CN112391087A - Porous molybdenum carbide MXene/reduced graphene oxide-based conductive ink and preparation method thereof - Google Patents
Porous molybdenum carbide MXene/reduced graphene oxide-based conductive ink and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of porous molybdenum carbide MXene/reduced graphene oxide-based conductive ink, which comprises the following steps: preparing a working electrode, preparing a molybdenum carbide/graphite oxide material, preparing a molybdenum carbide MXene/reduced graphene oxide dispersion liquid, preparing a particulate resin slurry, and preparing a molybdenum carbide MXene/reduced graphene oxide-based conductive ink. In the working electrode preparation step, graphite powder and molybdenum aluminum carbide powder are mixed to serve as a working electrode, the working electrode serves as an etching base material for subsequent electrolytic etching to realize primary stripping, molybdenum carbide MXene and reduced graphene oxide are further prepared by stripping through probe ultrasound and water bath ultrasound, and finally the porous molybdenum carbide MXene/reduced graphene oxide conductive ink is prepared by mixing with resin, particle powder and other additives. The invention also provides porous molybdenum carbide MXene/reduced graphene oxide-based conductive ink.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to porous molybdenum carbide MXene/reduced graphene oxide-based conductive ink and a preparation method of the porous molybdenum carbide MXene/reduced graphene oxide-based conductive ink.
Background
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, convenience and rapidness in zone control, stability in 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.
Graphene is a molecule formed by the passage of carbon atoms through sp2The hybridized orbitals form a hexagonal two-dimensional nano material which is in a honeycomb lattice structure and only has one layer of carbon atom thickness. 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 (5300W/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.
In the prior art, graphene is generally prepared into graphene slurry, ink or paint, and then prepared into a graphene heating coating and the like through a printing method. However, the graphene heating coating prepared by the methods has the defects of poor thickness controllability, uneven heat generation, large sheet resistance, general heat conducting property, limited infrared emissivity and the like, and the existing graphene heating coating has the problems of poor flexibility, low electric conductor concentration, easy embrittlement after long-term use and the like, so that the existing graphene heating coating is short in service life and is not suitable for long-term use.
Disclosure of Invention
In view of the above, the invention provides a preparation method of porous molybdenum carbide MXene/reduced graphene oxide-based conductive ink, and the invention also provides the porous molybdenum carbide MXene/reduced graphene oxide-based conductive ink prepared by the preparation method of the porous molybdenum carbide MXene/reduced graphene oxide-based conductive ink, so as to solve the problems of poor thickness controllability, nonuniform heat generation, large sheet resistance, general heat conductivity, limited infrared emissivity, poor flexibility of a graphene heating coating, easy brittle fracture after long-term use and the like of the existing conductive ink.
In a first aspect, the invention provides a preparation method of porous molybdenum carbide MXene/reduced graphene oxide-based conductive ink, which comprises the following steps:
preparing a working electrode: providing graphite powder and molybdenum carbide powder, grinding the graphite powder and the molybdenum carbide powder to a fineness of more than 200 meshes, wherein the mass ratio of the graphite powder to the molybdenum carbide powder is 1-8: 1, and mixing the graphite powder and the molybdenum carbide powder and pressing into a working electrode;
preparing a molybdenum carbide/graphite oxide material: fixing the working electrode in an electrolytic cell, adding electrolyte into the electrolytic cell to enable the working electrode to be immersed in the electrolyte, wherein the electrolyte is fluorine-containing anion liquid and is used as an etching agent, the working electrode is used as a positive electrode, voltage is applied to enable the fluorine-containing anion liquid to be ionized to generate fluorine free radicals, and after electrolysis is finished, centrifuging and collecting precipitates for the electrolyte to obtain a molybdenum carbide/graphite oxide material;
preparing a molybdenum carbide MXene/reduced graphene oxide dispersion liquid: dissolving the molybdenum carbide/graphite oxide material in isopropanol according to the mass-volume ratio of 50-500 mg/ml, performing probe ultrasound on the isopropanol containing the molybdenum carbide/graphite oxide material, centrifuging the isopropanol containing the molybdenum carbide/graphite oxide material at 8000-15000 rpm for 10-30 min after the probe ultrasound is finished, collecting precipitates, immersing the precipitates in a reducing reagent for reduction, centrifuging, collecting the precipitates, drying, dispersing the dried precipitates in a first dispersing agent, and performing water bath ultrasound to obtain a molybdenum carbide MXene/reduced graphene oxide dispersion solution;
preparing a particle resin slurry: providing and mixing particulate matter powder and a second dispersing agent, adding resin into the second dispersing agent while stirring the second dispersing agent to prepare particulate matter resin slurry, wherein the diameter of the particulate matter powder is 0.1-1 mu m, the concentration of the particulate matter powder is 10-100 mg/ml, and the concentration of the resin is 50-500 mg/ml;
preparing molybdenum carbide MXene/reduced graphene oxide-based conductive ink: mixing the granular resin slurry, molybdenum carbide MXene/reduced graphene oxide dispersion liquid, polyacrylonitrile-maleic anhydride copolymer and a stabilizer according to the mass ratio of 500: 1000-10000: 1-50: 5-20, transferring the mixture to a protective gas environment, stirring at a constant temperature of 65-85 ℃ until the volume is 1/2-1/6, and preparing the porous molybdenum carbide MXene/reduced graphene oxide-based conductive ink;
the molybdenum aluminum carbide powder is Mo3AlC2And the particle powder is carbonate powder or metal oxide powder.
The preparation method of the porous molybdenum carbide MXene/graphene-based conductive ink comprises the steps of preparing a working electrode, preparing a molybdenum carbide/graphite oxide material, preparing a molybdenum carbide MXene/graphene oxide dispersion liquid, preparing a particulate resin slurry and preparing the molybdenum carbide MXene/graphene oxide ink. In the working electrode preparation step, graphite powder and molybdenum aluminum carbide powder are mixed to serve as a working electrode, and the working electrode serves as an etching base material for subsequent electrolytic etching. The ratio of the graphite powder to the molybdenum carbide powder can also control the ratio of molybdenum carbide MXene, reduced graphene oxide and graphite powder which is not completely stripped, the molybdenum carbide MXene, reduced graphene oxide and graphite powder in proper proportion can improve the conductivity, dispersion effect and conductivity uniformity of the conductive ink, and can also play a role in promoting stripping and dispersion of the molybdenum carbide MXene and the graphene oxide.
