CN113582668A - Full-printing preparation method of manganese nickel cobalt-based high-temperature-resistant flexible thermosensitive device - Google Patents
Full-printing preparation method of manganese nickel cobalt-based high-temperature-resistant flexible thermosensitive device Download PDFInfo
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Abstract
The invention discloses a full-printing preparation method of a manganese-nickel-cobalt-based high-temperature-resistant flexible thermosensitive device, which comprises the steps of firstly preparing carbon material @ thermosensitive oxide composite powder, putting the powder and an organic solvent into a vacuum stirring defoaming machine according to a certain proportion, uniformly mixing, grinding and preparing into slurry; and then uniformly coating the slurry on a high-temperature-resistant flexible substrate by adopting a screen printing technology to form a thick film, carrying out drying curing, vacuum packaging, cold isostatic pressing, high-temperature sintering and other processes on the prepared thick film, preparing an electrode on the fired heat-sensitive thick film by adopting the screen printing technology, and finally carrying out insulation packaging by adopting the screen printing technology to obtain the high-temperature-resistant flexible thermosensitive device. The invention realizes the preparation of the high-temperature-resistant flexible thermosensitive device, has good flexibility, simple structure, accurate and controllable thickness and high yield, can work at high temperature for a long time, is very suitable for batch production and has great application prospect.
Description
Technical Field
The invention relates to the technical field of thermosensitive devices, in particular to a full-printing preparation method of a manganese nickel cobalt-based high-temperature-resistant flexible thermosensitive device.
Background
Compared with the traditional rigid silicon-based electronics, the flexible electronic product has attracted much attention in the fields of artificial intelligence, internet of things and the like. The problem that the measurement precision is influenced because the traditional rigid temperature sensor cannot be in close contact with a non-uniform surface can be solved by constructing the all-inorganic flexible temperature sensor; the portable temperature measurement in real time in the fields of food logistics, remote operation robots, battery life monitoring, body temperature measurement and the like in a cold chain system can be realized; the technical bottleneck that the flexible temperature sensor containing the polymer or the organic material cannot meet the application in high-temperature environments (such as aerospace, metallurgical industry, underground energy exploration and the like) because the temperature of the flexible temperature sensor is low (not more than 350 ℃) by substrates (PI, PDMS, PU, PET, paper and fabrics) in the current reports at home and abroad can be broken through.
The fluorine crystal mica has the advantages of good insulation property (the resistivity is 1015-1016 omega-cm), high temperature resistance (the fluorine crystal mica can work in an environment of 1100 ℃ for a long time), strong chemical inertness (strong acid and strong alkali resistance), good stability and the like, and after being stripped to the thickness of less than about 20 mu m along the layered structure, the fluorine crystal mica with the characteristics of atomically smooth cleavage surface and strong flexibility can be used as a substrate for preparing a high-temperature resistant inorganic flexible film.
Therefore, it is necessary and important to develop the research on the preparation of high temperature resistant flexible thermosensitive devices based on the high performance thermosensitive thin film material with the fluorine crystal mica as the substrate.
Disclosure of Invention
The invention aims to provide a full-printing preparation method of a manganese nickel cobalt-based high-temperature-resistant flexible thermosensitive device, which adopts a screen printing technology to prepare a thermosensitive film on a flexible substrate capable of enduring the high temperature of 1100 ℃ for a long time, has simple and convenient operation and low cost, and the prepared high-temperature-resistant flexible thermosensitive device has good flexibility, simple structure, accurate and controllable thickness and high yield and can work at the high temperature for a long time.
The purpose of the invention is realized by the following technical scheme: a full printing preparation method of a manganese nickel cobalt-based high temperature resistant flexible thermosensitive device mainly comprises a high temperature resistant flexible substrate, a thermosensitive thick film, an electrode and an insulating layer, and the preparation method comprises the following steps:
(1) preparation of nanoscale thermal sensitive oxide powder
Adding a proper amount of deionized water into the weighed metal salt raw material, heating in a water bath, and stirring until a saturated metal salt solution is formed; dissolving alkali in deionized water to form an alkali solution, slowly adding a saturated metal salt solution into the alkali solution under the stirring of a water bath, and stirring and standing to obtain a precipitate; washing, filtering and freeze-drying the obtained precipitate to obtain product powder; pre-sintering the product powder at constant temperature, ball-milling, freezing and drying to prepare nanoscale thermosensitive oxide powder;
(2) preparation of carbon material @ thermal sensitive oxide powder
Adding carbon material dispersion liquid accounting for 0.3-4 wt% of the prepared nanoscale oxide powder, uniformly stirring in a vacuum stirring defoaming machine, performing vacuum freeze drying treatment, and then grinding for 30min to obtain dry and dispersed carbon material @ thermosensitive oxide powder;
(3) preparation of organic vehicle
Mixing 50-70 parts by weight of terpineol, 4-8 parts by weight of ethyl cellulose, 10-20 parts by weight of diethylene glycol butyl ether, 8-16 parts by weight of diethylene glycol butyl ether acetate and 5-10 parts by weight of span 85, and uniformly stirring to obtain an organic carrier;
(4) preparing slurry
