the titanium quantum dot dispersion liquid comprises the steps of providing 500mg of titanium powder, peeling the titanium raw material by a liquid phase peeling method, centrifuging and resuspending to obtain 5-80 mg/m L of the titanium quantum dot dispersion liquid, adding 500mg of the titanium powder into 100m L of N-methylpyrrolidone, selecting probe ultrasonic for 250W, carrying out ultrasonic for 15h, selecting ultrasonic on/off time to be 2/4s, carrying out ultrasonic in an ice bath environment, carrying out water bath ultrasonic after the probe ultrasonic is finished, wherein the water bath ultrasonic power is 360W, the ultrasonic time is 12h, keeping the water bath temperature at 10 ℃, carrying out centrifugation to obtain the required metal simple substance titanium quantum dot after the ultrasonic treatment, keeping the size range to be less than 10nm, and carrying out centrifugal force of 5000g and centrifugation for 35min to prepare the 25mg/m L of the titanium quantum dot dispersion liquid, and collecting precipitates to obtain the titanium quantum dot dispersion liquid with the concentration of 25mg/m L.

Preparing graphene-carbon black color paste, namely taking 300m L of 4 mol/L sulfuric acid solution and 0.5Kg of ethyl cellulose, respectively adding the sulfuric acid solution and the ethyl cellulose into ethanol, stirring and complementing the ethanol to 2500m L to obtain a first dispersing agent, taking 1250m L first dispersing agent and stirring the first dispersing agent, slowly adding 250m L graphene dispersion liquid and 150g of conductive carbon black into the first dispersing agent, and continuously stirring at 2000rpm for 45min to obtain the graphene carbon black color paste.

And (3) preparing titanium quantum dot slurry, namely taking the rest 1250m L first dispersing agent and stirring the first dispersing agent, respectively and slowly adding 800m L titanium quantum dot dispersion liquid, 60g of acrylic resin and 20g of water-based alkyd resin into the first dispersing agent, and continuously stirring at 2500rpm for 200min to obtain the titanium quantum dot slurry.

And (2) preparing a titanium quantum dot doped graphene-based mixed solution, namely, slowly dropwise adding the prepared titanium quantum dot slurry, 600m L ethylene glycol and 900m L isopropanol into the graphene carbon black color paste while stirring, wherein the stirring speed is 200rpm, after dropwise adding is completed, the mixed solution is transferred to a microwave digestion instrument for microwave digestion for 5min, the microwave digestion temperature is 70 ℃, the power is 330W, the mixed solution subjected to microwave digestion is transferred to a stainless steel high-pressure reaction kettle at 80 ℃, the reaction is carried out for 1h, the mixed solution is naturally cooled after the reaction is completed, and stirring is carried out at 200rpm in the reaction process, so that the titanium quantum dot doped graphene-based mixed solution is prepared.

Preparing titanium quantum dot doped graphene-based conductive ink: while stirring the titanium quantum dot doped graphene-based mixed solution at 300rpm, adding 15g of a structure stabilizer, 10g of a polyacrylonitrile-maleic anhydride copolymer and 90g of a leveling agent into the titanium quantum dot doped graphene-based mixed solution, wherein the 15g of the structure stabilizer comprises 6g of ethylenediamine and 9g of p-methylphenol, the polymerization degree of the polyacrylonitrile-maleic anhydride copolymer is 200, and the 90g of the leveling agent comprises 80g of polypyrrole and 10g of polyethylene glycol. And after the addition is finished, stirring at 4000rpm for 3 hours to prepare the titanium quantum dot doped graphene-based conductive ink.