The working electrode is fixed in an electrolytic cell, fluorine-containing anion liquid is ionized near the anode to generate fluorine free radicals (F), the fluorine free radicals etch graphite powder on the surface of the electrode to enable the graphite powder to fall off from the electrode, and at the moment, a large number of active groups such as hydroxyl groups are formed on the surface of the graphite powder to play a role in primarily stripping the graphite powder. Meanwhile, the fluorine free radicals also etch metal aluminum in the molybdenum carbide powder, and the molybdenum carbide powder is separated from the electrode and forms flaky multilayer net-shaped molybdenum carbide. The graphite powder and the molybdenum carbide powder are doped and distributed, and the graphite powder and the molybdenum carbide powder can be etched simultaneously through the fluorine free radical etching process, so that the stripping efficiency of the graphite powder and the molybdenum carbide powder is improved, and the subsequent preparation of graphene oxide and molybdenum carbide MXene is facilitated. Further dissolving the molybdenum carbide/graphite oxide material in isopropanol (stripping dispersion liquid) to carry out probe ultrasonic liquid phase stripping, carrying out common probe ultrasonic treatment on the preliminarily stripped molybdenum carbide with the multi-layer network structure and the preliminarily stripped graphite powder, further stripping the molybdenum carbide with the multi-layer network structure to obtain molybdenum carbide MXene, and stripping the graphite powder to obtain graphene oxide. The pulse oscillation process of probe supersound can realize the formation of molybdenum carbide MXene and graphite oxide, can also ensure to be unlikely to too big power, lead to the preparation sheet incomplete, size undersize. The molybdenum carbide with the multi-layer net-shaped structure is poor in dispersibility in stripping dispersion liquid, the primarily stripped graphene is added into the stripping dispersion liquid of the molybdenum carbide with the multi-layer net-shaped structure, probe ultrasound is carried out together, the molybdenum carbide with the multi-layer net-shaped structure is effectively stripped to form molybdenum carbide MXene under the assistance of the primarily stripped graphene, graphite powder is stripped to form graphene oxide, good doping of the molybdenum carbide MXene and the graphene oxide can be promoted in the common stripping process, and secondary stacking is prevented. And centrifuging isopropanol containing the molybdenum carbide/graphite oxide material, collecting precipitate, immersing the precipitate into a reducing reagent for reduction, wherein the precipitate comprises molybdenum carbide MXene, graphene oxide and graphite powder which is not completely stripped, and reducing the graphene oxide into reduced graphene oxide to play a role in stabilizing the lamellar structures of the graphene and the molybdenum carbide MXene. And centrifuging the reduced mixed solution again, collecting the precipitate, drying, dispersing the dried precipitate in a first dispersing agent, and further dispersing the molybdenum carbide MXene, the graphene oxide and the graphite powder which is not completely stripped in the first dispersing agent by water bath ultrasound to obtain the molybdenum carbide MXene/reduced graphene oxide dispersion liquid.
In the step of preparing the particulate resin slurry, the particulate powder and the second dispersant are mixed, and the resin is added to the second dispersant while stirring the second dispersant to prepare the particulate resin slurry. The second dispersing agent can promote the good mixing of the resin and the particle powder and also can effectively promote the mixing and dissolution of the particle resin slurry and the molybdenum carbide MXene/reduced graphene oxide dispersion liquid. The particulate powder is carbonate powder or metal oxide powder, and after the conductive film is formed by printing, printing or coating, the particulate powder is mostly fixed on the surface of the conductive film due to the thin film layer. After film formation, the conductive film is immersed in an acid solution, surface particle powder is dissolved in an acid liquid to enable the conductive film to form a surface porous structure, the cleaned and dried conductive film has the surface porous structure, the surface infrared emission amount of the conductive film is higher, the heat release of the conductive film is facilitated, and the thermal conductivity is higher.
In the step of preparing the molybdenum carbide MXene/reduced graphene oxide-based conductive ink, the granular resin slurry, the molybdenum carbide MXene/reduced graphene oxide dispersion liquid, the polyacrylonitrile-maleic anhydride copolymer and the stabilizer are uniformly mixed in a constant-temperature water bath mode, meanwhile, the molybdenum carbide MXene and the reduced graphene oxide can be promoted to be connected with active groups on the surfaces of resin particles in a heating process, so that the conductive particles with high conductivity of the molybdenum carbide MXene and high flexibility of the reduced graphene oxide are formed, and finally, the film is formed by means of the resin particles. The single molybdenum carbide MXene is poor in flexibility and easy to oxidize, the conductive capacity of the oxidized MXene is reduced rapidly, the stripping and dispersion of the molybdenum carbide MXene can be promoted in the process of stripping the molybdenum carbide MXene and the reduced graphene oxide together, the molybdenum carbide MXene and the reduced graphene oxide are blended in the printing ink, and the effect of preventing the molybdenum carbide MXene from being oxidized can be achieved by means of the high conductivity and flexibility of the reduced graphene oxide and the reductive protection effect of the stabilizer, and the flexibility of the conductive film can also be enhanced. The polyacrylonitrile-maleic anhydride copolymer has the main functions of harmonizing the uniformity of the ink, reducing the viscosity and surface tension of the ink, and simultaneously playing the roles of maintaining the long-term stability of the ink structure and preventing brittle fracture in the using process.
Preferably, in the step of preparing the working electrode, the graphite powder and the molybdenum aluminum carbide powder are ground to 300-mesh fineness, and the mass ratio of the graphite powder to the molybdenum aluminum carbide powder is 2-6: 1. The graphite powder and the molybdenum carbide powder are ground to 300-mesh fineness, so that the graphite powder and the molybdenum carbide powder can be efficiently etched in the subsequent etching process, the doping of the preliminarily stripped multilayer net-shaped molybdenum carbide and the preliminarily stripped graphite powder can be promoted, and the subsequent stripping process is facilitated.
Preferably, in the step of preparing the molybdenum carbide/graphite oxide material, the fluorine-containing anion liquid is an organic solvent containing fluorine anions, wherein the fluorine-containing anions in the fluorine-containing anion liquid are at least one of tetrafluoroborate ions and hexafluorophosphate ions. The tetrafluoroborate ions and the hexafluorophosphate ions are organic fluorine-containing anions, and can be ionized to generate fluorine free radicals in the ionization process of the tetrafluoroborate ions and the hexafluorophosphate ions in the electrolysis process, and the fluorine free radicals only remain near the anode, so that the electrolyzed water is prevented from generating hydrogen ions, graphite powder and molybdenum aluminum carbide powder are etched through the fluorine free radicals, and meanwhile, the organic solvent containing the fluorine anions has a certain protective effect on the preliminarily etched multilayer net-shaped structure molybdenum carbide.
Preferably, in the step of preparing the molybdenum carbide/graphite oxide material, the fluorine-containing anion liquid includes at least one of 1-ethyl-3-methylimidazole tetrafluoroborate, 1-ethyl-3-methylimidazole hexafluorophosphate, 1-butyl-3-methylimidazole tetrafluoroborate, 1-butyl-3-methylimidazole hexafluorophosphate, 1-octyl-3-methylimidazole tetrafluoroborate, 1-octyl-3-methylimidazole hexafluorophosphate, 1-hexyl-3-methylimidazole tetrafluoroborate and 1-hexyl-3-methylimidazole hexafluorophosphate. Therefore, by selecting the fluorine-containing organic salt, the fluorine-containing organic salt can be effectively dissolved in an organic solvent, a good mass transfer function is realized, fluorine free radicals can be generated by high-efficiency ionization, and the normal operation of an etching process is ensured.
Preferably, in the step of preparing the molybdenum carbide/graphite oxide material, the organic solvent of the organic solvent containing fluoride anions is at least one of acetonitrile, ethanol, isopropanol, acetone, N-methylpyrrolidone, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran and dichloromethane. Therefore, efficient mass transfer can be ensured through the organic solvent, fluorine-containing anions in the electrolyte can be promoted to be electrophoresed to the vicinity of the anode for ionization to generate fluorine radicals, and the fluorine radicals are active and can only exist temporarily, namely the fluorine radicals only exist in the vicinity of the electrode and not in all electrolyte of the electrolytic cell, so that the electrode can be efficiently etched, and the molybdenum carbide with the multi-layer mesh structure which is preliminarily stripped can be protected.
