CN115849898B - Thermal sensitive ceramic material, preparation method thereof and thermistor - Google Patents
Thermal sensitive ceramic material, preparation method thereof and thermistor Download PDFInfo
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title abstract description 29
- 229910004247 CaCu Inorganic materials 0.000 claims abstract description 90
- 239000000919 ceramic Substances 0.000 claims abstract description 47
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 108
- 239000002243 precursor Substances 0.000 claims description 57
- 150000002500 ions Chemical class 0.000 claims description 51
- 239000003431 cross linking reagent Substances 0.000 claims description 40
- 239000000178 monomer Substances 0.000 claims description 39
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 35
- 239000003999 initiator Substances 0.000 claims description 33
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 33
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000005245 sintering Methods 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 22
- 239000011575 calcium Substances 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 19
- 238000006116 polymerization reaction Methods 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 159000000007 calcium salts Chemical class 0.000 claims description 17
- 150000001879 copper Chemical class 0.000 claims description 17
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000003825 pressing Methods 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000005469 granulation Methods 0.000 claims description 8
- 230000003179 granulation Effects 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000001354 calcination Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 10
- 230000007547 defect Effects 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 3
- 239000011858 nanopowder Substances 0.000 abstract description 3
- 239000011572 manganese Substances 0.000 description 17
- 239000000499 gel Substances 0.000 description 12
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 10
- 239000011240 wet gel Substances 0.000 description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000977 initiatory effect Effects 0.000 description 5
- 210000001161 mammalian embryo Anatomy 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- -1 Cu2+ ions Chemical class 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 230000000087 stabilizing effect Effects 0.000 description 4
- 150000003746 yttrium Chemical class 0.000 description 4
- 239000010949 copper Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 150000003754 zirconium Chemical class 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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Abstract
The application provides a thermosensitive ceramic material which is CaCu 3Ti4O12 with a body-centered cubic perovskite-like structure doped with metal M, and the molecular formula is CaCu 3Ti4‑xMxO12, wherein M is at least one selected from Y, al, zr, mn, and x is more than 0 and less than or equal to 0.6. The application also provides a thermistor comprising the thermosensitive ceramic material and a preparation method of the thermosensitive ceramic material. The CaCu 3Ti4‑xMxO12 -based nano powder material with a single-phase structure and controllable particle size can be prepared by adopting the preparation method, so that the obtained CaCu 3Ti4‑xMxO12 thermistor has uniform chemical components, narrow ceramic grain size distribution and single-phase structure, and can well overcome the defect of non-ideal product performance consistency caused by non-uniformity of chemical components and non-uniformity of microstructures of a mixture.
Description
Technical Field
The application relates to a thermosensitive ceramic material, a preparation method thereof and a thermosensitive resistor comprising the thermosensitive ceramic material.
Background
The thermistor is a resistor whose resistance value changes with a change in temperature. The positive temperature coefficient thermistor (PTC thermistor, positive Temperature Coefficient thermistor) and the negative temperature coefficient thermistor (NTC thermistor, negative Temperature Coefficient thermistor) are classified according to temperature coefficients. The resistance value of the positive temperature coefficient thermistor increases with an increase in temperature, and the resistance value of the negative temperature coefficient thermistor decreases with an increase in temperature.
Most of the NTC thermistors commercialized at present are composed of a mixture of two or more transition metal oxides, and the main component is a mixture of two or more oxides among the transition metal oxides Mn, ni, fe, co, li, zn, sn, cu, al. With the development of motor technology and the progress of industrial technology, the defects of the current commercialized NTC thermistor materials restrict the application of the components in the advanced electronic system. Firstly, as most NTC thermistors are composed of a mixture of various oxides, and the volatilization temperature of part of the oxides is low, the NTC thermistor materials are extremely easy to generate uneven chemical components in the preparation process, especially for small-size thermistor elements, and finally the problems of poor consistency and poor interchangeability of NTC thermistor products are caused; secondly, as chemical components are not uniform and are used in an environment with temperature change for a long time, the resistance of the thermistor is not easy to stabilize, the testing precision can change along with the use time, and the stability of a thermistor product is poor.
Disclosure of Invention
The embodiment of the application provides a thermosensitive ceramic material which is CaCu 3Ti4O12 with a body-centered cubic perovskite-like structure doped with metal M and has a molecular formula of CaCu 3Ti4-xMxO12, wherein M is at least one selected from Y, al, zr, mn, and x is more than 0 and less than or equal to 0.6.
The thermosensitive ceramic material has single phase structure, good high-temperature stability and good product consistency.
In the embodiment of the application, the thermosensitive ceramic material has a negative temperature coefficient characteristic in a temperature range of-50 ℃ to 300 ℃.
The working temperature range of the thermosensitive ceramic material is wider than that of the traditional thermosensitive ceramic material.
In an embodiment of the present application, the thermal ceramic material has a B constant of 5000 to 8000K.
The B constant of the thermosensitive ceramic material is higher than that of the conventional commercial NTC material, and the high B constant can improve the sensitivity and measurement accuracy of the negative temperature coefficient thermistor.
In an embodiment of the present application, the room temperature resistivity of the thermal ceramic material is 10 7Ω·cm～109 Ω·cm.
The room temperature resistivity of the thermal sensitive ceramic material is higher than that of the conventional commercial NTC thermal sensitive ceramic, and the thermal sensitive ceramic material is used as a sensor for real-time temperature monitoring, particularly as a storage battery for real-time monitoring, and has lower power consumption.