Mixing carbon material @ thermal sensitive oxide powder and an organic carrier in a ratio of 8: 2. 7: 3. 6: 4. 5: weighing the mass ratio of 5, mixing and size mixing by adopting a vacuum stirring defoaming machine, wherein the rotating speed is 1000-3000rpm, the time is 2-8min, the defoaming time is 1-4min, grinding the mixed slurry by adopting a three-roll grinder, the grinding speed is 100-200 revolutions per minute, the grinding time is 20-40min, and the grinding times are 5-10 times to obtain the slurry;
(5) preparation of a Heat-sensitive Thick film
Uniformly coating the prepared slurry on a high-temperature-resistant flexible substrate by adopting a screen printing technology to form a heat-sensitive thick film with the thickness of 0.5-50 mu m;
(6) post-treatment of heat-sensitive thick films
Drying the heat-sensitive thick film in a constant-temperature oven at 150 ℃ for 12 hours for curing, covering a high-temperature-resistant flexible substrate with the same size and shape on the cured heat-sensitive thick film, then packaging by adopting vacuum packaging equipment, and carrying out cold isostatic pressing in an isostatic pressing machine, wherein the pressure is set to be 100-300MPa, and the pressure maintaining time is 1-5 min; after cold isostatic pressing, stripping the packaging layer and the high-temperature-resistant flexible substrate, taking out the thermosensitive thick film, placing the thermosensitive thick film on a corundum plate, and sintering under the protection of nitrogen;
(7) printed electrode
Firstly, preparing an electrode on a processed thermosensitive thick film by adopting a screen printing technology, then drying the thermosensitive thick film in a constant-temperature drying box at the temperature of 150 ℃ for 2 hours, then transferring the thermosensitive thick film to a box-type furnace for annealing the electrode, wherein the annealing temperature of the electrode is 400-1000 ℃ and the time is 20-60min, and finally welding an outer lead on the electrode by adopting a bonding technology to obtain a high-temperature-resistant flexible thermosensitive device body layer;
(8) preparing an insulating layer
And printing polyester resin, parylene or epoxy resin on the high-temperature-resistant flexible thermosensitive device body layer by adopting a screen printing technology for insulating packaging, then putting the high-temperature-resistant flexible thermosensitive device body layer into an oven, and drying for 4 hours at the temperature of 80 ℃ to obtain the high-temperature-resistant flexible thermosensitive device.
Further, the step (1) of preparing the nanometer thermal sensitive oxide powder comprises the following specific preparation method: adding a proper amount of deionized water into the weighed metal salt raw materials, and heating and stirring in a water bath at 40 ℃ until a saturated metal salt solution is formed; dissolving alkali in deionized water to form an alkali solution with the pH value of 9-14, slowly adding a saturated metal salt solution into the alkali solution under the stirring of a water bath at the temperature of 30-50 ℃, continuously stirring for 2-5 hours, and then standing for 10-12 hours to obtain a precipitate; washing the obtained precipitate with deionized water and ethanol to neutrality, vacuum filtering, and freeze drying in a vacuum freeze dryer at-40 deg.C for 10 hr to obtain fluffy dry product powder; pre-sintering the resultant powder at the constant temperature of 500-800 ℃ for 1-2h, and then ball-milling for 12h, and freeze-drying for 48h at-40 ℃ to obtain the nano-scale thermosensitive oxide powder.
Further, the metal salt raw materials are manganese sulfate, cobalt sulfate heptahydrate and nickel sulfate hexahydrate, and the alkali is sodium hydroxide.
Further, the carbon material in the step (2) is one or more of carbon fiber, graphene oxide, carbon nanotubes and glassy carbon.
Further, the carbon material dispersion liquid in the step (2) is formed by dispersing the carbon material in ethanol, and the adding amount of the carbon material dispersion liquid is 0.3-4 wt%.
Further, the concentration of the carbon material in the carbon material dispersion liquid in the step (2) is 2 mg/mL.
Further, the printing process parameters of the screen printing technology in the steps (5), (7) and (8) are as follows: the distance between the sample stage and the plate is 5-15 μm, the mesh number of the screen is 250-400 meshes, and the printing speed is 70-80 mm/s.
Further, the high-temperature-resistant flexible substrate is fluorine crystal mica.
Further, the sintering in the step (6) adopts a two-step method: firstly, carrying out glue discharging treatment, heating to 800 ℃ at a heating rate of 3 ℃/min, and keeping the temperature for 1 h; and secondly, after the heat preservation at 800 ℃ is finished, continuously heating to 1000-1200 ℃ at the speed of 3 ℃/min and preserving the heat for 2-4 h.
Further, the electrode raw material in the step (7) is gold slurry or platinum slurry.
The invention has the beneficial effects that:
1. the high-temperature resistant flexible thermosensitive device has the characteristics of high temperature resistance and flexibility by two-part design and realization. The substrate of the temperature sensing element is the fluorine crystal mica, and the fluorine crystal mica has the characteristics of atomic-level flatness, transparency, stripping, flexibility and strong corrosion resistance, and is an ideal nano material growth substrate. Can work at high temperature of 1100 ℃ for a long time without damaging the flexibility of the product, and widens the application field due to strong light transmission. Secondly, the toughness of the thermistor material is improved by compounding with the carbon material, a fine crystal strengthening mechanism, a hole collapse deformation toughening mechanism similar to that of porous metal, and a carbon material crack transfer deflection and crack bridging mechanism exist in the carbon material composite ceramic, and the overall toughening effect is finally achieved. In addition, the addition of the carbon material can cause the material to be difficult to sinter and compact, and the invention prepares the carbon material @ oxide ceramic composite material with better micro-morphology and comprehensive performance by adjusting the preparation process, thereby obtaining the heat-sensitive thick film with good crystallinity, compactness and flexibility.