Example 6

The preparation method of the Graphene dispersion liquid comprises the steps of providing 500mg of graphite powder, preparing Graphene Oxide (GO) by a modified Hummers method, further transferring the prepared Graphene Oxide to a high-temperature carbonization furnace for high-temperature carbonization for 90s, filling nitrogen into the high-temperature carbonization furnace, wherein the temperature of the high-temperature carbonization furnace is 500 ℃, in order to further obtain few-layer Graphene Oxide, placing the high-temperature expanded Graphene Oxide in an ice water bath, carrying out ultrasonic treatment for 20 minutes at 350W power by using an ultrasonic dispersion instrument, collecting the Graphene Oxide, transferring the primarily dispersed Graphene Oxide into a microfluidic reactor, wherein the pressure of a feeding pump of the microfluidic reactor is 100MPa, the strong-pressure shearing time is 15s, collecting the Graphene Oxide, carrying out ultrasonic treatment for 20 minutes at 250W power by using the ultrasonic dispersion instrument again, taking supernatant, centrifuging, and preparing the Graphene Oxide dispersion liquid with the thickness range of 1-5 layers and the transverse dimension of 700-1000 nm, and centrifuging and concentrating according to requirements to adjust the concentration of the Graphene Oxide dispersion liquid to be 20 mg/L m.

The preparation method of the titanium quantum dot dispersion liquid comprises the steps of providing 500mg of titanium powder, peeling the titanium raw material by a liquid phase peeling method, centrifuging and resuspending to obtain 5-80 mg/m L titanium quantum dot dispersion liquid, adding 500mg of titanium powder into 100m L isopropanol, then selecting probe ultrasonic for 250W, carrying out ultrasonic for 15h, selecting ultrasonic on/off time to be 2/4s, carrying out ultrasonic in an ice bath environment, then adopting water bath ultrasonic, carrying out water bath ultrasonic power to be 360W, carrying out ultrasonic time to be 12h, keeping water bath temperature to be 10 ℃, carrying out centrifugation to obtain required metal elementary titanium quantum dots by a centrifugation method after ultrasonic treatment, wherein the size range is less than 10nm, and carrying out centrifugation for 35min by adopting 5000g for preparing 10mg/m L titanium quantum dot dispersion liquid, and collecting and precipitating to prepare 10mg/m L titanium quantum dot dispersion liquid by centrifugal force.

Preparing graphene-carbon black color paste, namely taking 5 mol/L hydrochloric acid solution 200m L, 0.1Kg of methyl cellulose and 0.05Kg of ethyl cellulose, respectively adding the hydrochloric acid solution, the methyl cellulose and the ethyl cellulose into ethanol, and complementing the ethanol to 2000m L while stirring to obtain a first dispersing agent, taking 1000m L of the first dispersing agent and stirring the first dispersing agent, slowly adding 360m L of graphene dispersion liquid and 200g of conductive carbon black into the first dispersing agent, and continuously stirring at 4000rpm for 15min to obtain the graphene carbon black color paste.

And (3) preparing titanium quantum dot slurry, namely taking the residual 1000m L first dispersing agent and stirring the first dispersing agent, slowly adding 600m L titanium quantum dot dispersion liquid, 25g of phenolic resin and 40g of silicone-acrylate resin into the first dispersing agent respectively, and continuously stirring at 2000rpm for 250min to obtain the titanium quantum dot slurry.

And (2) preparing a titanium quantum dot doped graphene-based mixed solution, namely, respectively slowly dropwise adding the prepared titanium quantum dot slurry and 1800m L isopropanol into the graphene carbon black color paste while stirring, wherein the stirring speed is 150rpm, after dropwise addition is completed, transferring the stirred mixed solution into a 75-DEG C stainless steel high-pressure reaction kettle, reacting for 1.5h, naturally cooling after the reaction is completed, and stirring at 150rpm continuously in the reaction process to obtain the titanium quantum dot doped graphene-based mixed solution.

Preparing titanium quantum dot doped graphene-based conductive ink: while stirring the titanium quantum dot doped graphene-based mixed solution at 200rpm, 10g of a structural stabilizer, 15g of a polyacrylonitrile-maleic anhydride copolymer and 80g of a leveling agent were added to the titanium quantum dot doped graphene-based mixed solution. Wherein, 10g of the structure stabilizer comprises 5g of ethylenediamine and 5g of p-methylphenol, the polymerization degree of the polyacrylonitrile-maleic anhydride copolymer is 300, and 80g of the flatting agent comprises 60g of polypyrrole and 20g of polyvinyl alcohol. And after the addition is finished, stirring at 4500rpm for 2 hours to obtain the titanium quantum dot doped graphene-based conductive ink.