The second aspect of the embodiment of the application provides a preparation method of a thermosensitive ceramic material, which comprises the following steps:
Preparing an aqueous solution containing Ca 2+、Cu2+ and a doping ion M, wherein the doping ion M is at least one selected from Y 3+、Al3+、Zr4+、Mn2 +, and preparing a solution containing Ti 4+ ion complex;
Mixing and stirring the aqueous solution and the solution containing the Ti 4+ ion complex to obtain a precursor solution;
adding a monomer compound and a cross-linking agent into the precursor solution, and stirring;
continuously adding an initiator into the precursor solution to initiate the monomer compound and the cross-linking agent to carry out polymerization reaction so as to obtain blue gel;
drying the blue gel to obtain xerogel;
And (3) placing the xerogel into a sintering furnace for roasting, wherein the sintering furnace is heated to 650-850 ℃ from room temperature, and the CaCu 3Ti4-xMxO12 powder is obtained, wherein x is more than 0 and less than or equal to 0.6.
The CaCu 3Ti4-xMxO12 -based nano powder material with a single-phase structure and controllable particle size can be prepared by adopting the preparation method of the application, so that the obtained CaCu 3Ti4-xMxO12 thermistor has uniform chemical components, narrow ceramic grain size distribution and single-phase structure, and can well overcome the defect of non-ideal product performance consistency caused by non-uniformity of chemical components and non-uniformity of microstructures of a mixture.
In an embodiment of the application, preparing an aqueous solution containing Ca 2+、Cu2+ and dopant ions and preparing a solution containing Ti 4+ ion complex comprises: the water-soluble calcium salt, the water-soluble copper salt, the water-soluble ion-doped salt and the Ti 4+ ion complex are metered according to the stoichiometric ratio of CaCu 3Ti4-xMxO12, the metered water-soluble calcium salt, the water-soluble copper salt and the water-soluble ion-doped salt are dissolved in deionized water, and the metered Ti 4+ ion complex is dissolved in an organic solvent.
In the step of preparing the solution containing the Ti 4+ ion complex, the Ti 4+ ion complex adopts tetrabutyl titanate, the organic solvent adopts a mixed solution of ice ethanol and absolute ethanol, and a proper amount of acetylacetone is added.
In the step of adding a monomer compound and a crosslinking agent to the precursor solution, the monomer compound is acrylamide, the crosslinking agent is N, N' -methylenebisacrylamide, and the amount of the crosslinking agent added to the precursor solution is as follows: the mass of the cross-linking agent in each 100ml of precursor solution is 2.03 g-2.13 g, and the molar ratio of the cross-linking agent to the monomer compound is 1: (3-4.5).
In the embodiment of the application, the initiator is azodiisobutyronitrile, and the addition amount of the initiator is as follows: the mass of the initiator in each 100ml of the precursor solution is 10-20% of the total mass of the monomer compound and the crosslinking agent.
In the embodiment of the application, the temperature rising rate of the sintering furnace to 650-850 ℃ is 3-6 ℃/min, and the sintering time is at least 3 hours at 650-850 ℃.
In an embodiment of the present application, the preparation method further includes: pressing the CaCu 3Ti4-xMxO12 powder into a ceramic blank, and roasting the ceramic blank for 2-3 hours at 950-1100 ℃.
In an embodiment of the application, forming the ceramic body comprises grinding the CaCu 3Ti4-xMxO12 powder, adding a binder for granulation, and pressing the granulated powder under the pressure of 10-20 MPa to form the ceramic body.
In the embodiment of the application, the binder in the ceramic blank body is also required to be discharged through high-temperature heating before sintering the ceramic blank body.
According to a third aspect of the embodiment of the application, a thermosensitive ceramic material is provided, which is prepared by the preparation method according to the second aspect of the embodiment of the application.
A fourth aspect of the embodiment of the present application provides a thermistor, including a ceramic sheet and an electrode connected to the ceramic sheet, where the ceramic sheet includes the thermal ceramic material according to the first aspect or the third aspect of the embodiment of the present application.
Drawings
FIG. 1 is an X-ray diffraction pattern of a thermal sensitive ceramic material CaCu 3Ti3.4Al0.3Y0.3O12 ceramic according to an embodiment of the application.
Fig. 2 is a schematic diagram of a thermistor according to an embodiment of the present application.
Fig. 3A and 3B are graphs of resistance temperature characteristics of a thermal ceramic material according to an embodiment of the present application.
Description of the main reference signs
Thermistor 100
Ceramic wafer 10
Electrode 20
Electrode lead 30
Detailed Description
Embodiments of the present application will be described below with reference to the accompanying drawings in the embodiments of the present application. The parameter ranges referred to in the present application include the end values unless otherwise specified.
The traditional NTC thermistor is composed of a mixture of various oxides, however, the NTC thermistor material is extremely easy to generate uneven chemical components in the preparation process, especially for small-size thermistor elements, and finally the problems of poor consistency and poor interchangeability of NTC thermistor products are caused; and secondly, as chemical components are not uniform and are used in a temperature-changing environment for a long time, the resistance of the thermistor is not easy to stabilize, the testing precision can change along with the extension of the service time, and the stability of a thermistor product is poor.
The application provides a thermosensitive ceramic material which is at least one doped CaCu 3Ti4O12 (CCTO) in Y, al, zr, mn. The thermosensitive ceramic material has the characteristics of single phase, high thermosensitive B constant, high room temperature resistivity, adjustable room temperature resistivity, wide working temperature, good linearity and consistency.
The molecular formula of the thermosensitive ceramic material is CaCu 3Ti4-xMxO12, wherein M is at least one selected from Y, al, zr, mn, and x is more than 0 and less than or equal to 0.6.