Preferably, in the step of preparing the molybdenum carbide/graphite oxide material, the concentration of the fluorine-containing anion liquid is 1-3 mol/L, the voltage is + 4-10V, and the electrolysis time is 5-15 h;
the temperature of the electrolyte in the electrolysis process is 35-45 ℃, the electrolyte is continuously stirred in the electrolysis process, and the stirring revolution is 150-300 rpm. The proper fluorine-containing anion concentration, voltage, electrolysis time and temperature can promote the etching process and simultaneously prevent over-etching from reducing the yield of graphene oxide and molybdenum carbide MXene. The continuous stirring of the electrolyte in the electrolysis process can promote the graphite powder and the molybdenum aluminum carbide powder which are initially stripped to be rapidly separated from the electrode area (namely the fluorine radical etching area), and the function of preventing excessive etching is achieved.
More preferably, in the step of preparing the molybdenum carbide/graphite oxide material, the fluorine-containing anion liquid has a concentration of 2 mol/L, the voltage is + 6V, and the electrolysis time is 10 h.
Preferably, in the step of preparing the molybdenum carbide/graphite oxide material, the electrolyte is sieved by a 400-mesh sieve and then centrifuged to collect precipitates, wherein the centrifugation speed is 5000-10000 rpm, and the centrifugation time is 20-60 min. The electrolyte can be effectively removed by sieving the electrolyte with a 400-mesh sieve, so that the efficiency of subsequent liquid-phase ultrasonic stripping is improved, the electrolyte and the graphite powder can also promote the mixing of the graphite powder, the graphene and the molybdenum carbide, and the electrolyte is centrifugally collected and precipitated for the subsequent stripping process.
Preferably, in the step of preparing the molybdenum carbide MXene/reduced graphene oxide dispersion liquid, the ultrasonic power of the probe is 300-500W, the ultrasonic time of the probe is 3-10 h, and the temperature of isopropanol of the molybdenum carbide/graphite oxide material in the ultrasonic process of the probe is lower than 15 ℃. After the etching process, the graphite powder and the molybdenum aluminum carbide powder are easier to be stripped into flaky nanometer materials. The isopropanol used as the dispersion liquid has a good dispersion effect, has the effect of stabilizing the structures of the molybdenum carbide MXene and the graphene oxide, and prevents the molybdenum carbide MXene or the graphene oxide from being stacked or agglomerated again. In the ultrasonic process of the probe, molybdenum carbide with a multi-layer mesh structure can be effectively stripped to form molybdenum carbide MXene and graphite is stripped to form graphene oxide by means of pulse ultrasonic waves, the graphene oxide and the molybdenum carbide MXene are ultrasonically stripped together, the stripping efficiency of the graphene oxide and the molybdenum carbide MXene is improved, and on the other hand, the stripped graphene oxide and the molybdenum carbide MXene are uniformly doped, so that the molybdenum carbide MXene is protected, and the molybdenum carbide MXene is prevented from being oxidized and degraded.
Preferably, the working frequency of the probe ultrasound is set to work for 5 s and pause for 5 s. The ultrasonic frequency setting of the probe ultrasonic can effectively promote the stripping of the graphene oxide and the molybdenum carbide MXene, and meanwhile, the local temperature rise and degradation caused by the continuous ultrasonic process can be avoided.
Preferably, the reducing agent is at least one of hydroiodic acid, hydrazine hydrate, ascorbic acid, and sodium borohydride. The reduction of the graphene oxide in the precipitate to reduced graphene oxide can be promoted by the reducing reagent, and the molybdenum carbide MXene is also stabilized to a certain extent.
Preferably, the power of the water bath ultrasound is 200-300W, the time of the water bath ultrasound is 8-24 h, and the temperature of the first dispersing agent in the water bath ultrasound process is lower than 15 ℃. The proper power, time and temperature of the water bath ultrasound can ensure that the graphite powder, the reduced graphene oxide and the molybdenum carbide MXene are uniformly dispersed in the first dispersing agent, and the effect of stabilizing the structure of the molybdenum carbide MXene is achieved.
Preferably, the first dispersant is one or more of propylene glycol, cyclohexanol, terpineol, ethanol, ethylene glycol and isopropanol. The first dispersing agent plays a role in dispersing graphite powder, reduced graphene oxide and molybdenum carbide MXene, and when the uniformly dispersed graphite powder, reduced graphene oxide and molybdenum carbide MXene are mixed with other components in the printing ink, the uniformly dispersed graphite powder, reduced graphene oxide and molybdenum carbide MXene are conveniently dispersed, and the overall uniformity of the printing ink is improved.
Preferably, in the step of preparing the resin slurry of particulate matter, the second dispersant is a cellulose derivative, and the cellulose derivative is one or more of methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, cellulose acetate and cellulose nitrate in combination. The second dispersing agent plays a role in promoting mixing and dispersion of the particulate powder and the resin, the particulate powder and the resin are dispersed in advance through the second dispersing agent, and then the particulate resin slurry is mixed with the molybdenum carbide MXene/reduced graphene oxide dispersion liquid to promote uniform mixing of the whole printing ink, so that the surface porous structure (the porous structure formed after pickling) of the film-formed conductive film is more uniform, the infrared ray release amount, the conductivity and the heat conductivity of the unit area are higher, and the local temperature is prevented from being too high.
Preferably, in the step of preparing the particulate resin slurry, the 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. The conductive ink has the advantages that the film forming effect of the resin is beneficial to the overall film forming of the conductive ink, the resin has certain flexibility and brittle fracture resistance after film forming, and the conductive film after film forming has excellent flexibility, brittle fracture resistance and adhesion performance and can be attached to a required substrate to form a film based on requirements.
Preferably, in the step of preparing the porous molybdenum carbide MXene/reduced graphene oxide ink, the stabilizer comprises at least one of ethylenediamine, propylenediamine, hexamethylenediamine, phenylenediamine, glycine, 6-aminocaproic acid and octadecylamine. The stabilizer has the functions of stabilizing molybdenum carbide MXene and reducing graphene oxide structures, and maintains the long-term stability of ink structures, conductivity, infrared emissivity and the like.
Preferably, in the step of preparing the porous molybdenum carbide MXene/reduced graphene oxide ink, the protective gas is nitrogen or argon. The molybdenum carbide MXene/reduced graphene oxide ink is protected by protective gas in the heating and mixing process, so that the molybdenum carbide MXene is prevented from being oxidized or degraded, and the whole structure of the ink is protected to a certain extent. After the molybdenum carbide MXene/reduced graphene oxide ink is solidified and formed into a film, the reduced graphene oxide ink and the molybdenum carbide MXene are mutually doped and sealed in resin, so that the protective effect is quite good.
Preferably, in the step of preparing the porous molybdenum carbide MXene/reduced graphene oxide ink, stirring at a constant temperature of 75 ℃ until the volume is concentrated to 1/4 to prepare the porous molybdenum carbide MXene/reduced graphene oxide-based conductive ink. The prepared porous molybdenum carbide MXene/reduced graphene oxide-based conductive ink has proper viscosity, density and conductivity, and the film thickness and the leveling property of a film can be conveniently controlled.