2. The thermosensitive device prepared by the invention has the advantages that the base part and the thermosensitive detection unit are in interdependent relationship, the base provides support and flexibility improvement for the thermosensitive detection unit, the phenomenon of pulverization of the thermosensitive detection unit due to poor mechanical performance is prevented, the thermosensitive detection unit is the core part of the thermosensitive resistance element and provides functional support for the element, and when a load is borne, the thermosensitive resistance element can be prevented from being damaged due to mismatching of the base and the temperature detection unit as far as possible.
3. The thermistor can work under the high-temperature condition without damaging the flexibility, has simple structure, accurate and controllable thickness and high yield, can work at the high temperature for a long time, is very suitable for batch production, and has great application prospect.
Drawings
FIG. 1 is an XRD pattern of a nanoscale thermally sensitive oxide powder prepared in example 4 of the present invention;
FIG. 2 is an XRD pattern of graphite oxide @ thermal oxide powder prepared in example 4 of the present invention;
FIG. 3 SEM image of thermally sensitive thick film post-processed in example 4 of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
The reagents or instruments used in the present invention are not indicated by manufacturers, and are all conventional products commercially available.
Example 1
1. With Mn1.56Co0.96Ni0.48O4For the target thermosensitive material, 30 parts by weight of manganese sulfate, 30 parts by weight of cobalt sulfate heptahydrate, 14 parts by weight of nickel sulfate hexahydrate, and 26 parts by weight of sodium hydroxide were weighed, respectively. And dissolving the weighed metal salt into a proper amount of deionized water at the temperature of 40 ℃ by stirring to form a saturated metal salt solution. Sodium hydroxide is fully dissolved into a proper amount of deionized water to form a sodium hydroxide solution with the pH value of 10. Then slowly dripping the saturated metal salt solution into the sodium hydroxide solution under the stirring of the water bath at the temperature of 30 ℃, continuously stirring for 5 hours, and then standing for 10 hours to obtain a precipitate. Washing the obtained precipitate with deionized water and ethanol to neutrality, filtering, freeze-drying in a vacuum freeze-drying machine at-40 deg.C for 10 hr to obtain dried fluffy product powder, pre-sintering at 500 deg.C for 2 hr, ball-milling for 12 hr, and freeze-drying at-40 deg.C for 48 hr to obtain nanometer thermal sensitive oxide powder.
2. Adding graphene oxide dispersion liquid accounting for 0.3 wt% into the prepared superfine thermosensitive oxide powder, wherein the concentration of graphene oxide in the graphene oxide dispersion liquid is 2mg/mL, uniformly mixing by using a vacuum stirring and defoaming machine, precooling for 2 hours in a vacuum freeze dryer at-40 ℃, opening a vacuum pump for treating for 48 hours, taking out and grinding for 30 minutes to obtain the graphene oxide @ thermosensitive oxide powder.
3. 70 parts by weight of terpineol, 4 parts by weight of ethyl cellulose, 10 parts by weight of diethylene glycol butyl ether, 8 parts by weight of diethylene glycol butyl ether acetate and 10 parts by weight of span 85 are stirred in a water bath at 90 ℃ until the components are uniformly mixed to obtain the organic carrier.
4. Preparing slurry: the graphene oxide @ thermal sensitive oxide powder comprises the following components in percentage by mass: weighing the organic carrier at a ratio of 6:4, mixing and size mixing by using a vacuum stirring defoaming machine, wherein the rotating speed is 2000rpm in the mixing process, the mixing time is 4min, the defoaming time is 2min, and the mixed size is ground by using a three-roll grinder, the grinding speed is 200 rpm, the grinding time is 20min, and the grinding times are 6 times.
5. The prepared slurry was coated on the fluorine crystal mica by a screen printing technique to form a heat sensitive thick film having a thickness of 5 μm.
6. Post-treatment of the heat-sensitive thick film: and (3) drying the heat-sensitive thick film in a constant-temperature oven at 150 ℃ for 12 hours for curing, covering and pressing a high-temperature-resistant flexible substrate with the same size and shape on the cured heat-sensitive thick film, then packaging by adopting vacuum packaging equipment, carrying out cold isostatic pressing in an isostatic pressing machine, setting the pressure to be 200MPa, and keeping the pressure for 3 min. And (3) after cold isostatic pressing, stripping the packaging layer and the high-temperature-resistant flexible substrate, taking out the thermosensitive thick film, placing the thermosensitive thick film on a corundum plate, and sintering under the protection of nitrogen. The sintering adopts a two-step method: firstly, carrying out glue discharging treatment, heating to 800 ℃ at a heating rate of 3 ℃/min, and keeping the temperature for 1 h; and step two, after the heat preservation at 800 ℃ is finished, continuously heating to 1100 ℃ at the speed of 3 ℃/min and preserving the heat for 3 h.
7. Printing an electrode: printing an electrode on the processed thermosensitive thick film by using a platinum paste through a screen printing technology, drying the thermosensitive thick film with the electrode in a constant-temperature drying box at 150 ℃ for 2 hours, transferring the thermosensitive thick film into a box furnace for electrode annealing at the electrode annealing temperature of 800 ℃ for 30 minutes, and welding an outer lead on the electrode through a bonding technology to obtain the high-temperature-resistant flexible thermosensitive device body layer.
8. Preparing an insulating layer: and printing epoxy resin on the high-temperature-resistant flexible thermosensitive device body layer by adopting a screen printing technology for insulation packaging, and then putting the whole body into an oven to dry for 4 hours at the temperature of 80 ℃ to obtain the high-temperature-resistant flexible thermosensitive device.
Wherein, the printing technological parameters of the silk-screen printing technology are as follows: the distance between the sample stage and the plate is 5 μm, the mesh number of the screen is 250 meshes, and the printing speed is 70 mm/s.