Example 7

The preparation method of the Graphene dispersion liquid comprises the steps of providing 500mg of graphite powder, and preparing Graphene Oxide (GO) by adopting a modified Hummers method, placing Graphene Oxide in an ice water bath, performing ultrasonic treatment for 10 minutes at 350W power by using an ultrasonic dispersion instrument, repeating the steps once, taking supernate, centrifuging and re-suspending to obtain the Graphene Oxide dispersion liquid with the thickness of 2-20 layers and the transverse dimension of 700-1000 nm, and performing centrifugal concentration according to requirements to adjust the concentration of the Graphene Oxide dispersion liquid to 5mg/m L.

The preparation method of the titanium quantum dot dispersion liquid comprises the steps of providing 500mg of titanium powder, peeling the titanium raw material by a liquid phase peeling method, centrifuging and resuspending to obtain 5-80 mg/m L of the titanium quantum dot dispersion liquid, in the embodiment, adding 500mg of titanium powder into 100m L of ethanol, selecting probe ultrasound for 250W, performing ultrasound for 10h, selecting ultrasound on/off time as 2/4s, performing ultrasound in an ice bath environment, then performing water bath ultrasound, wherein the water bath ultrasound power is 360W, the ultrasound time is 8h, keeping the water bath temperature at 10 ℃, performing centrifugation to obtain the required metal elementary substance titanium quantum dot after ultrasound, wherein the size range is less than 20nm, and in order to prepare the 5mg/m L of the titanium quantum dot dispersion liquid, firstly performing centrifugal force of 5000g, centrifuging for 35min, collecting and precipitating to obtain the 5mg/m L of titanium quantum dot dispersion liquid.

Preparing graphene-carbon black color paste, namely taking 1 mol/L sulfuric acid solution 180m L and 0.2Kg cellulose acetate, respectively adding the sulfuric acid solution and the cellulose acetate into ethanol, stirring and complementing the ethanol to 1000m L to obtain a first dispersing agent, taking 500m L first dispersing agent and stirring the first dispersing agent, slowly adding 150m L graphene dispersion liquid and 250g of conductive carbon black into the first dispersing agent, and continuously stirring at 5000rpm for 10min to obtain the graphene-carbon black color paste.

And (3) preparing titanium quantum dot slurry, namely taking the residual 500m L first dispersing agent and stirring the first dispersing agent, slowly adding 400m L titanium quantum dot dispersion liquid, 30g epoxy resin and 20g water-based alkyd resin into the first dispersing agent respectively, and continuously stirring at 500rpm for 300min to obtain the titanium quantum dot slurry.

And (2) preparing a titanium quantum dot doped graphene-based mixed solution, namely, respectively slowly dropwise adding the prepared titanium quantum dot slurry and 500m L ethyl acetate into graphene carbon black color paste while stirring, wherein the stirring speed is 100rpm, after dropwise addition is completed, transferring the stirred mixed solution into a stainless steel high-pressure reaction kettle at 70 ℃, reacting for 2 hours, naturally cooling after the reaction is completed, and stirring at 100rpm continuously in the reaction process to prepare the titanium quantum dot doped graphene-based mixed solution.

Preparing titanium quantum dot doped graphene-based conductive ink: while stirring the titanium quantum dot doped graphene-based mixed solution at 200rpm, 5g of a structural stabilizer, 5g of a polyacrylonitrile-maleic anhydride copolymer and 50g of a leveling agent were added to the titanium quantum dot doped graphene-based mixed solution. Wherein, 5g of the structure stabilizer comprises 2g of ethylenediamine and 3g of p-methylphenol, the polymerization degree of the polyacrylonitrile-maleic anhydride copolymer is 300, and 50g of the flatting agent comprises 29g of polypyrrole and 21g of polyvinyl alcohol. And after the addition is finished, stirring at 5000rpm for 1h to prepare the titanium quantum dot doped graphene-based conductive ink.

Comparative example 1

Preparation method of graphene dispersion a graphene oxide dispersion having a concentration of 80mg/m L was prepared with reference to example 4.

Preparation method of titanium quantum dot dispersion liquid a titanium quantum dot dispersion liquid with a concentration of 60mg/m L was prepared with reference to example 4.