In a second aspect, the invention further provides the porous molybdenum carbide MXene/graphene-based conductive ink prepared by the preparation method of the porous molybdenum carbide MXene/graphene-based conductive ink in the first aspect of the invention.
The porous molybdenum carbide MXene/graphene-based conductive ink comprises graphite powder, molybdenum carbide MXene, reduced graphene oxide, resin, particulate matter powder, polyacrylonitrile-maleic anhydride copolymer, a stabilizer, a first dispersing agent and a second dispersing agent. The conductive body part of the ink is formed by molybdenum carbide MXene, reduced graphene oxide and graphite powder, and the molybdenum carbide MXene and the reduced graphene oxide are doped with each other to play a role in protecting the molybdenum carbide MXene. The molybdenum carbide MXene, the reduced graphene oxide and the graphite powder are mixed with resin, particle powder and the like to form a conductive body resin mixture, the molybdenum carbide MXene and the reduced graphene oxide can be connected with groups on the surface of the resin to form flexible conductive resin, and the molybdenum carbide MXene and the reduced graphene oxide are further protected, so that the conductive resin has excellent electronic conductivity, good flexibility, excellent heat conductivity, infrared emission performance and structural stability. The resin has good film forming property, and the conductive resin is fully dispersed and then cured to form a film, so that the flexible conductive film with excellent conductivity, good flexibility, uniform resistance, good heat conduction and high infrared emissivity is formed. The particle powder is dispersed in the flexible conductive film, the film is immersed in acidic liquid after film formation, the surface particle powder is leached out and forms a surface porous structure, the surface porous structure can increase the infrared radiation surface of the conductive film, and the infrared radiation efficiency and the heat conduction performance are improved; the unleached particle powder also has certain high-temperature resistance, and the conductive resin is prevented from being locally heated too high to be softened and deformed.
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.
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 examples are provided to describe in detail the preparation method of the porous molybdenum carbide MXene/reduced graphene oxide-based conductive ink of the present invention and the porous molybdenum carbide MXene/reduced graphene oxide-based conductive ink prepared by the examples. The preparation method of the porous molybdenum carbide MXene/reduced graphene oxide-based conductive ink comprises the following steps.
Preparing a working electrode: providing graphite powder and molybdenum aluminum carbide powder (Mo)3AlC2) Grinding graphite powder and molybdenum aluminum carbide powder, mixing uniformly, and pressing the ground graphite powder and molybdenum aluminum carbide powder into a cylindrical working electrode. The amount of graphite powder, molybdenum-aluminum carbide powder, and the fineness of grinding (mesh number of sieve) in each example are shown in table 1.
TABLE 1 amount of graphite powder and molybdenum-aluminum carbide powder used and fineness of grinding
Preparing a molybdenum carbide/graphite oxide material: fixing the working electrode prepared in the previous step as a positive electrode in an electrolytic cell, adding an electrolyte into the electrolytic cell to immerse the working electrode in the electrolyte, and specifically: the upper end of the working electrode is connected with a lead, and the lower part of the working electrode is immersed in electrolyte (the lead is ensured not to be in contact with the electrolyte, and the lead is prevented from ionizing to generate impurity substances). The working electrode is electrified to be electrolyzed, the electrolytic cell is cooled through cooling equipment in the electrolysis process, and the electrolyte is stirred through a stirring device, such as a magnetic stirrer. The electrolyte is an organic solvent containing fluorine anions, and an etchant is generated in the electrolysis process of the fluorine anions, specifically, the type of the fluorine anions, the type of the organic solvent (two or more organic solvents are mixed organic solvents, and equal amount combination is adopted in the embodiment), the concentration of the fluorine anion-containing liquid, the voltage, the electrolysis time and the temperature maintained by the electrolyte are shown in table 2. After the electrolysis, the electrolyte is sieved by a 400-mesh sieve and then centrifuged to collect precipitates, and the centrifugal rotating speed and time are shown in table 2.
TABLE 2 preparation of molybdenum carbide/graphite oxide Material
| Fruit of Chinese wolfberry Applying (a) to Example (b) | Fluorine-containing anions | Organic solvent | Anion containing fluorine Concentration of seed （mol/ml） | Voltage of （V） | Electrolysis Time of day （h） | Electrolyte solution Temperature of （℃） | Stirring the mixture Rotational speed （rpm） | Centrifugation Rotational speed （rpm） | Centrifugation Time of day (min) |
| Fruit of Chinese wolfberry Applying (a) to Example (b) 1 | 1-ethyl-3- Methylimidazolium tetra (methyl imidazole) Fluoroborate salt | Acetonitrile | 3 | 4 | 15 | 35 | 300 | 5000 | 60 |
| Fruit of Chinese wolfberry Applying (a) to Example (b) 2 | 1-ethyl-3- Methyl imidazole hexa Fluorophosphate salts | Isopropanol (I-propanol) | 2.5 | 5 | 12 | 35 | 270 | 5000 | 60 |
| Fruit of Chinese wolfberry Applying (a) to Example (b) 3 | 1-butyl-3- Methylimidazolium tetra (methyl imidazole) Fluoroborate salt | Acetone, N-methyl Radical pyrrolidine Ketones | 2.5 | 5 | 10 | 38 | 250 | 7500 | 45 |
| Fruit of Chinese wolfberry Applying (a) to Example (b) 4 | 1-butyl-3- Methyl imidazole hexa Fluorophosphate salts | N-methylpyridine Pyrrolidinone, di Methyl sulfoxide | 2 | 6 | 10 | 38 | 220 | 7500 | 45 |
| Fruit of Chinese wolfberry Applying (a) to Example (b) 5 | 1-octyl-3- Methylimidazolium tetra (methyl imidazole) Fluoroborate salt | Dimethyl methyl Amides of carboxylic acids | 2 | 7 | 8 | 40 | 200 | 9000 | 30 |
| Fruit of Chinese wolfberry Applying (a) to Example (b) 6 | 1-octyl-3- Methyl imidazole hexa Fluorophosphate salts | Dimethyl sulfoxide Sulfone | 1.5 | 8 | 8 | 40 | 180 | 9000 | 30 |
| Fruit of Chinese wolfberry Applying (a) to Example (b) 7 | 1-hexyl-3- Methylimidazolium tetra (methyl imidazole) Fluoroborate salt | Tetrahydrofuran (THF) | 1.5 | 9 | 5 | 42 | 160 | 10000 | 20 |
| Fruit of Chinese wolfberry Applying (a) to Example (b) 8 | 1-hexyl-3- Methyl imidazole hexa Fluorophosphate salts | Dichloromethane, dichloromethane, Acetonitrile, N-methyl Radical pyrrolidine Ketones | 1 | 10 | 5 | 45 | 150 | 10000 | 20 |
Preparing molybdenum carbide MXene/reduced graphene oxide dispersion liquid: and dissolving the prepared molybdenum carbide/graphite oxide material precipitate in isopropanol to prepare isopropanol containing the molybdenum carbide/graphite oxide material, wherein the mass-volume ratio of the molybdenum carbide/graphite oxide material to the isopropanol is shown in table 3. Probe ultrasound was performed on isopropanol containing molybdenum carbide/graphite oxide material, and the power of probe ultrasound (abbreviated as "probe ultrasound power"), time (abbreviated as "probe ultrasound time"), frequency, and temperature maintained during the ultrasound process (abbreviated as "probe ultrasound temperature", which refers to the temperature set in the constant temperature water bath) are shown in table 3. After the probe ultrasound is finished, primarily centrifuging isopropanol containing molybdenum carbide/graphite oxide materials at 8000-15000 rpm for 10-30 min, and collecting primary precipitates. The rotation speed and time of the primary centrifugation are shown in Table 3.
