CN115849898A - 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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Abstract
The application provides a thermal sensitive ceramic material which is CaCu with a body-centered cubic perovskite structure doped with metal M 3 Ti 4 O 12 Molecular formula of CaCu 3 Ti 4‑x M x O 12 Wherein M is at least one selected from Y, al, zr and Mn, and is 0<x is 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. By adopting the preparation method, the CaCu with a single-phase structure and controllable particle size can be prepared 3 Ti 4‑x M x O 12 Based on a nano-powder material, caCu obtained therefrom 3 Ti 4‑x M x O 12 The thermistor not only has uniform chemical components and narrow ceramic grain size distribution, but also is a compound with a single phase structure, and can well overcome the defect that the product performance consistency of a mixture is not ideal due to nonuniformity of chemical components and nonuniform microstructure.
Description
Technical Field
The application relates to a thermal sensitive ceramic material, a preparation method thereof and a thermistor comprising the thermal sensitive ceramic material.
Background
A thermistor is a resistance whose resistance value changes with a change in temperature. They are classified into Positive Temperature Coefficient thermistors (PTC thermistors, i.e., positive Temperature Coefficient thermistors) and Negative Temperature Coefficient thermistors (NTC thermistors, i.e., negative Temperature Coefficient thermistors) according to their 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 transition metal oxides such as Mn, ni, fe, co, li, zn, sn, cu, and Al. With the development of motor technology and the progress of industrial technology, the defects of the current commercialized NTC thermistor material restrict the application of the components in advanced electronic systems. Firstly, most NTC thermistors are composed of a mixture of a plurality of oxides, and the volatilization temperature of part of the oxides is low, so that the NTC thermistor material is easy to have uneven chemical components in the preparation process, and particularly for small-size thermistor elements, the problems of poor product performance consistency and poor interchangeability of the NTC thermistors are finally caused; secondly, because the chemical components are not uniform and the thermistor is used in a temperature change environment for a long time, the resistance value of the thermistor is not stable easily, and the test precision can change along with the use time, so that the stability of the thermistor product is poor.
Disclosure of Invention
According to a first aspect of the embodiments of the present application, there is provided a thermal sensitive ceramic material, which is CaCu doped with metal M and having a body-centered cubic perovskite structure 3 Ti 4 O 12 Molecular formula of CaCu 3 Ti 4-x M x O 12 Wherein M is at least one selected from Y, al, zr and Mn, and is 0<x≤0.6。
The thermosensitive ceramic material has the advantages of single phase structure, good high-temperature stability and good product consistency.
In the embodiment of the application, the heat-sensitive ceramic material has negative temperature coefficient characteristics in a temperature range of-50 ℃ to 300 ℃.
Compared with the existing heat-sensitive ceramic material, the heat-sensitive ceramic material has wider working temperature range.
In an embodiment of the present application, the B constant of the thermal sensitive ceramic material is 5000 to 8000K.
The B constant of the thermosensitive ceramic material is higher than that of the existing commercial NTC material, and the high B constant can improve the sensitivity and the measurement accuracy of the negative temperature coefficient thermistor.
In the embodiment of the application, the room temperature resistivity of the heat-sensitive ceramic material is 10 7 Ω·cm～10 9 Ω·cm。
The room temperature resistivity of the thermal sensitive ceramic material is higher than that of the existing commercial NTC thermal sensitive ceramic, and the thermal sensitive ceramic material is used as a sensor for real-time temperature monitoring, particularly used for real-time monitoring of a storage battery, and has lower power consumption.
In a second aspect, the present embodiments provide a method for preparing a heat-sensitive ceramic material, including:
preparation of Ca-containing 2+ 、Cu 2+ And an aqueous solution of a doping ion M selected from Y 3+ 、Al 3+ 、Zr 4+ 、Mn 2 + And is formulated to contain Ti 4+ A solution of an ionic complex;
will be describedThe aqueous solution and the Ti-containing solution 4+ Mixing and stirring the solution of the ionic 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 perform polymerization reaction to obtain blue gel;
drying the blue gel to obtain dry gel;
the xerogel is put into a sintering furnace for roasting, the temperature of the sintering furnace is raised from room temperature to 650-850 ℃ for heat preservation, and CaCu is obtained 3 Ti 4-x M x O 12 Powder of which 0<x≤0.6。
By adopting the preparation method, the CaCu with a single-phase structure and controllable particle size can be prepared 3 Ti 4-x M x O 12 Based on a nano-powder material, caCu obtained therefrom 3 Ti 4-x M x O 12 The thermistor not only has uniform chemical components and narrow ceramic grain size distribution, but also is a compound with a single phase structure, and can well overcome the defect of non-ideal product performance consistency of a mixture caused by non-uniform chemical components and non-uniform microstructures.