Preparing graphene-carbon black color paste: graphene carbon black paste was prepared according to example 4.

Preparing titanium quantum dot slurry: titanium quantum dot slurry was prepared with reference to example 4.

And (2) preparing a titanium quantum dot doped graphene-based mixed solution, namely, respectively slowly dropwise adding the prepared titanium quantum dot slurry, 800m L ethanol and 400m L terpineol into graphene carbon black color paste while stirring, wherein the stirring speed is 250rpm, after dropwise adding is finished, the mixed solution is transferred into a microwave digestion instrument to be subjected to microwave digestion for 15min, the microwave digestion temperature is 65 ℃, and the power is 280 W.250rpm and continuously stirred for 1h to prepare the titanium quantum dot doped graphene-based mixed solution.

Comparative example 2

Preparing graphene-carbon black color paste, namely taking 0.1Kg of hydroxymethyl cellulose and 0.1Kg of cellulose nitrate, respectively adding the hydroxymethyl cellulose and the cellulose nitrate into ethanol, stirring and complementing the ethanol to 3000m L to obtain a first dispersing agent, taking 1500m L of the first dispersing agent, stirring the first dispersing agent, slowly adding 300m L of graphene dispersion liquid and 120g of conductive carbon black into the first dispersing agent, and continuously stirring at 3000rpm for 30min to obtain the graphene-carbon black color paste.

And (3) preparing titanium quantum dot slurry, namely taking the rest 1500m L first dispersing agent and stirring the first dispersing agent, and adding 900m L titanium quantum dot dispersion liquid, 60g of polycarbonate resin, 30g of polyurethane resin and 30g of epoxy resin slowly into the first dispersing agent in half, and continuously stirring at 3000rpm for 120min to obtain the titanium quantum dot slurry.

Comparative example 3

Preparing a titanium quantum dot doped graphene-based mixed solution: a titanium quantum dot doped graphene-based mixed solution was prepared with reference to example 4.

Preparing titanium quantum dot doped graphene-based conductive ink: while stirring the titanium quantum dot doped graphene-based mixed solution at 300rpm, 13g of polyacrylonitrile-maleic anhydride copolymer and 75g of a leveling agent were added to the titanium quantum dot doped graphene-based mixed solution. Wherein the polymerization degree of the polyacrylonitrile-maleic anhydride copolymer is 150, and 75g of the flatting agent comprises 60g of polypyrrole and 15g of polyvinyl alcohol. And after the addition is finished, stirring is continuously carried out at 3500rpm for 4 hours, so that the titanium quantum dot doped graphene-based conductive ink is prepared.

Effect embodiment:

(1) adhesion Performance test

Respectively blade-coating the titanium quantum dot doped graphene-based conductive inks prepared in examples 1 to 7 and comparative examples 1 to 3 on an aluminum foil, a PE (polyethylene) plate and a ceramic plate, wherein the aluminum foil plate is transferred to an air-blast drying oven at 80 ℃ to be dried for 1 hour to obtain a graphene conductive ink film; transferring the PE plate to a 70 ℃ forced air drying oven to be dried for 1h to obtain a graphene conductive ink film; and (3) transferring the ceramic plate to a 70 ℃ forced air drying oven to be dried for 1h to obtain the graphene conductive ink film. Hardness was tested according to the national standard GB/T6739-1996 using a Chinese pencil, and the results are shown in Table 1. According to the national standard GB/T13217.4-2008, the adhesive force is tested by using the 3M special adhesive tape, and the test result is shown in Table 1.