TABLE 3 parameters of the Probe ultrasonic and Primary centrifugation Process
And adding the collected primary precipitate into a reducing reagent for reduction, and uniformly stirring and mixing the reducing reagent to ensure that the primary precipitate is fully dispersed in the reducing reagent. Wherein the kind of the reducing agent, the concentration of the reducing agent, the ratio of the primary precipitate to the mass volume of the reducing agent (referred to as "mass volume ratio"), and the reduction time are shown in Table 4. And after the reduction is finished, centrifuging the reducing reagent again, collecting the reduced precipitate, and drying. The re-centrifugation rotation speed and re-centrifugation time are shown in table 4. The drying is completed by a freezing vacuum drying device. After drying, dispersing the dried precipitate in a first dispersing agent (wherein the mixture of the two dispersing agents in any proportion is adopted in the embodiment, and equal amount combination is adopted in the embodiment), and performing water bath ultrasound to obtain a molybdenum carbide MXene/reduced graphene oxide dispersion liquid. Wherein, the species of the first dispersant, the ultrasonic power of the water bath, the ultrasonic time of the water bath, the ultrasonic temperature of the water bath, and the like are shown in table 4.
TABLE 4 reductive reagent and parameters of the Water bath sonication Process
Preparing granular resin slurry: a particulate powder and a second dispersant are provided and mixed, wherein the type of particulate powder, the diameter of the particulate powder, the type of second dispersant, and the ratio of the particulate powder to the second dispersant by mass to volume (referred to as "mass to volume ratio") are shown in table 5. Resin was added to the second dispersion while stirring the second dispersion to produce a resin slurry of the particles, wherein the resin type (mixture of resins including a mixture of resins in any ratio, in the example, in equal combination) and the resin concentration are shown in Table 5.
TABLE 5 parameters in the step of preparing a resin slurry of particulate matter
Preparing molybdenum carbide MXene/reduced graphene oxide-based conductive ink: 500 mg of the particulate resin slurry, the molybdenum carbide MXene/reduced graphene oxide dispersion liquid, the polyacrylonitrile-maleic anhydride copolymer and the stabilizer are mixed, wherein the quality of the molybdenum carbide MXene/reduced graphene oxide dispersion liquid, the quality of the polyacrylonitrile-maleic anhydride copolymer and the quality of the stabilizer (containing various stabilizers, the various stabilizers can be combined in any proportion, and the same amount of stabilizer is combined in the embodiment) and the type of the stabilizer are shown in Table 6. After mixing, the mixture was transferred to a protective gas atmosphere and then stirred in a constant temperature water bath until the volume was concentrated, and the specific protective gas type, water bath temperature and concentration factor (volume of the concentrated liquid compared with the original liquid volume) are shown in table 6. After concentration, the mixed solution has proper film forming property and leveling property, and the porous molybdenum carbide MXene/reduced graphene oxide-based conductive ink is prepared.
TABLE 6 preparation of molybdenum carbide MXene/reduced graphene oxide inks
Comparative example 1
Comparative example 1 the setup was made with reference to example 4, comparative example 1 differing from example 4 only in that: in the working electrode preparation step, only graphite powder is provided and used for preparing the working electrode.
The preparation method of the porous reduced graphene oxide-based conductive ink comprises the following steps.
Preparing a working electrode: providing graphite powder, grinding the graphite powder, and pressing the ground graphite powder into a cylindrical working electrode. The amount and grinding fineness of graphite powder were the same as in example 4.
Preparing a graphite oxide material: same as in example 4.
Preparing a reduced graphene oxide dispersion liquid: same as in example 4.
Preparing granular resin slurry: same as in example 4.
Preparing reduced graphene oxide ink: same as in example 4.
Comparative example 2
The preparation method of the porous molybdenum carbide MXene-based conductive ink comprises the following steps.
Preparing a working electrode: and providing molybdenum aluminum carbide powder, grinding and uniformly mixing the molybdenum aluminum carbide powder, and pressing the ground molybdenum aluminum carbide powder into a cylindrical working electrode. The amount and the grinding fineness of the molybdenum aluminum carbide powder were the same as those in example 4.
Preparing a molybdenum carbide material: same as in example 4.
Preparing molybdenum carbide MXene dispersion liquid: same as in example 4.
Preparing granular resin slurry: same as in example 4.
Preparing molybdenum carbide MXene ink: same as in example 4.
Comparative example 3
The preparation method of the porous molybdenum carbide MXene/reduced graphene oxide-based conductive ink comprises the following steps.
Preparing molybdenum carbide MXene/reduced graphene oxide dispersion liquid: providing a molybdenum carbide MXene material and a reduced graphene oxide material, adding the molybdenum carbide MXene material and the reduced graphene oxide material into isopropanol, stirring and uniformly mixing to obtain the isopropanol containing the molybdenum carbide MXene/reduced graphene oxide. In isopropanol containing molybdenum carbide MXene/reduced graphene oxide, the mass ratio of the molybdenum carbide MXene to the reduced graphene oxide is 1:7, and the concentration of the molybdenum carbide MXene/reduced graphene oxide is 300 mg/ml. And stirring the isopropanol containing the molybdenum carbide MXene/reduced graphene oxide by using an electromagnetic stirrer overnight to obtain the molybdenum carbide MXene/reduced graphene oxide dispersion liquid.
Preparing granular resin slurry: same as in example 4.
Preparing molybdenum carbide MXene ink: same as in example 4.
Effects of the embodiment
(1) Adhesion Performance test
The porous molybdenum carbide MXene/reduced graphene oxide-based conductive ink prepared in examples 1 to 8 and the conductive ink prepared in comparative examples 1 to 3 were respectively coated on a PET film by scraping, and then the PET film was transferred to a 70 ℃ forced air drying oven to be dried for 1 hour, and then the dried conductive film was immersed in a dilute acid solution (in this example, 0.5 mol/L dilute hydrochloric acid was used for immersion, and in other examples, dilute sulfuric acid, phosphoric acid and the like were used for immersion) overnight, washed, and dried to obtain a porous conductive film (hereinafter, referred to as "a porous conductive film corresponding to a conductive ink or a porous conductive film corresponding to an example"). Hardness was tested according to the national standard GB/T6739-1996 using a Chinese pencil, and the results are shown in Table 7. The adhesion was tested according to the national standard GB/T13217.4- - -2008 using 3M special adhesive tape, the test results are shown in Table 7.