In the embodiment of the present application, ca is prepared 2+ 、Cu 2+ And doping the aqueous solution of ions and preparing Ti-containing solution 4+ The solution of ionic complexes comprises: according to CaCu 3 Ti 4-x M x O 12 In a stoichiometric ratio of water-soluble calcium salt, water-soluble copper salt, water-soluble salt of a dopant ion, ti 4+ An ionic complex, dissolving the measured amounts of water-soluble calcium salt, water-soluble copper salt and water-soluble doped ion salt in deionized water, and measuring the amount of Ti 4+ The ionic complex is dissolved in an organic solvent.
In the embodiment of the present application, ti is formulated 4+ In the step of preparing a solution of an ionic complex, the Ti 4+ The ionic complex adopts tetrabutyl titanate, the organic solvent adopts a mixed solution of glacial ethanol and absolute ethanol, and a proper amount of ethyl is addedAn acylacetone.
In an embodiment of the present invention, in the step of adding a monomer compound and a cross-linking agent to the precursor solution, the monomer compound is acrylamide, the cross-linking agent is N, N' -methylenebisacrylamide, and the amount of the cross-linking 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).
In the embodiment of the present application, the initiator is azobisisobutyronitrile, and the addition amount of the initiator is: 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 cross-linking agent.
In the embodiment of the application, the heating rate of the sintering furnace when the temperature is raised to 650-850 ℃ is 3-6 ℃/min, and the time of heat preservation and sintering at 650-850 ℃ is at least 3 hours.
In an embodiment of the present application, the preparation method further comprises: subjecting the CaCu to 3 Ti 4-x M x O 12 Pressing the powder into a ceramic green body, and roasting the ceramic green body at 950-1100 ℃ for 2-3 hours.
In an embodiment of the present application, forming the ceramic body comprises forming the CaCu 3 Ti 4-x M x O 12 Grinding the powder, adding a binder for granulation, and pressing the granulated powder under the pressure of 10-20 MPa to form the ceramic blank.
In the embodiment of the present application, the binder in the ceramic body needs to be discharged by high-temperature heating before sintering the ceramic body.
In a third aspect of the embodiments of the present application, there is provided a heat-sensitive ceramic material, which is prepared by the preparation method described in the second aspect of the embodiments of the present application.
A fourth aspect of the embodiments 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 sensitive ceramic material described in the first aspect or the third aspect of the embodiments of the present application.
Drawings
FIG. 1 shows a thermal sensitive ceramic material CaCu according to an embodiment of the present application 3 Ti 3.4 Al 0.3 Y 0.3 O 12 X-ray diffraction pattern of the ceramic.
Fig. 2 is a schematic diagram of a thermistor according to an embodiment of the present application.
Fig. 3A and 3B are resistance temperature characteristic graphs of the thermal sensitive ceramic material according to the embodiment of the present application.
Description of the main elements
Thermistor 100
Electrode 20
Electrode lead 30
Detailed Description
The embodiments of the present application will be described below with reference to the drawings. The parameter ranges referred to in this application are inclusive of the endpoints unless specifically stated otherwise.
The traditional NTC thermistor is composed of a mixture of various oxides, however, in the preparation process of the NTC thermistor material, the problems of poor consistency and poor interchangeability of the product performance of the NTC thermistor are easily caused, particularly for small-size thermistor elements; secondly, because the chemical components are not uniform and the thermistor is used in a temperature change environment for a long time, the resistance value of the thermistor is not stable easily, and the test precision can change along with the prolonging of the use time, so that the stability of the thermistor product is poor.
The application provides a thermal sensitive ceramic material, which is CaCu doped with at least one of Y, al, zr and Mn 3 Ti 4 O 12 (CCTO). The thermal sensitive ceramic material has the characteristics of single phase, high thermal sensitive B constant, high room temperature resistivity, adjustable room temperature resistivity, wide working temperature, good linearity and consistency.