As shown in the X-ray diffraction pattern of the thermosensitive ceramic material in fig. 1, it is known that the thermosensitive ceramic material has a single body-centered cubic perovskite-like structure. The thermosensitive ceramic material has single phase structure, good high-temperature stability and good product consistency.
The thermosensitive ceramic material has obvious negative temperature coefficient characteristics in the temperature range of-50 ℃ to 300 ℃, and the relation between ln (R/R 0) and 1000 (T -1-T0 -1) is shown in fig. 3A and 3B. The working temperature range of the thermosensitive ceramic material is wider than that of the traditional thermosensitive ceramic material.
The room temperature resistivity of the thermal sensitive ceramic material is adjustable within the range of 10 7Ω·cm～109 ohm cm after being doped in a trace amount, and the B constant of the thermal sensitive ceramic material is adjustable within the range of 5000-8000K. The room temperature resistivity of the thermal sensitive ceramic material is higher than that of the conventional commercial NTC thermal sensitive ceramic, and the thermal sensitive ceramic material is used as a sensor for real-time temperature monitoring, particularly as a storage battery for real-time monitoring, and has lower power consumption. The B constant of the thermosensitive ceramic material is higher than that of the conventional commercial NTC material, even the B constant is nearly doubled compared with that of the conventional NTC material, and the high B constant can improve the sensitivity and measurement accuracy of the negative temperature coefficient thermistor. In some embodiments, the thermal sensitive ceramic material may have a thermal B 25/300 constant of >7000K.
As shown in fig. 2, the present application also provides a thermistor 100 using the thermal ceramic material, the thermistor 100 including a ceramic sheet 10, a pair of electrodes 20 connected to the ceramic sheet 10, and electrode leads 30 respectively connected to the electrodes 20, the ceramic sheet 10 containing the thermal ceramic material. The electrodes 20 may be formed of conductive paste (e.g., conductive silver paste, conductive platinum paste) respectively coated on opposite sides of the ceramic sheet 10. The thermistor 100 can be used in a temperature sensor or the like, but is not limited thereto.
The application also provides a preparation method of the thermosensitive ceramic material, which is a sol-gel method and comprises the following steps.
S1: an aqueous solution containing Ca 2+、Cu2+ and a dopant ion selected from at least one of Y 3+、Al3+、Zr4+、Mn2+ is formulated.
The step of preparing an aqueous solution containing Ca 2+、Cu2+ and doped ions comprises: the water-soluble calcium salt, the water-soluble copper salt and the salt of the water-soluble doping ion are metered according to the stoichiometric ratio of CaCu 3Ti4-xMxO12, and the metered water-soluble calcium salt, the water-soluble copper salt and the salt of the water-soluble doping ion are dissolved in deionized water, wherein M represents the doping ion, and x is more than 0 and less than or equal to 0.6.
In some embodiments, the water-soluble calcium salt is Ca (CH 3COO)2·H2 O or Ca (NO 3)2·4H2 O, the water-soluble copper salt is Cu (the water-soluble salt of NO 3)2·3H2O,Y3+ is Y (the water-soluble salt of NO 3)3·6H2O,Al3+ is Al (the water-soluble salt of NO 3)3·9H2O,Zr4+ is Zr (the water-soluble salt of NO 3)·5H2O,Mn2+ is Mn (CH 3COO)2·H2 O, but not limited thereto).
In some embodiments, the aqueous solution is stirred at a temperature of 25-40 ℃ under normal pressure until the aqueous solution is in a clear and transparent state, so that an aqueous solution with a concentration of Ca 2+ of 0.01-0.05M, a concentration of Cu 2+ of 0.03-0.15M and a concentration of doped ion M of less than or equal to 0.02M is formed.
S2: a solution containing Ti 4+ ion complex was prepared.
With reference to the above step, the Ti 4+ ion complex is metered according to the stoichiometric ratio of CaCu 3Ti4-xMxO12, and then the metered Ti 4+ ion complex is mixed with an organic solvent to form a transparent and uniform solution. In some embodiments, the Ti 4+ ion concentration in the solution comprising the Ti 4+ ion complex is 0.04M to 0.2M.
In some embodiments, the Ti 4+ ion complex adopts tetrabutyl titanate, the organic solvent adopts a mixed solution of ice ethanol and absolute ethanol, a clear and transparent solution is formed at normal temperature and normal pressure, and a proper amount of acetylacetone can be added to stabilize the solution containing the Ti 4+ ion complex.
S3: and mixing and stirring the aqueous solution and the solution containing the Ti 4+ ion complex to obtain a precursor solution.
In the step S3, mixing and stirring are carried out at the temperature of 25+/-15 ℃ under normal pressure for at least 15-20 minutes, and then standing is carried out for at least 40 minutes to obtain the stable CaCu 3Ti4-xMxO12 precursor solution.
S4: a monomer compound and a crosslinking agent are added to the precursor solution and stirred.
And (S4) stirring and mixing to completely dissolve the monomer compound and the crosslinking agent to obtain a transparent solution.
In one embodiment, the monomer compound is acrylamide, the crosslinking agent is N, N' -methylenebisacrylamide, and the crosslinking agent is added to the precursor solution in an amount of: the mass of the cross-linking agent in each 100ml of precursor solution is 2.03 g-2.13 g, and the molar ratio of the cross-linking agent to the monomer compound is 1: (3-4.5).
S5: and continuously adding an initiator into the precursor solution to initiate the monomer compound and the cross-linking agent to carry out polymerization reaction, so as to obtain blue gel.
In one embodiment, the initiator used in step S5 is azobisisobutyronitrile, and the initiator is added in the following amount: the mass of the initiator in each 100ml of precursor solution is 10-20% of the total mass of the monomer compound and the cross-linking agent.