TABLE 7 results of adhesion Property measurement test
| Examples | Hardness of | Adhesion force |
| Example 1 | 3H | 100% |
| Example 2 | 3H | 100% |
| Example 3 | 3H | 100% |
| Example 4 | 3H | 100% |
| Example 5 | 3H | 100% |
| Example 6 | 3H | 100% |
| Example 7 | 3H | 100% |
| Example 8 | 3H | 100% |
| Comparative example 1 | 1H | 85% |
| Comparative example 2 | 4H | 50% |
| Comparative example 3 | 2H | 80% |
From the results in table 7, it can be seen that the porous conductive thin films formed by printing the porous molybdenum carbide MXene/reduced graphene oxide-based conductive inks prepared in examples 1 to 8 have high hardness and good adhesion, and can meet the requirements of the porous conductive thin films on the performances such as peeling resistance and flexibility. The porous conductive film corresponding to the comparative example 1 does not contain porous molybdenum carbide MXene, the conductive components mainly comprise reduced graphene oxide and graphite powder which is not completely stripped, the porous conductive film has good flexibility but poor hardness (namely wear resistance), and the wear resistance requirement of the heating film applied to furniture, building materials and other heating or heat-insulating equipment is difficult to meet. The porous conductive film corresponding to the comparative example 2 does not contain reduced graphene oxide, the conductive component is mainly porous molybdenum carbide MXene, and the porous molybdenum carbide MXene has excellent conductivity, but poor flexibility and poor adhesion with a PET (polyethylene terephthalate) base material, so that the prepared porous conductive film has low flexibility and poor anti-stripping effect, and is easy to fall off and crack in a long-term use process. The porous conductive film corresponding to the comparative example 3 is not subjected to the common stripping process of molybdenum carbide and graphite powder, so that the prepared porous conductive film has general performances in the hardness and adhesion test processes, and may be related to incomplete stripping and doping of molybdenum carbide MXene and reduced graphene oxide.
(2) Service life test
The conductive inks prepared in examples 1 to 8 and comparative examples 1 to 3 were printed on a PET sheet by a printing technique, and the printed PET sheet was transferred to a forced air drying oven at a temperature of 70 ℃ to be dried and cured for 4 hours, thereby finally obtaining a porous conductive film having a thickness of 10 μm.
The initial sheet resistance test was performed by cutting a porous conductive film having a length and a width of 10cm with a blade, and the test results are shown in table 8. Inserting metal electrodes into opposite corners of two ends of the cut porous conductive film respectively and connecting the metal electrodes into commercial power to test the service life, wherein the test method comprises the following steps: the sheet resistance values of the porous conductive films corresponding to the above examples were measured every other week (W) while continuously supplying electricity to generate heat, and the results are shown in table 8.
TABLE 8 Life test results
| Examples | Initial sheet resistance (omega/□) | 1W time square resistance (omega/□) | 2W square resistance (omega/□) | 3W time square resistance (omega/□) | 4W square resistance (omega/□) | 5W time square resistance (omega/□) |
| Example 1 | 277 | 280 | 281 | 282 | 283 | 283 |
| Example 2 | 269 | 271 | 272 | 273 | 274 | 274 |
| Example 3 | 265 | 267 | 268 | 268 | 269 | 269 |
| Example 4 | 257 | 259 | 260 | 260 | 260 | 261 |
| Example 5 | 262 | 264 | 265 | 266 | 266 | 266 |
| Example 6 | 268 | 270 | 271 | 272 | 273 | 273 |
| Example 7 | 272 | 274 | 275 | 276 | 276 | 277 |
| Example 8 | 276 | 279 | 280 | 281 | 282 | 282 |
| Comparative example 1 | 457 | 472 | 478 | 482 | 485 | 487 |
| Comparative example 2 | 182 | 293 | 372 | 425 | 461 | 480 |
| Comparative example 3 | 323 | 335 | 341 | 346 | 349 | 352 |
From the results in Table 8, it is understood that the porous conductive films according to examples 1 to 8, which are continuously energized to generate heat at 5W, do not change much in the overall sheet resistance and can be used for the heat-generating layer of the electric heating apparatus which is heated for a long time. After the porous conductive films corresponding to the comparative examples 1-3 are continuously electrified and heated by 5W, the overall sheet resistance value of the porous conductive films is greatly changed, which may be related to unstable molybdenum carbide MXene, obvious improvement of resistance value after oxidation and the like, and also related to incomplete stripping, uneven doping and the like of the molybdenum carbide MXene and the reduced graphene oxide.
(3) Antibacterial testing
The conductive films corresponding to the conductive inks prepared in examples 1 to 8 and comparative examples 1 to 3 were cut into conductive films having a length, width and thickness of 20 cm and a thickness of about 0.1 mm by a blade, and electrodes were inserted into both ends of the conductive films for heat generation by energization and an antibacterial test. The test method is as follows: the culture solution (rejuvenated) of model strains (escherichia coli, candida albicans, salmonella typhimurium, staphylococcus aureus) was spotted by means of an inoculating needle onto petri dishes (containing conventional solid medium for bacterial culture), each petri dish was inoculated with a single strain 10 times and each strain 200 times (divided into 20 dishes). After inoculation, all the culture dishes are divided into two groups and respectively placed in two culture chambers for simulating living environment. One of them is the laboratory group culture room, is provided with a plurality of aforementioned conductive film and circular telegram heat production in the laboratory group culture room, and the culture dish is 5~ 30 cm apart from conductive film, and the laboratory group culture room is supplied energy by the conductive film heat production, and the temperature control in the culture room is about 37 ℃, and another culture room is the control group culture room, and the temperature that sets up the control group culture room equally is 37 ℃, is supplied heat by the air conditioner, and statistics laboratory group bacterial colony growth condition after 12 h all cultivateed in laboratory group culture room and control group culture room. The average colony size (diameter of colony) of each bacterial colony in the control group is calculated, the average colony size is used as a reference value, the colony with the diameter less than or equal to half of the reference value in the experimental group is marked as bacteriostasis, the colony which does not grow at the point of sample application is marked as sterilization, and the colony with the diameter more than or equal to half of the reference value is marked as normal growth. The results of the statistical percentages are shown in Table 9.
TABLE 9 antibacterial test results
As is clear from the results in Table 9, the conductive films of examples 1 to 8 all showed more than 99% of bactericidal activity against Escherichia coli, Candida albicans, and Salmonella typhimurium and more than 95% of bactericidal activity against Staphylococcus aureus when energized. After being doped with each other, the molybdenum carbide MXene and the reduced graphene oxide can be promoted to be in direct contact with and doped with the reduced graphene oxide, the molybdenum carbide MXene or the reduced graphene oxide is prevented from being stacked or partially aggregated, a single two-dimensional material is promoted to be stripped into few layers of nanosheets, and the nanosheets are mixed with dispersed graphite powder to form a conductive network structure with stable molybdenum carbide MXene-reduced graphene oxide-graphite particles. After the conductive films corresponding to embodiments 1-8 are electrified, the surface area can be increased by virtue of a large number of gap structures existing on the surfaces of the conductive films, which is helpful for releasing a large number of infrared rays and has a sterilization effect. In addition, by means of carrier transmission between the molybdenum carbide MXene and the graphene sheet layer, a small amount of active oxygen free radicals can be generated at a heterojunction between the molybdenum carbide MXene and the graphene sheet layer, and the effects of assisting sterilization and cleaning the surface are achieved.