The molecular formula of the thermal sensitive ceramic material is CaCu 3 Ti 4-x M x O 12 Wherein M is at least one selected from Y, al, zr and Mn,and 0<x≤0.6。
As shown in fig. 1, the X-ray diffraction pattern of the thermal sensitive ceramic material shows that the thermal sensitive ceramic material has a single body-centered cubic perovskite structure. The thermosensitive ceramic material has the advantages of single phase structure, good high-temperature stability and good product consistency.
The heat-sensitive ceramic material has obvious negative temperature coefficient characteristic in the temperature range of-50-300 ℃, and ln (R/R) of the heat-sensitive ceramic material 0 ) And 1000 (T) -1 -T 0 -1 ) The relationship is shown in fig. 3A and 3B. The working temperature range of the thermal sensitive ceramic material is wider than that of the existing thermal sensitive ceramic material.
Through trace doping, the room temperature resistivity of the thermal sensitive ceramic material is 10 7 Ω·cm～10 9 The range of omega cm is adjustable, 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 existing commercial NTC thermal sensitive ceramic, and the thermal sensitive ceramic material is used as a sensor for real-time temperature monitoring, particularly used for real-time monitoring of a storage battery, and has lower power consumption. The B constant of the thermosensitive ceramic material is higher than that of the existing commercial NTC material, even the B constant is nearly doubled higher than that of the existing NTC material, and the high B constant can improve the sensitivity and the measurement accuracy of the negative temperature coefficient thermistor. In some embodiments, the thermal sensitive B of the thermal sensitive ceramic material 25/300 Constant can be up to>7000K。
As shown in fig. 2, the present application further provides a thermistor 100 using the thermal sensitive ceramic material, where the thermistor 100 includes 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, and the ceramic sheet 10 contains the thermal sensitive ceramic material. The electrodes 20 may be formed of conductive paste (e.g., conductive silver paste, conductive platinum paste) coated on the opposite surfaces of the ceramic sheet 10, respectively. The thermistor 100 can be used in a temperature sensor and 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: preparation of Ca-containing 2+ 、Cu 2+ And an aqueous solution of a dopant ion selected from the group consisting of Y 3+ 、Al 3+ 、Zr 4+ 、Mn 2+ At least one of (1).
Preparation of Ca-containing 2+ 、Cu 2+ And the step of doping the aqueous solution of ions comprises: according to CaCu 3 Ti 4-x M x O 12 The water-soluble calcium salt, the water-soluble copper salt and the water-soluble salt of the doping ion are metered according to the stoichiometric ratio, the metered water-soluble calcium salt, the metered water-soluble copper salt and the metered 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) 3 COO) 2 ·H 2 O or Ca (NO) 3 ) 2 ·4H 2 O, the water-soluble copper salt is Cu (NO) 3 ) 2 ·3H 2 O，Y 3+ The water-soluble salt of (2) is Y (NO) 3 ) 3 ·6H 2 O，Al 3+ The water-soluble salt of (2) is Al (NO) 3 ) 3 ·9H 2 O，Zr 4+ The water-soluble salt of (2) is Zr (NO) 3 )·5H 2 O，Mn 2+ The water-soluble salt of (2) is Mn (CH) 3 COO) 2 ·H 2 O, but not limited thereto.
In some embodiments, the aqueous solution is stirred at 25 ℃ to 40 ℃ under normal pressure to form Ca in a clear and transparent state 2+ The concentration is 0.01M-0.05M 2+ 0.03-0.15M concentration, and the concentration of doping ion M is less than or equal to 0.02M.
S2: preparing Ti-containing 4+ A solution of an ionic complex.
The above step is carried out according to CaCu 3 Ti 4-x M x O 12 Stoichiometric ratio of (2) to Ti 4+ Ionic complex, then Ti in a metered amount 4+ The ionic complex is mixed with an organic solvent to form a clear, homogeneous solution. In some embodiments, the Ti-containing compound 4+ Solution of ionic complex of Ti 4+ The ion concentration is 0.04M-0.2M.
In some embodiments, ti 4+ The ion complex adopts tetrabutyl titanate, the organic solvent adopts a mixed solution of glacial 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 Ti-containing 4+ A solution of an ionic complex.