Example 2
1. Preparing thermistor powder: with Mn1.56Co0.96Ni0.48O430 parts by weight of manganese sulfate, 30 parts by weight of cobalt sulfate heptahydrate, 14 parts by weight of nickel sulfate hexahydrate, and 26 parts by weight of sodium hydroxide, which are required as the target thermosensitive material, were weighed, respectively. And dissolving the weighed metal salt into a proper amount of deionized water at the temperature of 40 ℃ by stirring to form a saturated metal salt solution. Sodium hydroxide is fully dissolved into a proper amount of deionized water to form a sodium hydroxide solution with the pH value of 12. Then slowly dripping the saturated metal salt solution into the sodium hydroxide solution under the stirring of a water bath at 50 ℃, continuously stirring for 2 hours, and then standing for 12 hours to obtain a precipitate. Washing the obtained precipitate with deionized water and ethanol to neutrality, filtering, freeze-drying in a vacuum freeze-drying machine at-40 deg.C for 10 hr to obtain dried fluffy product powder, pre-sintering at 800 deg.C for 1 hr, ball-milling for 12 hr, and freeze-drying at-40 deg.C for 48 hr to obtain nanometer thermal sensitive oxide powder.
2. Adding carbon fiber dispersion liquid accounting for 0.5 wt% into the prepared superfine thermosensitive oxide powder, uniformly mixing the carbon fibers in the carbon fiber dispersion liquid by using a vacuum stirring defoaming machine, precooling the mixture for 2 hours at-40 ℃ in a vacuum freeze dryer, opening a vacuum pump for treating the mixture for 48 hours, and taking out and grinding the mixture for 30 minutes to obtain the carbon fiber @ thermosensitive oxide powder.
3. 60 parts by weight of terpineol, 6 parts by weight of ethyl cellulose, 15 parts by weight of diethylene glycol butyl ether, 14 parts by weight of diethylene glycol butyl ether acetate and 8 parts by weight of span 85 are stirred in a water bath at 90 ℃ until the components are uniformly mixed, and the organic carrier is obtained.
4. Preparing slurry: carbon fiber @ thermal sensitive oxide powder: weighing the organic carrier at a ratio of 8:2, mixing and size mixing by using a vacuum stirring defoaming machine, wherein the rotating speed is 1000rpm in the mixing process, the mixing time is 8min, the defoaming time is 4min, and the mixed size is ground by using a three-roll grinder, the grinding speed is 100 rpm, the grinding time is 40min, and the grinding times are 10 times.
5. The prepared slurry was coated on the fluorine crystal mica by a screen printing technique to form a heat sensitive thick film having a thickness of 6 μm.
6. Post-treatment of the heat-sensitive thick film: and (3) drying the heat-sensitive thick film in a constant-temperature oven at 150 ℃ for 12 hours for curing, covering and pressing a high-temperature-resistant flexible substrate with the same size and shape on the cured heat-sensitive thick film, then packaging by adopting vacuum packaging equipment, carrying out cold isostatic pressing in an isostatic pressing machine, setting the pressure to be 100MPa, and keeping the pressure for 5 minutes. And (3) after cold isostatic pressing, stripping the packaging layer and the high-temperature-resistant flexible substrate, taking out the thermosensitive thick film, placing the thermosensitive thick film on a corundum plate, and sintering under the protection of nitrogen. The sintering adopts a two-step method: firstly, carrying out glue discharging treatment, heating to 800 ℃ at a heating rate of 3 ℃/min, and keeping the temperature for 1 h; and step two, after the heat preservation at 800 ℃ is finished, continuously heating to 1000 ℃ at the speed of 3 ℃/min and preserving the heat for 4 hours.
7. Printing an electrode: printing an electrode on the processed thermosensitive thick film by using a platinum paste through a screen printing technology, drying the thermosensitive thick film with the electrode in a constant-temperature drying box at 150 ℃ for 2 hours, transferring the thermosensitive thick film into a box furnace for electrode annealing at the electrode annealing temperature of 1000 ℃ for 20 minutes, and welding an outer lead on the electrode through a bonding technology to obtain the high-temperature-resistant flexible thermosensitive device body layer.
8. Preparing an insulating layer: and printing epoxy resin on the high-temperature-resistant flexible thermosensitive device body layer by adopting a screen printing technology for insulation packaging, and then putting the whole body into an oven to dry for 4 hours at the temperature of 80 ℃ to obtain the high-temperature-resistant flexible thermosensitive device.
Wherein, the printing technological parameters of the silk-screen printing technology are as follows: the distance between the sample stage and the plate is 6 μm, the mesh number of the screen is 300 meshes, and the printing speed is 80 mm/s.
Example 3
1. Preparing thermistor powder: with Mn1.56Co0.96Ni0.48O4For the target thermosensitive material, 30 parts by weight of manganese sulfate, 30 parts by weight of cobalt sulfate heptahydrate, 14 parts by weight of nickel sulfate hexahydrate, and 26 parts by weight of sodium hydroxide were weighed, respectively. Stirring and dissolving the weighed metal salt at the temperature of 40 DEG CDissolving the mixture into a proper amount of deionized water to form a saturated metal salt solution. Sodium hydroxide is dissolved sufficiently in an appropriate amount of deionized water to form a sodium hydroxide solution having a pH of 14. Then slowly dripping the saturated metal salt solution into the sodium hydroxide solution under the stirring of the water bath at the temperature of 40 ℃, continuing stirring for 3 hours, and then standing for 11 hours to obtain a precipitate. Washing the obtained precipitate with deionized water and ethanol to neutrality, filtering, freeze-drying in a vacuum freeze-drying machine at-40 deg.C for 10 hr to obtain dried fluffy product powder, pre-sintering at 600 deg.C for 1 hr, ball-milling for 12 hr, and freeze-drying at-40 deg.C for 48 hr to obtain nanometer thermal sensitive oxide powder.