In contrast, the conductive film corresponding to comparative example 1 has a sterilization rate of only 72% for escherichia coli, candida albicans, and salmonella typhimurium, and a sterilization rate of only 60% for staphylococcus aureus. The reason may be related to that the conductive film corresponding to comparative example 1 has a relatively low infrared emissivity, and the conductive film corresponding to comparative example 1 only contains reduced graphene oxide, graphite and other electric conductors and lacks the auxiliary effect of molybdenum carbide MXene, so that the conductive film has a relatively low infrared emissivity and cannot generate active radicals. The sterilization rate of the conductive film corresponding to the comparative example 2 on escherichia coli, candida albicans and salmonella typhimurium reaches 61%, and the sterilization rate on staphylococcus aureus reaches only 54%. The conductive film corresponding to the comparative example 2 only contains the conductive body molybdenum carbide MXene, and lacks the reduced graphene oxide and graphite powder, so that the conductive film has the advantages of high resistance, nonuniform heat generation, low infrared emissivity, low yield of active free radicals and low antibacterial efficiency. The sterilization rate of the conductive film corresponding to the comparative example 3 on escherichia coli, candida albicans and salmonella typhimurium reaches 85% and the sterilization rate on staphylococcus aureus reaches only 74%. In the conductive film corresponding to the comparative example 3, based on the fact that the common water bath ultrasound of the molybdenum carbide MXene and the reduced graphene oxide is not performed in the comparative example 3, the molybdenum carbide MXene cannot be peeled off with the assistance of the reduced graphene oxide, and an effective molybdenum carbide MXene/graphene mutual doping structure cannot be formed, so that the defects that the corresponding conductive film is uneven in dispersion of a conductor, low in infrared emissivity, low in yield of active free radicals, low in antibacterial efficiency and the like are caused.
(4) Infrared wavelength and normal emissivity testing
The conductive films corresponding to the embodiments 1-8 and the comparative examples 1-3 were tested for the infrared wavelength range and the normal emissivity according to the national standard GB/T7287-. The calculation data show that the conductive thin film corresponding to the embodiment 1-8 can release 3-20 micrometers of far infrared rays, the far infrared ray content of the band of 4-16 micrometers exceeds 86%, the normal emissivity exceeds 89%, and the electrothermal conversion rate is over 99%, so that the conductive thin film can be widely applied to the fields of floor heating, physiotherapy, clothes and the like. In contrast, the conductive film corresponding to comparative example 1-3 has a far infrared ray content of 4 to 16 μm wavelength band of less than 77% (62% for the graphene-based conductive film in comparative example 1), a normal emissivity of less than 82% (66% for the conductive film corresponding to comparative example 1), and an electrothermal conversion rate of less than 95%. The reason for this is probably related to the circuit network structure formed by the conductive film, i.e. the molybdenum carbide MXene and the reduced graphene oxide are doped with each other, so that the uniform distribution of the conductor is increased, the resistance value of the conductive film is reduced, the uniformity of the conductive film is improved, and the like.
(5) Stability and leakage safety testing
The conductive films corresponding to the examples 1 to 8 and the comparative examples 1 to 3 are cut into conductive films with the length, the width and the thickness of 20 cm and the thickness of about 0.1 mm by a blade, electrodes are inserted into two ends of each conductive film, the conductive films are connected with commercial power to generate heat, and the uniformity of the heating temperature is assessed by an infrared imaging instrument. Any two heating temperature differences of each conductive film are less than or equal to 5 ℃ and more than 2.5 ℃, the conductive film is qualified, the conductive film is excellent when the heating temperature difference is less than or equal to 2.5 ℃, the conductive film is unqualified when the heating temperature difference is more than 5 ℃, and the statistical result is shown in table 10.
And continuously electrifying the conductive film for testing the heat generation uniformity to generate heat for testing the heat generation stability. The statistical method, the heat production is carried out for 90000 hours by continuous electrification, and compared with the beginning of the heat production, the disqualification is marked when the heat production power is reduced by more than 2.5 percent after the 90000 hours of the heat production; the heat production power is reduced by less than or equal to 2.5 percent and is greater than 1 percent, and the product is marked as qualified; the decrease of heat generation power less than or equal to 1% is marked as excellent, and the statistical results are shown in Table 10.
Insulating polymer films (such as PET or PI) are adopted to hot-press two surfaces of the composite conductive film, and after 90000 hours of electrification and heat generation, the electrification and the heat generation are continued for leakage safety test. The specific test method was measured with reference to GB/T12113 (idt IEC 60990). The leakage current is less than or equal to 0.05 mA and greater than 0.02 mA and is marked as qualified; the leakage current is less than 0.02 mA and is marked as excellent; the leakage current is greater than 0.05 mA and is marked as unqualified. The results of the measurements are shown in Table 10.
TABLE 10 stability and leakage safety test data
| Examples | Temperature uniformity | Stability of heat generation | Leakage safety test |
| Example 1 | Is excellent in | Is excellent in | Is excellent in |
| Example 2 | Is excellent in | Is excellent in | Is excellent in |
| Example 3 | Is excellent in | Is excellent in | Is excellent in |
| Example 4 | Is excellent in | Is excellent in | Is excellent in |
| Example 5 | Is excellent in | Is excellent in | Is excellent in |
| Example 6 | Is excellent in | Is excellent in | Is excellent in |
| Example 7 | Is excellent in | Is excellent in | Is excellent in |
| Example 8 | Is excellent in | Is excellent in | Is excellent in |
| Comparative example 1 | Fail to be qualified | Fail to be qualified | Qualified |
| Comparative example 2 | Fail to be qualified | Fail to be qualified | Qualified |
| Comparative example 3 | Qualified | Fail to be qualified | Qualified |
As can be seen from the results in table 10, the conductive films according to examples 1 to 8 all showed excellent test results in the temperature uniformity test, the heat generation stability test, and the leakage safety test, indicating that the conductive films according to examples 1 to 8 of the present invention have excellent heat generation uniformity, heat generation stability, and leakage safety. The conductive film corresponding to the comparative example 1 is unqualified in temperature uniformity test and heat generation stability test, the conductive film corresponding to the comparative example 2 is unqualified in temperature uniformity test and heat generation stability test, the conductive film corresponding to the comparative example 3 is unqualified in heat generation stability test, qualified in temperature uniformity test and qualified in leakage safety test. In summary, the conductive films corresponding to the comparative examples 1-2 may fail in the temperature uniformity test and the heat generation stability test, and may be related to the non-uniform dispersion of the conductor, insufficient peeling of the nanomaterial, instability of the conductor under the condition of power-on, easy aging, and the like. The conductive film corresponding to comparative example 3 may generally be related to the performance of the conductive film in the temperature uniformity test, the heat generation stability test, the leakage safety test and the like, which is not subjected to the common ultrasonic peeling, the titanium carbide MXene and the reduced graphene oxide are not uniformly doped, and the like.