S3: mixing said aqueous solution with said Ti-containing solution 4+ And mixing and stirring the solution of the ionic complex to obtain a precursor solution.
In the step S3, the raw materials are mixed and stirred at the temperature of 25 +/-15 ℃ under normal pressure for at least 15-20 minutes, and then are kept stand for at least 40 minutes to obtain stable CaCu 3 Ti 4-x M x O 12 A precursor solution.
S4: and adding a monomer compound and a cross-linking agent into the precursor solution, and stirring.
And S4, stirring and mixing to completely dissolve the monomer compound and the cross-linking agent to obtain a transparent solution.
In one embodiment, the monomer compound is acrylamide, the cross-linking agent is N, N' -methylenebisacrylamide, and the amount of the cross-linking 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).
S5: and continuously adding an initiator into the precursor solution to initiate the polymerization reaction of the monomer compound and the cross-linking agent to obtain the blue gel.
In one embodiment, the initiator used in step S5 is azobisisobutyronitrile, and the addition amount of the initiator is: 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 cross-linking agent.
The precursor solution with the monomeric compound, the cross-linking agent and the initiator added is heated to 40 ℃ to 80 ℃ under normal pressure, for example, by oil bath, and is kept stirring continuously in the process. The polymerization was complete to give a blue gel. Step S4 and step S5 effectively accelerate the process of obtaining the gel.
S6: drying the blue gel to obtain dry gel, putting the dry gel into a sintering furnace for roasting, heating the temperature from room temperature to 650-850 ℃ for heat preservation roasting to obtain doped CaCu 3 Ti 4-x M x O 12 And (3) powder.
The drying method of the blue gel is various, such as oven drying, vacuum drying, rotary evaporation drying and the like, preferably the rotary evaporation drying method, wherein a rotary evaporator is used for the rotary evaporation drying, the drying temperature is 60-80 ℃, and the drying time is at least 4h.
The temperature rising rate of the sintering furnace when the temperature rises to 650-850 ℃ is 3-6 ℃/min, and the time of heat preservation and roasting at 650-850 ℃ is at least 3 hours. And in the roasting process, the xerogel is put into a sintering furnace and roasted in the atmosphere of normal pressure and air. Cooling the roasted product to room temperature along with the furnace after roasting is finished to obtain the CaCu of the pure body-centered cubic perovskite phase 3 Ti 4- x M x O 12 And (4) nano micro powder.
S7: pressing the powder into a ceramic blank with a certain shape and size, and sintering the ceramic blank at 950-1100 ℃ for 2-3 hours. The sintering in this step is to make CaCu 3 Ti 4-x M x O 12 The powder particles densify 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 granulated material is pressed into ceramic blank with required shape and size under the pressure of 10-20 MPa.
The ceramic body can be subjected to high-temperature heat treatment to remove the binder in the ceramic body before sintering, for example, the binder is removed by plastic removal at 550 ℃ for 5 hours. Electrodes connected to the ceramic sheet are formed on the sintered ceramic sheet, and silver electrodes are formed by, for example, applying conductive silver paste, to obtain a thermistor.
By the preparation method described in the application, theThe CaCu with a single-phase structure and controllable particle size is prepared 3 Ti 4- x M x O 12 Based on a nano-powder material, caCu obtained therefrom 3 Ti 4-x M x O 12 The thermistor not only has uniform chemical components and narrow ceramic grain size distribution, but also is a compound with a single phase structure, and can well overcome the defect of non-ideal product performance consistency of a mixture caused by non-uniform chemical components and non-uniform microstructures.
The examples of the present application are further described below with reference to specific examples.
Example 1: caCu 3 Ti 4 O 12 Thermistor and its preparation
(1) Preparation of Ca-containing 2+ 、Cu 2+ Aqueous solutions of ions
According to CaCu 3 Ti 4 O 12 The water-soluble calcium salt and the water-soluble copper salt are measured according to the stoichiometric ratio, the measured water-soluble calcium salt and the measured water-soluble copper salt are dissolved in deionized water, mixed and stirred at normal pressure and room temperature until the mixed solution is in a clear and transparent state to form Ca 2+ Concentration 0.05M and Cu 2+ 0.15M aqueous solution.