2. Adding 4 wt% of graphene oxide @ carbon nanotube dispersion liquid into the prepared superfine thermosensitive oxide powder, wherein the concentration of the graphene oxide @ carbon nanotube in the graphene oxide @ carbon nanotube dispersion liquid is 2mg/mL, and the mass ratio of the graphene oxide to the carbon nanotube in the dispersion liquid is 1: 1, uniformly mixing by using a vacuum stirring defoaming machine, precooling for 2 hours in a vacuum freeze dryer at-40 ℃, opening a vacuum pump for processing for 48 hours, and then taking out and grinding for 30min to obtain carbon nanotube @ graphite oxide @ thermosensitive oxide powder.
3. 50 parts by weight of terpineol, 8 parts by weight of ethyl cellulose, 18 parts by weight of diethylene glycol butyl ether, 12 parts by weight of diethylene glycol butyl ether acetate and 6 parts by weight of span 85 are stirred in a water bath at 90 ℃ until the components are uniformly mixed, and the organic carrier is obtained.
4. Preparing slurry: carbon nano tube @ thermal sensitive oxide powder: weighing the organic carriers at a ratio of 7:3, mixing and size mixing by using a vacuum stirring defoaming machine, wherein the rotating speed is 1500rpm in the mixing process, the mixing time is 5min, the defoaming time is 3min, and the mixed size is ground by using a three-roll grinder, the grinding speed is 150 rpm, the grinding time is 35min, and the grinding times are 8 times.
5. The prepared slurry was coated on the fluorine crystal mica by a screen printing technique to form a heat sensitive thick film having a thickness of 8 μm.
6. Post-treatment of the heat-sensitive thick film: and (3) drying the heat-sensitive thick film in a constant-temperature oven at 150 ℃ for 12 hours for curing, covering and pressing a high-temperature-resistant flexible substrate with the same size and shape on the cured heat-sensitive thick film, then packaging by adopting vacuum packaging equipment, carrying out cold isostatic pressing in an isostatic pressing machine, setting the pressure to be 150MPa, and keeping the pressure for 4 minutes. And (3) after cold isostatic pressing, stripping the packaging layer and the high-temperature-resistant flexible substrate, taking out the thermosensitive thick film, placing the thermosensitive thick film on a corundum plate, and sintering under the protection of nitrogen. The sintering adopts a two-step method: firstly, carrying out glue discharging treatment, heating to 800 ℃ at a heating rate of 3 ℃/min, and keeping the temperature for 1 h; and step two, after the heat preservation at 800 ℃ is finished, continuously heating to 1200 ℃ at the speed of 3 ℃/min and preserving the heat for 2 h.
7. Printing an electrode: printing an electrode on the processed thermosensitive thick film by using a platinum paste through a screen printing technology, drying the thermosensitive thick film with the electrode in a constant-temperature drying box at 150 ℃ for 2 hours, transferring the thermosensitive thick film into a box furnace for electrode annealing at the electrode annealing temperature of 500 ℃ for 50 minutes, and welding an outer lead on the electrode through a bonding technology to obtain the high-temperature-resistant flexible thermosensitive device body layer.
8. Preparing an insulating layer: and printing polyester resin on the high-temperature-resistant flexible thermosensitive device body layer by adopting a screen printing technology for insulating packaging, and then putting the whole into an oven to dry for 4 hours at the temperature of 80 ℃ to obtain the high-temperature-resistant flexible thermosensitive device.
Wherein, the printing technological parameters of the silk-screen printing technology are as follows: the distance between the sample stage and the plate is 8 μm, the mesh number of the screen is 400 meshes, and the printing speed is 80 mm/s.
Example 4
1. Preparing thermistor powder: with Mn1.56Co0.96Ni0.48O4For the target thermosensitive material, 30 parts by weight of manganese sulfate, 30 parts by weight of cobalt sulfate heptahydrate, 14 parts by weight of nickel sulfate hexahydrate, and 26 parts by weight of sodium hydroxide were weighed, respectively. And dissolving the weighed metal salt into a proper amount of deionized water at the temperature of 40 ℃ by stirring to form a saturated metal salt solution. Sodium hydroxide is dissolved sufficiently in an appropriate amount of deionized water to form a sodium hydroxide solution having a pH of 14. Then slowly dripping the saturated metal salt solution into the sodium hydroxide solution under the stirring of water bath at 40 ℃, and continuing to addStirred for 3 hours and then left to stand for 12 hours to obtain a precipitate. Washing the obtained precipitate with deionized water and ethanol to neutrality, filtering, freeze-drying in a vacuum freeze-drying machine at-40 deg.C for 10 hr to obtain dried fluffy product powder, pre-sintering at 600 deg.C for 1 hr, ball-milling for 12 hr, and freeze-drying at-40 deg.C for 48 hr to obtain nanometer thermal sensitive oxide powder.
2. Adding a graphene oxide dispersion liquid accounting for 1.2 wt% into the prepared superfine thermosensitive oxide powder, uniformly mixing the graphene oxide dispersion liquid with the concentration of 2mg/mL by using a vacuum stirring and defoaming machine, precooling the mixture for 2 hours in a vacuum freeze dryer at-40 ℃, starting a vacuum pump for 48 hours, taking out and grinding the mixture for 30 minutes to obtain the graphite oxide @ thermosensitive oxide powder.