The precursor solution, to which the monomer compound, the crosslinking agent and the initiator are added, is heated to 40-80 c at normal pressure, for example by oil bath, while maintaining continuous stirring. The polymerization was completed to obtain a blue gel. Step S4 and step S5 effectively accelerate the process of obtaining the gel.
S6: and drying the blue gel to obtain xerogel, putting the xerogel into a sintering furnace for roasting, and heating the xerogel from room temperature to 650-850 ℃ for heat preservation and roasting to obtain doped CaCu 3Ti4-xMxO12 powder.
The drying mode of the blue gel is various, such as oven drying, vacuum drying, rotary evaporation drying and the like, preferably rotary evaporation drying mode, wherein a rotary evaporator is used for rotary evaporation drying, the drying temperature is 60-80 ℃, and the drying time is at least 4 hours.
The temperature rising rate of the sintering furnace to 650-850 ℃ is 3-6 ℃/min, and the heat preservation and roasting time is at least 3 hours at 650-850 ℃. In the roasting process, the xerogel is put into a sintering furnace and roasted in an atmosphere of normal pressure and air. And cooling the baked product to room temperature along with a furnace after the baking is finished, and obtaining the CaCu 3Ti4- xMxO12 nanometer micropowder of the pure body-centered cubic perovskite phase.
S7: pressing the powder into a ceramic blank with a certain shape and size, and sintering the ceramic blank for 2-3 hours at 950-1100 ℃. The sintering in this step is to densify the CaCu 3Ti4-xMxO12 powder particles to form a ceramic.
The preparation method of the ceramic body specifically comprises the following steps:
Grinding the powder obtained after roasting and cooling;
then adding a binder into the ground powder for granulation;
the material obtained by pelleting is pressed into a ceramic blank with the required shape and size under the pressure of 10 MPa-20 MPa.
The binder in the ceramic body can be removed by high-temperature heat treatment before sintering, for example, plastic discharge is carried out for 5 hours at 550 ℃. Electrodes connected with the ceramic sheet are formed on the sintered ceramic sheet, for example, silver electrodes are formed by coating conductive silver paste, and the thermistor is obtained.
The CaCu 3Ti4- xMxO12 -based nano powder material with a single-phase structure and controllable particle size can be prepared by adopting the preparation method, so that the obtained CaCu 3Ti4-xMxO12 thermistor has uniform chemical components, narrow ceramic grain size distribution and single-phase structure, and can well overcome the defect of non-ideal product performance consistency caused by non-uniformity of chemical components and non-uniformity of microstructures of a mixture.
The embodiments of the present application will be further described with reference to the following examples.
Example 1: caCu 3Ti4O12 thermistor and preparation thereof
(1) Preparing aqueous solution containing Ca 2+、Cu2+ ions
The water-soluble calcium salt and the water-soluble copper salt are metered according to the stoichiometric ratio of CaCu 3Ti4O12, the metered water-soluble calcium salt and water-soluble copper salt are dissolved in deionized water, and the mixture is mixed and stirred at normal pressure and room temperature until the mixed solution is in a clear and transparent state, so that an aqueous solution with the concentration of Ca 2+ of 0.05M and the concentration of Cu 2+ of 0.15M is formed.
(2) Preparing a solution containing a metal Ti 4+ ion complex
Tetrabutyl titanate is used as a solute, a mixed solution of glacial ethanol and absolute ethanol is used as a solvent, the mixture reacts at normal temperature and normal pressure to form a clear and transparent solution, and a proper amount of acetylacetone stabilizing solution is added; the reaction is carried out at normal temperature and normal pressure to form a complex solution with the metal Ti 4+ ion concentration of 0.2M.
(3) Preparation of CaCu 3Ti4O12 precursor solution
Mixing the aqueous solution containing Ca 2+、Cu2+ ions and the complex solution containing Ti 4+ ions, stirring and mixing at normal pressure and 25 ℃ for 15 minutes, and then standing for 40 minutes to obtain a stable CaCu 3Ti4O12 precursor solution.
(4) Adding monomer and adhesive
Adding monomer acrylamide and a cross-linking agent N, N ' -methylene bisacrylamide into the CaCu 3Ti4O12 precursor solution, stirring and mixing until the monomer acrylamide and the cross-linking agent N, N ' -methylene bisacrylamide are completely dissolved to obtain a transparent solution, wherein the volume of the solution and the amount of the monomer acrylamide and the cross-linking agent N, N ' -methylene bisacrylamide in the solution are 100ml of the CaCu 3Ti4O12 precursor solution, the mass of the N, N ' -methylene bisacrylamide is 2.03g, and the molar ratio of the N, N ' -methylene bisacrylamide to the acrylamide is 1:4.5.
(5) Initiating polymerization reaction by adding initiator
In the above solution, azobisisobutyronitrile was added as an initiator for polymerization, and the temperature was raised to 70℃in an oil bath under normal pressure, and the process was continuously stirred. After 10 minutes the polymerization was completed, resulting in a blue gel. The amount of initiator azobisisobutyronitrile is: the mass of the initiator azobisisobutyronitrile in 100ml of CaCu 3Ti4O12 precursor solution was (mass of N, N' -methylenebisacrylamide + mass of acrylamide) ×10%.
(6) Drying and roasting CaCu 3Ti4O12 precursor wet gel
Drying the CaCu 3Ti4O12 precursor wet gel obtained in the step (5) to obtain xerogel, then placing the xerogel into a sintering furnace, heating the xerogel from room temperature to 800 ℃ in an air atmosphere at normal pressure, and carrying out heat preservation and roasting for 3 hours, and cooling the xerogel to room temperature along with the furnace after roasting is finished to obtain the pure body-centered cubic perovskite-like CaCu 3Ti4O12 nanometer micropowder.