(2) Preparation of Metal-containing Ti 4+ Solutions of ionic complexes
Reacting tetrabutyl titanate serving as a solute with a mixed solution of glacial ethanol and absolute ethanol serving as a solvent at normal temperature and normal pressure to form a clear and transparent solution, and adding a proper amount of acetylacetone to stabilize the solution; reacting at normal temperature and normal pressure to form metal Ti 4+ Complex solution with ion concentration of 0.2M.
(3) Preparation of CaCu 3 Ti 4 O 12 Precursor solution
Adding the above Ca 2+ 、Cu 2+ Aqueous solution of ions and Ti-containing solution 4+ Mixing the ionic complex solution, stirring and mixing at 25 ℃ under normal pressure for 15 minutes, and standing for 40 minutes to obtain stable CaCu 3 Ti 4 O 12 A precursor solution.
(4) Adding monomer and cross-linking agent
Adding monomer acrylamide and cross-linking agent N, N' -methylene bisacrylamide to the CaCu 3 Ti 4 O 12 Stirring and mixing the precursor solution until the precursor solution is completely dissolved to obtain a transparent solution, wherein the volume of the solution and the amount of monomer acrylamide and cross-linking agent N, N' -methylene bisacrylamide contained in the solution are 100ml of CaCu 3 Ti 4 O 12 The mass of N, N '-methylene-bisacrylamide in the precursor solution is 2.03g, and the molar ratio of N, N' -methylene-bisacrylamide to acrylamide is 1:4.5.
(5) Initiator is added to initiate polymerization
Adding azobisisobutyronitrile as the initiator for polymerization, heating in oil bath to 70 deg.c under normal pressure, and stirring. After 10 minutes the polymerization was complete to give a blue gel. The amount of the initiator azobisisobutyronitrile is as follows: 100ml of CaCu 3 Ti 4 O 12 The mass of the initiator azobisisobutyronitrile in the precursor solution is (mass of N, N' -methylenebisacrylamide + mass of acrylamide) × 10%.
(6)CaCu 3 Ti 4 O 12 Drying and firing of precursor wet gel
CaCu obtained in the step (5) 3 Ti 4 O 12 Drying the precursor wet gel to obtain dry gel, then putting the dry gel into a sintering furnace, heating the dry gel from room temperature to 800 ℃ in the atmosphere of normal pressure and air, keeping the temperature and roasting for 3h, and cooling the dried gel to room temperature along with the furnace after roasting is finished to obtain the pure body-centered cubic perovskite phase CaCu 3 Ti 4 O 12 And (4) nano micropowder.
(7) Preparation of thermistor
Adding CaCu 3 Ti 4 O 12 Grinding the nanometer powder, adding binder, granulating, and pressing under 20Mpa to obtain ceramic blank with diameter of 0.8cm and thickness of 0.5 cm. Removing plastic at 550 deg.C for 5 hr, and sintering at 1050 deg.C for 3 hr to obtain CaCu 3 Ti 4 O 12 A thermistor. And preparing silver electrodes on two surfaces of the sintered ceramic wafer respectively.
The true bookCaCu prepared by example 3 Ti 4 O 12 The results of the resistance temperature characteristics of the thermistor are shown in table 1.
Example 2: caCu 3 Ti 3.7 Al 0.3 O 12 Thermistor and its preparation
(1) According to CaCu 3 Ti 3.7 Al 0.3 O 12 The water-soluble calcium salt, the water-soluble copper salt and the water-soluble yttrium salt are measured according to the stoichiometric ratio, the measured water-soluble calcium salt, the measured water-soluble copper salt and the measured water-soluble yttrium salt are dissolved in deionized water, and the mixture is mixed and stirred under normal pressure and a greenhouse until the mixed solution is in a clear and transparent state to form Ca 2+ Concentration 0.05M, cu 2+ Concentration 0.15M and Al 3+ 50mL of 0.015M aqueous solution.
(2) Preparation of Metal-containing Ti 4+ Solution of ionic complex: reacting tetrabutyl titanate serving as a solute with a mixed solution of glacial ethanol and absolute ethanol serving as a solvent at normal temperature and normal pressure to form a clear and transparent solution, and adding a proper amount of acetylacetone to stabilize the solution; reacting at normal temperature and normal pressure to form metal Ti 4+ 50mL of complex solution with an ion concentration of 0.185M.