3. 70 parts by weight of terpineol, 8 parts by weight of ethyl cellulose, 14 parts by weight of diethylene glycol butyl ether, 16 parts by weight of diethylene glycol butyl ether acetate and 10 parts by weight of span 85 are stirred in a water bath at 90 ℃ until the components are uniformly mixed to obtain the organic carrier.
4. Preparing slurry: graphite oxide @ thermal sensitive oxide powder: weighing the organic carrier at a ratio of 5:5, mixing and size mixing by using a vacuum stirring defoaming machine, wherein the rotating speed is 1500rpm in the mixing process, the mixing time is 5min, the defoaming time is 3min, and the mixed size is ground by using a three-roll grinder, the grinding speed is 200 rpm, the grinding time is 25min, and the grinding times are 5 times.
5. The prepared slurry was coated on the fluorine crystal mica by a screen printing technique to form a heat sensitive thick film having a thickness of 5 μm.
6. Post-treatment of the heat-sensitive thick film: and (3) drying the heat-sensitive thick film in a constant-temperature oven at 150 ℃ for 12 hours for curing, covering and pressing a high-temperature-resistant flexible substrate with the same size and shape on the cured heat-sensitive thick film, then packaging by adopting vacuum packaging equipment, carrying out cold isostatic pressing in an isostatic pressing machine, setting the pressure to be 300MPa, and keeping the pressure for 1 min. And (3) after cold isostatic pressing, stripping the packaging layer and the high-temperature-resistant flexible substrate, taking out the thermosensitive thick film, placing the thermosensitive thick film on a corundum plate, and sintering under the protection of nitrogen. The sintering adopts a two-step method: firstly, carrying out glue discharging treatment, heating to 800 ℃ at a heating rate of 3 ℃/min, and keeping the temperature for 1 h; and step two, after the heat preservation at 800 ℃ is finished, continuously heating to 1150 ℃ at the speed of 3 ℃/min and preserving the heat for 2 h.
7. Printing an electrode: and printing an electrode on the processed thermosensitive thick film by using a screen printing technology, drying the thermosensitive thick film with the electrode in a constant-temperature drying box at 150 ℃ for 2 hours, transferring the thermosensitive thick film into a box furnace for electrode annealing at the electrode annealing temperature of 400 ℃ for 60 minutes, and welding an outer lead on the electrode by using a bonding technology to obtain the high-temperature-resistant flexible thermosensitive device body layer.
8. Preparing an insulating layer: and printing epoxy resin on the high-temperature-resistant flexible thermosensitive device body layer by adopting a screen printing technology for insulation packaging, and then putting the whole body into an oven to dry for 4 hours at the temperature of 80 ℃ to obtain the high-temperature-resistant flexible thermosensitive device.
Wherein, the printing technological parameters of the silk-screen printing technology are as follows: the distance between the sample stage and the plate is 5 μm, the mesh number of the screen is 350 meshes, and the printing speed is 70 mm/s.
Example 5
1. Preparing thermistor powder: with Mn1.56Co0.96Ni0.48O4For the target thermosensitive material, 30 parts by weight of manganese sulfate, 30 parts by weight of cobalt sulfate heptahydrate, 14 parts by weight of nickel sulfate hexahydrate, and 26 parts by weight of sodium hydroxide were weighed, respectively. And dissolving the weighed metal salt into a proper amount of deionized water at the temperature of 40 ℃ by stirring to form a saturated metal salt solution. Sodium hydroxide is fully dissolved in a proper amount of deionized water to form a sodium hydroxide solution with a pH value of 13. Then slowly dripping the saturated metal salt solution into the sodium hydroxide solution under the stirring of the water bath at the temperature of 30 ℃, continuously stirring for 3 hours, and then standing for 12 hours to obtain a precipitate. Washing the obtained precipitate with deionized water and ethanol to neutrality, filtering, freeze-drying in a vacuum freeze-drying machine at-40 deg.C for 10 hr to obtain dried fluffy product powder, pre-sintering at 700 deg.C for 1 hr, ball-milling for 12 hr, and freeze-drying at-40 deg.C for 48 hr to obtain nanometer thermal sensitive oxide powder.
2. Adding a glassy carbon @ carbon nanotube dispersion liquid accounting for 2 wt% into the prepared superfine thermosensitive oxide powder, wherein the concentration of glassy carbon @ carbon nanotubes in the glassy carbon @ carbon nanotube dispersion liquid is 2mg/mL, and the mass ratio of glassy carbon to carbon nanotubes in the dispersion liquid is 1: 1, uniformly mixing by using a vacuum stirring defoaming machine, precooling for 2 hours in a vacuum freeze dryer at-40 ℃, opening a vacuum pump for processing for 48 hours, and then taking out and grinding for 30min to obtain glassy carbon @ carbon nanotube @ thermosensitive oxide powder.
3. 55 parts by weight of terpineol, 7 parts by weight of ethyl cellulose, 12 parts by weight of diethylene glycol butyl ether, 10 parts by weight of diethylene glycol butyl ether acetate and 5 parts by weight of span 85 are stirred in a water bath at 90 ℃ until the components are uniformly mixed to obtain the organic carrier.