TABLE 1

As can be seen from the results in table 1, the graphene conductive ink films formed by respectively blade-coating the titanium quantum dot doped graphene conductive inks prepared in examples 1 to 7 have good adhesion to aluminum foils, PE plates, and ceramic plates, which indicates that the titanium quantum dot doped graphene conductive ink prepared according to the present invention can be applied to the preparation of external heating wall paintings, wallpaper, or floors, and is disposed on a heating substrate by blade coating, spin coating, direct writing, screen printing, silk printing, inkjet printing, or electrostatic spinning, and after curing, a graphene conductive ink film (graphene conductive film) can be obtained. Compared with the titanium quantum dot doped graphene-based conductive inks prepared in examples 1 to 7, the titanium quantum dot doped graphene-based conductive inks prepared in comparative examples 1 to 3 have poor adhesion to aluminum foils, PE plates, and ceramic plates. According to the titanium quantum dot doped graphene-based conductive ink corresponding to the comparative example 1, the prepared graphene oxide is not sufficiently doped with the titanium quantum dot, and meanwhile, an active group of the graphene oxide exposed on the surface is not reacted with resin, so that the adhesion effect of the prepared ink film with a metal substrate, a PE substrate and ceramic is poor. In comparative example 2, a strong acid solution having a catalytic effect is not added, and active groups of graphene oxide exposed on the surface do not sufficiently react with the resin, so that the prepared ink film has a poor adhesion effect with a metal substrate, a PE substrate, and ceramics. In comparative example 3, no structural stabilizer was added, and graphene oxide in the prepared titanium quantum dot doped graphene-based conductive ink was not reduced and was in an unstable state, which also affected the adhesion effect of the ink film to the metal substrate, the PE substrate, and the ceramic.

The graphene conductive ink films formed by the titanium quantum dot doped graphene-based conductive inks prepared in examples 1 to 7 and comparative example 3 have strong hardness, while the graphene conductive ink films formed by the titanium quantum dot doped graphene-based conductive inks in comparative example 1 and comparative example 2 have low hardness, which may be related to that the active groups exposed on the surface of the graphene oxide do not react with the resin or do not react sufficiently.

(2) High temperature resistance test and service life test

The titanium quantum dot doped graphene-based conductive ink prepared in examples 1 to 7 and comparative examples 1 to 3 was printed on a PI plate by a relief printing technique, and the printed PI plate was transferred to a forced air drying oven at 80 ℃ to be dried and cured for 4 hours, thereby finally obtaining a graphene conductive ink film with a thickness of 10 μm.

The graphene conductive ink film with the length and the width of 10cm is cut by a blade to carry out an initial sheet resistance test, and the test result is shown in table 2. And cutting the graphene conductive ink film printed on the PI plate into graphene conductive ink films with the length and the width of 10cm by adopting a blade, cutting three films corresponding to each embodiment, and dividing the films into A, B, C groups for carrying out a high temperature resistance test. The experimental method is as follows: placing the graphene conductive ink film of the group A in an oven at 100 ℃, and measuring the square resistance value every other day; placing the graphene conductive ink film of the group B in an oven at 200 ℃, and measuring the square resistance value every other day; the graphene conductive ink film of group C was placed in an oven at 300 ℃, and the square resistance was measured every other day, the measurement results are shown in table 2.

TABLE 2

From the results in table 2, it can be seen that the graphene conductive ink films corresponding to examples 1 to 7 are generally relatively high temperature resistant, and the sheet resistance of the graphene conductive ink films after long-time high-temperature treatment is not greatly changed, wherein the sheet resistance of the graphene conductive ink films corresponding to examples 1 to 7 is less than 500, and the graphene conductive ink films can be used as a heating layer of a high-power electrothermal device. In contrast, the sheet resistance of the graphene conductive ink film prepared in the comparative examples 1 to 3 is obviously changed, and the reason may be related to the instability of the titanium quantum dot doped graphene conductive ink prepared in the comparative examples 1 to 3, especially the instability of the graphene oxide structure, and as a result, the graphene conductive ink film is rapidly aged under high temperature conditions, and the service life is greatly shortened.

The graphene conductive ink film with the length and width of 1m is cut by a blade to perform an initial sheet resistance test, and the test results are shown in table 3. Inserting metal electrodes into opposite corners of two ends of the cut graphene conductive ink film respectively and connecting the metal electrodes into commercial power to test the service life, wherein the test method comprises the following steps: and continuously electrifying the graphene conductive ink film to generate heat, and testing the square resistance value of the graphene conductive ink film every other week (W).

TABLE 3

From the results in table 3, it is clear that the graphene conductive ink films according to examples 1 to 7 do not change much in the overall sheet resistance value after being continuously electrified for 5W to generate heat, and thus can be used for the heat generating layer of the electric heating device which is heated for a long time. The larger the change in sheet resistance of the graphene conductive ink films corresponding to comparative examples 1-3 may be related to the instability of the graphene oxide structure and the overall ink mixing system therein.