(7) Preparation of thermistor
Fully grinding CaCu 3Ti4O12 nanometer powder, adding adhesive for granulation, and pressing under 20Mpa pressure to obtain ceramic embryo with diameter of 0.8cm and thickness of 0.5 cm. And (3) plastic is discharged at 550 ℃ for 5 hours, and finally the CaCu 3Ti4O12 thermistor is obtained after sintering at 1050 ℃ for 3 hours. Silver electrodes are respectively prepared on two sides of the sintered ceramic plate.
The results of the resistance temperature characteristics of the CaCu 3Ti4O12 thermistor prepared in this example are shown in Table 1.
Example 2: caCu 3Ti3.7Al0.3O12 thermistor and preparation thereof
(1) The water-soluble calcium salt, the water-soluble copper salt and the water-soluble yttrium salt are metered according to the stoichiometric ratio of CaCu 3Ti3.7Al0.3O12, the metered water-soluble calcium salt, the water-soluble copper salt and the water-soluble yttrium salt are dissolved in deionized water, and the mixture is mixed and stirred under normal pressure and a greenhouse until the mixture is in a clear and transparent state, so that 50mL of an aqueous solution with the concentration of Ca 2+ of 0.05 and M, cu 2+ of 0.15M and the concentration of Al 3+ of 0.015M is formed.
(2) Preparing a solution containing a metal Ti 4+ ion complex: tetrabutyl titanate is used as a solute, a mixed solution of glacial ethanol and absolute ethanol is used as a solvent, the mixture reacts at normal temperature and normal pressure to form a clear and transparent solution, and a proper amount of acetylacetone stabilizing solution is added; the reaction was carried out at normal temperature and normal pressure to form 50mL of a complex solution of metal Ti 4+ having an ion concentration of 0.185M.
(3) Preparation of CaCu 3Ti3.7Al0.3O12 precursor solution
Mixing the aqueous solution containing Ca 2+、Cu2+、Fe3+ ions and the complex solution containing Ti 4+ ions, stirring and mixing at normal pressure and 20 ℃ for 15 minutes, and then standing for 40 minutes to obtain a stable CaCu 3Ti3.7Al0.3O12 precursor solution.
(4) Adding monomer and adhesive
Adding monomer acrylamide and a cross-linking agent N, N ' -methylene bisacrylamide into the CaCu 3Ti3.7Al0.3O12 precursor solution, stirring and mixing until the monomer acrylamide and the cross-linking agent N, N ' -methylene bisacrylamide are completely dissolved to obtain a transparent solution, wherein the volume of the solution and the amount of the monomer acrylamide and the cross-linking agent N, N ' -methylene bisacrylamide in the solution are 100mL of the CaCu 3Ti3.7Al0.3O12 precursor solution, the mass of the N, N ' -methylene bisacrylamide is 2.03g, and the molar ratio of the N, N ' -methylene bisacrylamide to the acrylamide is 1:4.
(5) Initiating polymerization reaction by adding initiator
In the above solution, azobisisobutyronitrile was added as an initiator for polymerization, and the temperature was raised to 70℃in an oil bath under normal pressure, and the process was continuously stirred. After 10 minutes the polymerization was completed, resulting in a blue gel. The amount of initiator azobisisobutyronitrile is: the mass of the initiator azobisisobutyronitrile in 100mL of the precursor solution of CaCu 3Ti3.7Al0.3O12 was (mass of N, N' -methylenebisacrylamide + mass of acrylamide) ×15%.
(6) Drying and roasting CaCu 3Ti3.7Al0.3O12 precursor wet gel
Drying the CaCu 3Ti3.7Al0.3O12 precursor wet gel obtained in the step (5) to obtain xerogel, then placing the xerogel into a sintering furnace, heating from room temperature to 750 ℃ in an air atmosphere at normal pressure, and roasting for 3 hours, and cooling to room temperature along with the furnace after roasting is finished to obtain the pure body-centered cubic perovskite-like CaCu 3Ti3.7Al0.3O12 nanometer micropowder.
(7) Preparation of thermistor
Fully grinding CaCu 3Ti3.7Al0.3O12 nanometer powder, adding adhesive for granulation, and pressing under 20Mpa pressure to obtain ceramic embryo with diameter of 0.8cm and thickness of 0.5 cm. And (3) plastic is discharged at 550 ℃ for 5 hours, and finally the material is sintered at 1100 ℃ for 3 hours, so as to obtain the CaCu 3Ti3.7Al0.3O12 thermistor. Silver electrodes are respectively prepared on two sides of the sintered ceramic plate.
The results of the resistance temperature characteristics of the CaCu 3Ti3.7Al0.3O12 thermistor prepared in this example are shown in Table 1.
Example 3: caCu 3Ti3.4 Al0.3Y0.3O12 thermistor and preparation thereof
(1) The water-soluble calcium salt, the water-soluble copper salt, the water-soluble aluminum salt and the water-soluble yttrium salt are metered according to the stoichiometric ratio of CaCu 3Ti3.4 Al0.3Y0.3O12, the metered water-soluble calcium salt, the water-soluble copper salt, the water-soluble aluminum salt and the water-soluble yttrium salt are dissolved in deionized water, and the mixture is mixed and stirred at normal pressure and room temperature until the mixture is in a clear and transparent state, thus forming 50mL of aqueous solution with 0.05-M, cu 2+ concentration Ca 2+, 0.15-M, al 3+ and 0.015-M concentration Y 3+.