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 (10)
1. The preparation method of the porous molybdenum carbide MXene/reduced graphene oxide-based conductive ink is characterized by comprising the following steps of:
preparing a working electrode: providing graphite powder and molybdenum carbide powder, grinding the graphite powder and the molybdenum carbide powder to a fineness of more than 200 meshes, wherein the mass ratio of the graphite powder to the molybdenum carbide powder is 1-8: 1, and mixing the graphite powder and the molybdenum carbide powder and pressing into a working electrode;
preparing a molybdenum carbide/graphite oxide material: fixing the working electrode in an electrolytic cell, adding electrolyte into the electrolytic cell to enable the working electrode to be immersed in the electrolyte, wherein the electrolyte is fluorine-containing anion liquid and is used as an etching agent, the working electrode is used as a positive electrode, voltage is applied to enable the fluorine-containing anion liquid to be ionized to generate fluorine free radicals, and after electrolysis is finished, centrifuging and collecting precipitates for the electrolyte to obtain a molybdenum carbide/graphite oxide material;
preparing a molybdenum carbide MXene/reduced graphene oxide dispersion liquid: dissolving the molybdenum carbide/graphite oxide material in isopropanol according to the mass-volume ratio of 50-500 mg/ml, performing probe ultrasound on the isopropanol containing the molybdenum carbide/graphite oxide material, centrifuging the isopropanol containing the molybdenum carbide/graphite oxide material at 8000-15000 rpm for 10-30 min after the probe ultrasound is finished, collecting precipitates, immersing the precipitates in a reducing reagent for reduction, centrifuging, collecting the precipitates, drying, dispersing the dried precipitates in a first dispersing agent, and performing water bath ultrasound to obtain a molybdenum carbide MXene/reduced graphene oxide dispersion solution;
preparing a particle resin slurry: providing and mixing particulate matter powder and a second dispersing agent, adding resin into the second dispersing agent while stirring the second dispersing agent to prepare particulate matter resin slurry, wherein the diameter of the particulate matter powder is 0.1-1 mu m, the concentration of the particulate matter powder is 10-100 mg/ml, and the concentration of the resin is 50-500 mg/ml;
preparing porous molybdenum carbide MXene/reduced graphene oxide-based conductive ink: mixing the granular resin slurry, molybdenum carbide MXene/reduced graphene oxide dispersion liquid, polyacrylonitrile-maleic anhydride copolymer and a stabilizer according to the mass ratio of 500: 1000-10000: 1-50: 5-20, transferring the mixture to a protective gas environment, stirring at a constant temperature of 65-85 ℃ until the volume is 1/2-1/6, and preparing the porous molybdenum carbide MXene/reduced graphene oxide-based conductive ink;
the molybdenum aluminum carbide powder is Mo3AlC2And the particle powder is carbonate powder or metal oxide powder.
2. The preparation method of the porous molybdenum carbide MXene/reduced graphene oxide-based conductive ink as claimed in claim 1, wherein in the working electrode preparation step, the graphite powder and the molybdenum carbide powder are ground to 300 meshes of fineness, and the mass ratio of the graphite powder to the molybdenum carbide powder is 2-6: 1.
3. The method for preparing the porous molybdenum carbide MXene/reduced graphene oxide-based conductive ink according to claim 1, wherein in the step of preparing the molybdenum carbide/graphite oxide material, the fluorine-containing anion liquid is an organic solvent containing fluorine anions, wherein the fluorine-containing anions in the fluorine-containing anion liquid are at least one of tetrafluoroborate ions and hexafluorophosphate ions.
4. The preparation method of the porous molybdenum carbide MXene/reduced graphene oxide-based conductive ink according to claim 3, characterized in that, in the step of preparing the molybdenum carbide/graphite oxide material, the fluorine-containing anion liquid includes at least one of 1-ethyl-3-methylimidazole tetrafluoroborate, 1-ethyl-3-methylimidazole hexafluorophosphate, 1-butyl-3-methylimidazole tetrafluoroborate, 1-butyl-3-methylimidazole hexafluorophosphate, 1-octyl-3-methylimidazole tetrafluoroborate, 1-octyl-3-methylimidazole hexafluorophosphate, 1-hexyl-3-methylimidazole tetrafluoroborate and 1-hexyl-3-methylimidazole hexafluorophosphate.
5. The method for preparing the porous molybdenum carbide MXene/reduced graphene oxide-based conductive ink according to claim 3, wherein in the step of preparing the molybdenum carbide/graphite oxide material, the organic solvent of the organic solvent containing fluoroanion is at least one of acetonitrile, ethanol, isopropanol, acetone, N-methylpyrrolidone, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, and dichloromethane.
6. The preparation method of the porous molybdenum carbide MXene/reduced graphene oxide-based conductive ink according to claim 3, wherein in the step of preparing the molybdenum carbide/graphite oxide material, the concentration of the fluorine-containing anion liquid is 1-3 mol/L, the voltage is +4 to + 10V, and the electrolysis time is 5-15 h;
the temperature of the electrolyte in the electrolysis process is 35-45 ℃, the electrolyte is continuously stirred in the electrolysis process, and the stirring revolution is 150-300 rpm.
7. The preparation method of the porous molybdenum carbide MXene/reduced graphene oxide-based conductive ink according to claim 1, wherein in the step of preparing the molybdenum carbide MXene/reduced graphene oxide dispersion liquid, the ultrasonic power of the probe is 300-500W, the ultrasonic time of the probe is 3-10 h, and the temperature of isopropanol of a molybdenum carbide/graphite oxide material in the ultrasonic process of the probe is lower than 15 ℃;
the power of the water bath ultrasound is 200-300W, the time of the water bath ultrasound is 8-24 h, and the temperature of isopropanol of the molybdenum carbide/graphite oxide material in the water bath ultrasound process is lower than 15 ℃.
8. The method for preparing the porous molybdenum carbide MXene/reduced graphene oxide-based conductive ink according to claim 1, wherein in the step of preparing the particulate resin slurry, the second dispersant is a cellulose derivative, and the cellulose derivative is one or a combination of methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, cellulose acetate and cellulose nitrate;
the resin is one or a combination of more of epoxy resin, polydimethylsiloxane resin, polycarbonate resin, polyurethane resin, acrylic resin, waterborne alkyd resin, phenolic resin and silicone-acrylate resin.
9. The method for preparing the porous molybdenum carbide MXene/reduced graphene oxide-based conductive ink according to claim 1, wherein in the step of preparing the porous molybdenum carbide MXene/reduced graphene oxide-based conductive ink, the stabilizer comprises at least one of ethylenediamine, propylenediamine, hexamethylenediamine, phenylenediamine, glycine, 6-aminocaproic acid, octadecylamine;
the protective gas is nitrogen or argon.
10. The porous molybdenum carbide MXene/reduced graphene oxide-based conductive ink prepared by the preparation method of the porous molybdenum carbide MXene/reduced graphene oxide-based conductive ink according to any one of claims 1 to 9.
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| CN114023511A (en) * | 2021-11-11 | 2022-02-08 | 中国有色桂林矿产地质研究院有限公司 | Method for preparing high-temperature electronic paste based on organic phosphorus salt |
| CN114420897A (en) * | 2022-03-09 | 2022-04-29 | 吉林师范大学 | Preparation method of MXene thin film electrode |
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|---|---|---|---|---|
| CN114023511A (en) * | 2021-11-11 | 2022-02-08 | 中国有色桂林矿产地质研究院有限公司 | Method for preparing high-temperature electronic paste based on organic phosphorus salt |
| CN114023511B (en) * | 2021-11-11 | 2023-10-31 | 中国有色桂林矿产地质研究院有限公司 | Method for preparing high-temperature electronic paste based on organic phosphorus salt |
| CN114420897A (en) * | 2022-03-09 | 2022-04-29 | 吉林师范大学 | Preparation method of MXene thin film electrode |
| CN114420897B (en) * | 2022-03-09 | 2024-01-02 | 吉林师范大学 | Preparation method of MXene thin film electrode |
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Application publication date: 20210223 |