(3) Test of anti-aging Performance

The graphene conductive ink film with the length and the width of 1m is cut by a blade to carry out an anti-aging performance test, and the test results are shown in table 4. And inserting metal electrodes into opposite corners of two ends of the cut graphene conductive ink film respectively and connecting the metal electrodes to mains supply to perform continuous heat production. Firstly, testing the initial heat generation power of the graphene conductive ink film by using instruments such as an ammeter and the like, continuously working for 300 hours, testing the heat generation power of the graphene conductive ink film by using instruments such as an ammeter and the like, and calculating the heat generation power attenuation rate of the graphene conductive ink film, wherein the results are shown in table 4.

After the continuous operation for 300h, as shown in fig. 1, 9 temperature sensors are sequentially arranged on the PI plate to measure the temperature of each position of the graphene conductive ink film, and the difference between the maximum value and the minimum value of the 9 temperature sensors is selected to be recorded as the temperature nonuniformity of the graphene conductive ink film.

TABLE 4

From the results in table 4, it can be seen that the power attenuation rate and the temperature non-uniformity of the graphene conductive ink thin films corresponding to examples 1 to 7 are not large, which indicates that the graphene conductive ink thin film prepared by the present invention can be used for long-term heat generation, and the variation of the heat generation power and the heat generation non-uniformity in the production period is not large. In contrast, the graphene conductive ink thin films corresponding to comparative examples 1 to 3 have large power attenuation rates and temperature non-uniformity, and are not suitable for long-term heat generation of the heat-generating conductive film, which may be related to the unstable structure of graphene oxide.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims

1. The titanium quantum dot doped graphene-based conductive ink is characterized by comprising the following components in parts by weight:

2. The titanium quantum dot doped graphene-based conductive ink according to claim 1, comprising the following components in parts by weight:

3. The titanium quantum dot doped graphene-based conductive ink as claimed in claim 1, wherein the first dispersant comprises 1-10 mol/L of a strong acid solution, ethanol and a cellulose derivative, wherein the ratio of the strong acid solution, the ethanol and the cellulose derivative is 10: 50-300: 5-20;

4. The titanium quantum dot doped graphene-based conductive ink of claim 1, wherein the second dispersant comprises a combination of one or more of propylene glycol, cyclohexanol, terpineol, ethanol, ethylene glycol, isopropanol, and ethyl acetate.

5. The titanium quantum dot doped graphene-based conductive ink according to claim 1, wherein the release resin is one or more of epoxy resin, polydimethylsiloxane resin, polycarbonate resin, polyurethane resin, acrylic resin, waterborne alkyd resin, phenolic resin, and silicone acrylic resin.

6. The titanium quantum dot doped graphene-based conductive ink as claimed in claim 1, wherein the leveling agent comprises polypyrrole, and the leveling agent further comprises polyvinyl alcohol or polyethylene glycol, wherein the mass ratio of the polypyrrole to the polyvinyl alcohol or the polyethylene glycol is 8: 1-5;

7. A preparation method of titanium quantum dot doped graphene-based conductive ink is characterized by comprising the following steps of:

the stirring speed is 100-5000 rpm.

8. The method for preparing the titanium quantum dot doped graphene-based conductive ink according to claim 7, wherein in the graphene dispersion liquid preparation process, the prepared graphene oxide is transferred to a high-temperature carbonization furnace to be carbonized at a high temperature for 30-90 s, the high-temperature carbonization furnace is filled with inert gas, the temperature of the high-temperature carbonization furnace is 500-1200 ℃, and the graphene oxide expanded at a high temperature is prepared into 5-150 mg/m L graphene dispersion liquid.

9. The method for preparing the titanium quantum dot doped graphene-based conductive ink as claimed in claim 7, wherein in the process of preparing the titanium quantum dot dispersion liquid, the titanium raw material is added into a polar solvent, and ultrasonic treatment is performed for 10-15h by using a probe under an ice bath environment;

10. Use of the titanium quantum dot doped graphene-based conductive ink as defined in any one of claims 1 to 6 for preparing a graphene conductive film.