(2) Preparing a solution containing a metal Ti 4+ ion complex
Tetrabutyl titanate is used as a solute, a mixed solution of glacial ethanol and absolute ethanol is used as a solvent, the mixture reacts at normal temperature and normal pressure to form a clear and transparent solution, and a proper amount of acetylacetone stabilizing solution is added. The reaction was carried out at normal temperature and normal pressure to form 50mL of a complex solution of metal Ti 4+ having an ion concentration of 0.17M.
(3) Preparation of CaCu 3Ti3.4 Al0.3Y0.3O12 precursor solution
Mixing the aqueous solution containing Ca 2+、Cu2+、Al3+、Y3+ ions and the complex solution containing Ti 4+ ions, stirring and mixing at normal pressure and 30 ℃ for 15 minutes, and then standing for 40 minutes to obtain a stable CaCu 3Ti3.4Al0.3Y0.3O12 precursor solution.
(4) Adding monomer and adhesive
Adding monomer acrylamide and a cross-linking agent N, N ' -methylene bisacrylamide into the CaCu 3Ti3.4Al0.3Y0.3O12 precursor solution, stirring and mixing until the monomer acrylamide and the cross-linking agent N, N ' -methylene bisacrylamide are completely dissolved to obtain a transparent solution, wherein the volume of the solution and the amount of the monomer acrylamide and the cross-linking agent N, N ' -methylene bisacrylamide in the solution are 100ml of the CaCu 3Ti3.4 Al0.3Y0.3O12 precursor solution, the mass of the N, N ' -methylene bisacrylamide is 2.03g, and the molar ratio of the N, N ' -methylene bisacrylamide to the acrylamide is 1:4.
(5) Initiating polymerization reaction by adding initiator
In the above solution, azobisisobutyronitrile was added as an initiator for polymerization, and the temperature was raised to 70℃in an oil bath under normal pressure, and the process was continuously stirred. After 10 minutes the polymerization was completed, resulting in a blue gel. The amount of initiator azobisisobutyronitrile is: the mass of the initiator azobisisobutyronitrile in 100mL of the precursor solution of CaCu 3Ti3.4 Al0.3Y0.3O12 was (mass of N, N' -methylenebisacrylamide + mass of acrylamide) ×15%.
(6) Drying and roasting CaCu 3Ti3.4 Al0.3Y0.3O12 precursor wet gel
Drying the CaCu 3Ti3.4 Al0.3Y0.3O12 precursor wet gel obtained in the step (5) to obtain xerogel, then placing the xerogel into a sintering furnace, heating the xerogel from room temperature to 650 ℃ in an air atmosphere at normal pressure, and roasting for 3 hours, and cooling the xerogel to room temperature along with the furnace after roasting is finished to obtain the pure body-centered cubic perovskite-like CaCu 3Ti3.4 Al0.3Y0.3O12 nanometer micropowder.
(7) Preparation of thermistor
Fully grinding CaCu 3Ti3.4 Al0.3Y0.3O12 nanometer powder, adding adhesive for granulation, and pressing under 20Mpa pressure to obtain ceramic embryo with diameter of 0.8cm and thickness of 0.5 cm. And (3) plastic is discharged at 550 ℃ for 5 hours, and finally the material is sintered at 1000 ℃ for 3 hours, so as to obtain the CaCu 3Ti3.4 Al0.3Y0.3O12 thermistor. Silver electrodes are respectively prepared on two sides of the sintered ceramic plate.
The results of the resistance temperature characteristics of the CaCu 3Ti3.4 Al0.3Y0.3O12 thermistor prepared in this example are shown in Table 1.
Example 4: caCu 3Ti3.95Zr0.05O12 thermistor and preparation thereof
(1) The water-soluble calcium salt, the water-soluble zirconium salt and the water-soluble copper salt are metered according to the stoichiometric ratio of CaCu 3Ti3.95Zr0.05O12, the metered water-soluble calcium salt, the water-soluble zirconium salt and the water-soluble copper salt are dissolved in deionized water, and are mixed and stirred at normal pressure and room temperature until the mixed solution is in a clear and transparent state, so that the calcium with the concentration of Ca 2+ of 0.02 and M, cu 2+ and the water solution with the concentration of Zr 4+ of 0.001M are formed.
(2) Preparing a solution containing a metal Ti 4+ ion complex
Tetrabutyl titanate is used as a solute, a mixed solution of glacial ethanol and absolute ethanol is used as a solvent, the mixture reacts at normal temperature and normal pressure to form a clear and transparent solution, and a proper amount of acetylacetone stabilizing solution is added. The reaction is carried out at normal temperature and normal pressure to form a complex solution with the metal Ti 4+ ion concentration of 0.079M.
(3) Preparation of CaCu 3Ti3.95Zr0.05O12 precursor solution
Mixing the aqueous solution containing Ca 2+、Cu2+、Zr4+ ions and the complex solution containing Ti 4+ ions, stirring and mixing at normal pressure and 40 ℃ for 20 minutes, and then standing for 40 minutes to obtain a stable CaCu 3Ti3.95Zr0.05O12 precursor solution.
(4) Adding monomer and adhesive
Then adding monomer acrylamide and a cross-linking agent N, N ' -methylene bisacrylamide into the CaCu 3Ti3.95Zr0.05O12 precursor solution, stirring and mixing until the monomer acrylamide and the cross-linking agent N, N ' -methylene bisacrylamide are completely dissolved to obtain a transparent solution, wherein the volume of the solution and the amount of the monomer acrylamide and the cross-linking agent N, N ' -methylene bisacrylamide in the solution are 100ml of CaCu 3Ti3.95Zr0.05O12 precursor solution, the mass of the N, N ' -methylene bisacrylamide is 2.13g, and the molar ratio of the N, N ' -methylene bisacrylamide to the acrylamide is 1:3.