4. Preparing slurry: the glass carbon @ carbon nanotube @ thermal sensitive oxide powder comprises the following components in percentage by mass: weighing the organic carrier at a ratio of 6:4, mixing and size mixing by using a vacuum stirring defoaming machine, wherein the rotating speed is 2000rpm in the mixing process, the mixing time is 4min, the defoaming time is 1min, and the mixed size is ground by using a three-roll grinder, the grinding speed is 200 rpm, the grinding time is 20min, and the grinding times are 10 times.
5. The prepared slurry was coated on the fluorine crystal mica by a screen printing technique to form a heat sensitive thick film having a thickness of 10 μm.
6. Post-treatment of the heat-sensitive thick film: and (3) drying the heat-sensitive thick film in a constant-temperature oven at 150 ℃ for 12 hours for curing, covering and pressing a high-temperature-resistant flexible substrate with the same size and shape on the cured heat-sensitive thick film, then packaging by adopting vacuum packaging equipment, carrying out cold isostatic pressing in an isostatic pressing machine, setting the pressure to be 250MPa, and keeping the pressure for 2 minutes. And (3) after cold isostatic pressing, stripping the packaging layer and the high-temperature-resistant flexible substrate, taking out the thermosensitive thick film, placing the thermosensitive thick film on a corundum plate, and sintering under the protection of nitrogen. The sintering adopts a two-step method: firstly, carrying out glue discharging treatment, heating to 800 ℃ at a heating rate of 3 ℃/min, and keeping the temperature for 1 h; and step two, after the heat preservation at 800 ℃ is finished, continuously heating to 1100 ℃ at the speed of 3 ℃/min and preserving the heat for 4 h.
7. Printing an electrode: and printing an electrode on the processed thermosensitive thick film by using a screen printing technology, drying the thermosensitive thick film with the electrode in a constant-temperature drying box at 150 ℃ for 2 hours, transferring the thermosensitive thick film into a box furnace for electrode annealing at the electrode annealing temperature of 600 ℃ for 40min, and welding an outer lead on the electrode by using a bonding technology to obtain the high-temperature-resistant flexible thermosensitive device body layer.
8. Preparing an insulating layer: and printing parylene on the high-temperature-resistant flexible thermosensitive device body layer by adopting a screen printing technology for insulating packaging, and then putting the whole into an oven to dry for 4 hours at the temperature of 80 ℃ to obtain the high-temperature-resistant flexible thermosensitive device.
Wherein, the printing technological parameters of the silk-screen printing technology are as follows: the distance between the sample stage and the plate is 15 μm, the mesh number of the screen is 350 meshes, and the printing speed is 70 mm/s.
Shown in FIG. 1 as Mn1.56Co0.96Ni0.48O4According to the XRD pattern of the compound, the sample forms a spinel structure, and has obvious peaks of (111), (220), (311), (222), (400), (422), (511), (440) and (533), the preferred orientation is (311), the diffraction peak is sharp and clear at about 36 degrees, and the crystallinity is good.
FIG. 2 shows graphite oxide @ Mn1.56Co0.96Ni0.48O4The XRD spectrogram shows that a sample forms a spinel phase, the preferred orientation in the spectrogram is (311) (400), the diffraction peak is sharp and clear, and the crystallinity is good. A diffuse peak appears between 25 degrees and 30 degrees of 2 theta, and is a corresponding peak of the graphene oxide.
Fig. 3 is an SEM image of the post-processed heat-sensitive thick film, and it can be seen that the heat-sensitive thick film is excellent in denseness.
The high temperature resistant flexible thermosensitive device prepared in examples 1-5 was subjected to a temperature resistance test, and the test results were as follows:
those skilled in the art to which the present invention pertains can also make appropriate alterations and modifications to the above-described embodiments, in light of the above disclosure. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (10)
1. The full-printing preparation method of the manganese nickel cobalt-based high-temperature-resistant flexible thermosensitive device mainly comprises a high-temperature-resistant flexible substrate, a thermosensitive thick film, an electrode and an insulating layer, and is characterized in that: the preparation method comprises the following steps:
(1) preparation of nanoscale thermal sensitive oxide powder
Adding a proper amount of deionized water into the weighed metal salt raw material, heating in a water bath, and stirring until a saturated metal salt solution is formed; dissolving alkali in deionized water to form an alkali solution, slowly adding a saturated metal salt solution into the alkali solution under the stirring of a water bath, and stirring and standing to obtain a precipitate; washing, filtering and freeze-drying the obtained precipitate to obtain product powder; pre-sintering the product powder at constant temperature, ball-milling, freezing and drying to prepare nanoscale thermosensitive oxide powder;
(2) preparation of carbon material @ thermal sensitive oxide powder
Adding the carbon material dispersion liquid into the prepared nanoscale oxide powder, uniformly stirring in a vacuum stirring and defoaming machine, putting into a vacuum freeze-drying machine, freeze-drying for 48 hours at-40 ℃, and then grinding for 30 minutes to obtain dry and dispersed carbon material @ thermosensitive oxide powder;
(3) preparation of organic vehicle
Mixing 50-70 parts by weight of terpineol, 4-8 parts by weight of ethyl cellulose, 10-20 parts by weight of diethylene glycol butyl ether, 8-16 parts by weight of diethylene glycol butyl ether acetate and 5-10 parts by weight of span 85, and uniformly stirring to obtain an organic carrier;
(4) preparing slurry