(5) Initiating polymerization reaction by adding initiator
In the above solution, azobisisobutyronitrile was added as an initiator for polymerization, and the temperature was raised to 60℃in an oil bath under normal pressure, and the process was continuously stirred. After 10 minutes the polymerization was completed, resulting in a blue gel. The amount of initiator azobisisobutyronitrile is: the mass of the initiator azobisisobutyronitrile in 100ml of CaCu 3Ti3.95Zr0.05O12 precursor solution was (mass of N, N' -methylenebisacrylamide + mass of acrylamide) ×10%.
(6) Drying and roasting CaCu 3Ti3.95Zr0.05O12 precursor wet gel
Drying the CaCu 3Ti4O12 precursor wet gel obtained in the step (5) to obtain xerogel, then placing the xerogel into a sintering furnace, heating from room temperature to 750 ℃ in an air atmosphere at normal pressure, and roasting for 3 hours, and cooling to room temperature along with the furnace after roasting is finished to obtain the pure body-centered cubic perovskite-like CaCu 3Ti3.95Zr0.05O12 nanometer micropowder.
(7) Preparation of thermistor
Fully grinding CaCu 3Ti3.95Zr0.05O12 nanometer powder, adding adhesive for granulation, and pressing under 15Mpa pressure to obtain ceramic embryo with diameter of 0.8cm and thickness of 0.5 cm. And (3) plastic is discharged at 550 ℃ for 5 hours, and finally the CaCu 3Ti3.95Zr0.05O12 thermistor is obtained after sintering at 1050 ℃ for 3 hours. Silver electrodes are respectively prepared on two sides of the sintered ceramic plate.
The results of the resistance temperature characteristics of the CaCu 3Ti3.95Zr0.05O12 thermistor prepared in this example are shown in Table 1.
Example 5: caCu 3Ti3.95Mn0.05O12 thermistor and preparation thereof
(1) The water-soluble calcium salt, the water-soluble manganese salt and the water-soluble copper salt are metered according to the stoichiometric ratio of CaCu 3Ti3.95Mn0.05O12, the metered water-soluble calcium salt, water-soluble manganese salt and water-soluble copper salt are dissolved in deionized water, and are mixed and stirred at normal pressure and 25 ℃ until the mixed solution is in a clear and transparent state, so that an aqueous solution with the concentration of Ca 2+ of 0.02 and M, cu 2+ of 0.06M and the concentration of Mn 2+ of 0.01M is formed.
(2) Preparing a solution containing a metal Ti 4+ ion complex
Tetrabutyl titanate is used as a solute, a mixed solution of glacial ethanol and absolute ethanol is used as a solvent, the mixture reacts at normal temperature and normal pressure to form a clear and transparent solution, and a proper amount of acetylacetone is added to stabilize the solution; the reaction is carried out at normal temperature and normal pressure to form a complex solution with the metal Ti 4+ ion concentration of 0.079M.
(3) Preparation of CaCu 3Ti3.95Mn0.05O12 precursor solution
Mixing the aqueous solution containing Ca 2+、Cu2+ ions and the complex solution containing Ti 4+ ions, stirring and mixing at normal pressure and 25 ℃ for 15 minutes, and then standing for 40 minutes to obtain a stable CaCu 3Ti3.95Mn0.05O12 precursor solution.
(4) Adding monomer and adhesive
Adding monomer acrylamide and a cross-linking agent N, N ' -methylene bisacrylamide into the CaCu 3Ti3.95Mn0.05O12 precursor solution, stirring and mixing until the monomer acrylamide and the cross-linking agent N, N ' -methylene bisacrylamide are completely dissolved to obtain a transparent solution, wherein the volume of the solution and the amount of the monomer acrylamide and the cross-linking agent N, N ' -methylene bisacrylamide in the solution are 100mL of the CaCu 3Ti3.95Mn0.05O12 precursor solution, the mass of the N, N ' -methylene bisacrylamide is 2.13g, and the molar ratio of the N, N ' -methylene bisacrylamide to the acrylamide is 1:4.
(5) Initiating polymerization reaction by adding initiator
In the above solution, azobisisobutyronitrile was added as an initiator for polymerization, and the temperature was raised to 60℃in an oil bath under normal pressure, and the process was continuously stirred. After 10 minutes the polymerization was completed, resulting in a blue gel. The amount of initiator azobisisobutyronitrile is: the mass of the initiator azobisisobutyronitrile in 100mL of the precursor solution of CaCu 3Ti3.95Mn0.05O12 was (mass of N, N' -methylenebisacrylamide + mass of acrylamide) ×15%.
(6) Drying and roasting CaCu 3Ti3.95Mn0.05O12 precursor wet gel
Drying the CaCu 3Ti3.95Mn0.05O12 precursor wet gel obtained in the step (5) to obtain xerogel, then placing the xerogel into a sintering furnace, heating the xerogel from room temperature to 850 ℃ in an air atmosphere at normal pressure, and roasting for at least 3 hours, and cooling the xerogel to room temperature along with the furnace after roasting is finished to obtain the pure body-centered cubic perovskite-like CaCu 3Ti3.95Mn0.05O12 nanometer micropowder.