Mixing carbon material @ thermal sensitive oxide powder and an organic carrier in a ratio of 8: 2. 7: 3. 6: 4. 5: weighing the mass ratio of 5, mixing and size mixing by adopting a vacuum stirring defoaming machine, wherein the rotating speed is 1000-3000rpm, the time is 2-8min, the defoaming time is 1-4min, grinding the mixed slurry by adopting a three-roll grinder, the grinding speed is 100-200 revolutions per minute, the grinding time is 20-40min, and the grinding times are 5-10 times to obtain the slurry;
(5) preparation of a Heat-sensitive Thick film
Uniformly coating the prepared slurry on a high-temperature-resistant flexible substrate by adopting a screen printing technology to form a thermosensitive thick film with the thickness of 5-10 mu m;
(6) post-treatment of heat-sensitive thick films
Drying the heat-sensitive thick film in a constant-temperature oven at 150 ℃ for 12 hours for curing, covering a high-temperature-resistant flexible substrate with the same size and shape on the cured heat-sensitive thick film, then packaging by adopting vacuum packaging equipment, and carrying out cold isostatic pressing in an isostatic pressing machine, wherein the pressure is set to be 100-300MPa, and the pressure maintaining time is 1-5 min; after cold isostatic pressing, stripping the packaging layer and the high-temperature-resistant flexible substrate, taking out the thermosensitive thick film, placing the thermosensitive thick film on a corundum plate, and sintering under the protection of nitrogen;
(7) printed electrode
Firstly, preparing an electrode on a processed thermosensitive thick film by adopting a screen printing technology, then drying the thermosensitive thick film in a constant-temperature drying box at the temperature of 150 ℃ for 2 hours, then transferring the thermosensitive thick film to a box-type furnace for annealing the electrode, wherein the annealing temperature of the electrode is 400-1000 ℃ and the time is 20-60min, and finally welding an outer lead on the electrode by adopting a bonding technology to obtain a high-temperature-resistant flexible thermosensitive device body layer;
(8) preparing an insulating layer
And printing polyester resin, parylene or epoxy resin on the high-temperature-resistant flexible thermosensitive device body layer by adopting a screen printing technology for insulating packaging, then putting the high-temperature-resistant flexible thermosensitive device body layer into an oven, and drying for 4 hours at the temperature of 80 ℃ to obtain the high-temperature-resistant flexible thermosensitive device.
2. The method for preparing the Mn-Ni-Co-based high temperature resistant flexible thermosensitive device according to claim 1, which comprises the following steps: the preparation method of the nanometer thermal sensitive oxide powder in the step (1) comprises the following specific steps: adding a proper amount of deionized water into the weighed metal salt raw materials, and heating and stirring in a water bath at 40 ℃ until a saturated metal salt solution is formed; dissolving alkali in deionized water to form an alkali solution with the pH value of 9-14, slowly adding a saturated metal salt solution into the alkali solution under the stirring of water bath at the temperature of 30-50 ℃, continuously stirring for 2-5 hours, and standing for 10-12 hours to obtain a precipitate; washing the obtained precipitate with deionized water and ethanol to neutrality, vacuum filtering, and freeze drying in a vacuum freeze dryer at-40 deg.C for 10 hr to obtain fluffy dry product powder; pre-sintering the resultant powder at the constant temperature of 500-800 ℃ for 1-2h, and then ball-milling for 12h, and freeze-drying for 48h at-40 ℃ to obtain the nano-scale thermosensitive oxide powder.
3. The method for preparing the Mn-Ni-Co-based high temperature resistant flexible thermosensitive device according to claim 2, wherein the method comprises the following steps: the metal salt raw materials are manganese sulfate, cobalt sulfate heptahydrate and nickel sulfate hexahydrate, and the alkali is sodium hydroxide.
4. The method for preparing the Mn-Ni-Co-based high temperature resistant flexible thermosensitive device according to claim 1, which comprises the following steps: the carbon material in the step (2) is one or more of carbon fiber, graphene oxide, carbon nano tube and glassy carbon.
5. The method for preparing the Mn-Ni-Co-based high temperature resistant flexible thermosensitive device according to claim 1, which comprises the following steps: the carbon material dispersion liquid in the step (2) is formed by dispersing a carbon material in ethanol, and the adding amount of the carbon material dispersion liquid is 0.3-4 wt%.
6. The method for preparing the Mn-Ni-Co-based high temperature resistant flexible thermosensitive device according to claim 1, which comprises the following steps: the concentration of the carbon material in the carbon material dispersion liquid in the step (2) is 2 mg/mL.
7. The method for preparing the Mn-Ni-Co-based high temperature resistant flexible thermosensitive device according to claim 1, which comprises the following steps: the printing technological parameters of the silk-screen printing technology in the steps (5), (7) and (8) are as follows: the distance between the sample stage and the plate is 5-15 μm, the mesh number of the screen is 250-400 meshes, and the printing speed is 70-80 mm/s.
8. The method for preparing the Mn-Ni-Co-based high temperature resistant flexible thermosensitive device according to claim 1, which comprises the following steps: the high-temperature resistant flexible substrate is fluorine crystal mica.
9. The method for preparing the Mn-Ni-Co-based high temperature resistant flexible thermosensitive device according to claim 1, which comprises the following steps: the sintering in the step (6) adopts a two-step method: firstly, carrying out glue discharging treatment, heating to 800 ℃ at a heating rate of 3 ℃/min, and keeping the temperature for 1 h; and secondly, after the heat preservation at 800 ℃ is finished, continuously heating to 1000-1200 ℃ at the speed of 3 ℃/min and preserving the heat for 2-4 h.
10. The method for preparing the Mn-Ni-Co-based high temperature resistant flexible thermosensitive device according to claim 1, which comprises the following steps: and (4) the raw material of the electrode in the step (7) is gold slurry or platinum slurry.
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