(7) Preparation of thermistor
Fully grinding CaCu 3Ti3.95Mn0.05O12 nanometer powder, adding adhesive for granulation, and pressing under 15Mpa pressure to obtain ceramic embryo with diameter of 0.8cm and thickness of 0.5 cm. And (3) plastic is discharged at 550 ℃ for 5 hours, and finally the CaCu 3Ti3.95Mn0.05O12 thermistor is obtained after sintering at 1050 ℃ for 3 hours. Silver electrodes are respectively prepared on two sides of the sintered ceramic plate.
The results of the resistance temperature characteristics of the CaCu 3Ti3.95Mn0.05O12 thermistor prepared in this example are shown in Table 1.
TABLE 1
As can be seen from examples 1 to 5, the CaCu 3Ti4-xMxO12 thermistor of the present application has a relatively high room temperature resistivity of 10 7 Ω & cm or more and a relatively high B constant of 5000 or more.
It should be noted that the above is only a specific embodiment of the present application, but the scope of the present application is not limited thereto, and any person skilled in the art can easily think about changes or substitutions within the technical scope of the present application, and the changes or substitutions are covered by the scope of the present application; the embodiments of the present application and features in the embodiments may be combined with each other without conflict. Therefore, the protection scope of the application is subject to the protection scope of the claims.
Claims (13)
1. The heat-sensitive ceramic material is characterized in that the heat-sensitive ceramic material is CaCu 3Ti4O12 with a body-centered cubic perovskite-like structure doped with metal M, the molecular formula is CaCu 3Ti4-xMxO12, M is selected from at least two of Y, al, zr, mn, x is more than 0 and less than or equal to 0.6, the heat-sensitive ceramic material has a negative temperature coefficient characteristic in a temperature range of-50 ℃ to 300 ℃, and the B constant of the heat-sensitive ceramic material is 5000K to 8000K.
2. The thermal ceramic material of claim 1, wherein the thermal ceramic material has a room temperature resistivity of 10 7Ω·cm～109 Ω -cm.
3. A method of preparing the thermal sensitive ceramic material of claim 1, comprising:
Preparing an aqueous solution containing Ca 2+、Cu2+ and a doping ion M, wherein the doping ion M is selected from at least two of Y 3+、Al3+、Zr4+、Mn2+, and preparing a solution containing Ti 4+ ion complex;
Mixing and stirring the aqueous solution and the solution containing the Ti 4+ ion complex to obtain a precursor solution;
adding a monomer compound and a cross-linking agent into the precursor solution, and stirring;
continuously adding an initiator into the precursor solution to initiate the monomer compound and the cross-linking agent to carry out polymerization reaction so as to obtain blue gel;
drying the blue gel to obtain xerogel;
And (3) placing the xerogel into a sintering furnace for roasting, wherein the sintering furnace is heated to 650-850 ℃ from room temperature, and the CaCu 3Ti4-xMxO12 powder is obtained, wherein x is more than 0 and less than or equal to 0.6.
4. The method of preparing a thermosensitive ceramic material according to claim 3, wherein preparing an aqueous solution containing Ca 2+、Cu2+ and doped ions and preparing a solution containing Ti 4+ ion complex comprises: the water-soluble calcium salt, the water-soluble copper salt, the water-soluble ion-doped salt and the Ti 4+ ion complex are metered according to the stoichiometric ratio of CaCu 3Ti4-xMxO12, the metered water-soluble calcium salt, the water-soluble copper salt and the water-soluble ion-doped salt are dissolved in deionized water, and the metered Ti 4+ ion complex is dissolved in an organic solvent.
5. The method according to claim 4, wherein in the step of preparing the solution containing the Ti 4+ ion complex, the Ti 4+ ion complex is tetrabutyl titanate, the organic solvent is a mixed solution of glacial ethanol and absolute ethanol, and a proper amount of acetylacetone is added.
6. The method of producing a heat-sensitive ceramic material according to claim 3, wherein in the step of adding a monomer compound and a crosslinking agent to the precursor solution, the monomer compound is acrylamide, the crosslinking agent is N, N' -methylenebisacrylamide, and the amount of the crosslinking agent added to the precursor solution is: the mass of the cross-linking agent in each 100ml of precursor solution is 2.03 g-2.13 g, and the molar ratio of the cross-linking agent to the monomer compound is 1: (3-4.5).
7. The method for preparing a thermal sensitive ceramic material according to claim 3, wherein the initiator is azobisisobutyronitrile, and the initiator is added in an amount of: the mass of the initiator in each 100ml of the precursor solution is 10-20% of the total mass of the monomer compound and the crosslinking agent.
8. The method for producing a heat-sensitive ceramic material according to claim 3, wherein the temperature of the sintering furnace is raised to 650 ℃ to 850 ℃ at a temperature-raising rate of 3 ℃/min to 6 ℃/min, and the time of heat-retaining calcination is at least 3 hours at 650 ℃ to 850 ℃.
9. A method of producing a thermal ceramic material according to claim 3, further comprising: pressing the CaCu 3Ti4-xMxO12 powder into a ceramic blank, and sintering the ceramic blank for 2-3 hours at 950-1100 ℃.
10. The method of producing a heat-sensitive ceramic material according to claim 9, wherein forming the ceramic body comprises grinding the CaCu 3Ti4-xMxO12 powder, adding a binder for granulation, and pressing the granulated powder under a pressure of 10MPa to 20MPa to form the ceramic body.
11. The method of claim 10, wherein the binder in the ceramic body is removed by heating prior to sintering the ceramic body.
12. A thermosensitive ceramic material, characterized in that it is produced by the production method according to any one of claims 3 to 11.
13. A thermistor comprising a ceramic sheet and electrodes connecting the ceramic sheet, characterized in that the ceramic sheet comprises a heat sensitive ceramic material according to any one of claims 1,2 and 12.
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