(3) Preparation of CaCu 3 Ti 3.7 Al 0.3 O 12 Precursor solution
Adding the above Ca 2+ 、Cu 2+ 、Fe 3+ Aqueous solution of ions and Ti-containing solution 4+ Mixing the ionic complex solution, stirring and mixing at 20 ℃ under normal pressure for 15 minutes, and standing for 40 minutes to obtain stable CaCu 3 Ti 3.7 Al 0.3 O 12 A precursor solution.
(4) Adding monomer and cross-linking agent
Adding monomer acrylamide and cross-linking agent N, N' -methylene bisacrylamide to the CaCu 3 Ti 3.7 Al 0.3 O 12 Stirring and mixing the precursor solution until the precursor solution is completely dissolved to obtain a transparent solution, wherein the volume of the solution and the amount of monomer acrylamide and cross-linking agent N, N' -methylene bisacrylamide in the solution are 100mL CaCu 3 Ti 3.7 Al 0.3 O 12 In the precursor solution of (A), N' -methylenedipropylenesThe mass of amide was 2.03g, the molar ratio of n, n' -methylenebisacrylamide to acrylamide was 1:4.
(5) Initiator is added to initiate polymerization
Adding azobisisobutyronitrile as the initiator for polymerization, heating in oil bath to 70 deg.c under normal pressure, and stirring. After 10 minutes the polymerization was complete to give a blue gel. The amount of the initiator azobisisobutyronitrile is as follows: 100mL CaCu 3 Ti 3.7 Al 0.3 O 12 The mass of the initiator azobisisobutyronitrile in the precursor solution is (mass of N, N' -methylenebisacrylamide + mass of acrylamide) × 15%.
(6)CaCu 3 Ti 3.7 Al 0.3 O 12 Drying and firing of precursor wet gel
CaCu obtained in the step (5) 3 Ti 3.7 Al 0.3 O 12 Drying the precursor wet gel to obtain dry gel, then putting the dry gel into a sintering furnace, heating the dry gel from room temperature to 750 ℃ in the atmosphere of normal pressure and air, keeping the temperature and roasting for 3 hours, and cooling the dried gel to room temperature along with the furnace after roasting is finished to obtain the pure body core cubic perovskite phase CaCu 3 Ti 3.7 Al 0.3 O 12 And (4) nano micro powder.
(7) Preparation of thermistor
Adding CaCu 3 Ti 3.7 Al 0.3 O 12 Grinding the nanometer powder, adding binder, granulating, and pressing under 20Mpa to obtain ceramic blank with diameter of 0.8cm and thickness of 0.5 cm. Removing plastic at 550 deg.C for 5 hr, and sintering at 1100 deg.C for 3 hr to obtain CaCu 3 Ti 3.7 Al 0.3 O 12 A thermistor. And preparing silver electrodes on two surfaces of the sintered ceramic wafer respectively.
CaCu prepared in this example 3 Ti 3.7 Al 0.3 O 12 The results of the resistance temperature characteristics of the thermistor are shown in table 1.
Example 3: caCu 3 Ti 3.4 Al 0.3 Y 0.3 O 12 Thermistor and its preparation
(1) According to CaCu 3 Ti 3.4 Al 0.3 Y 0.3 O 12 The water-soluble calcium salt, the water-soluble copper salt, the water-soluble aluminum salt and the water-soluble yttrium salt are measured according to the stoichiometric ratio, the measured water-soluble calcium salt, the measured water-soluble copper salt, the measured water-soluble aluminum salt and the measured water-soluble yttrium 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 to form Ca 2+ Concentration 0.05M, cu 2+ Concentration of 0.15M, al 3+ Concentrations of 0.015M and Y 3+ 50mL of 0.015M aqueous solution.
(2) Preparation of Metal-containing Ti 4+ Solutions of ionic complexes
Tetrabutyl titanate is used as a solute, a mixed solution of glacial ethanol and absolute ethanol is used as a solvent, the reaction is carried out 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. Reacting at normal temperature and normal pressure to form metal Ti 4+ 50mL of a complex solution having an ionic concentration of 0.17M.
(3) Preparation of CaCu 3 Ti 3.4 Al 0.3 Y 0.3 O 12 Precursor solution
Adding the above Ca 2+ 、Cu 2+ 、Al 3+ 、Y 3+ Aqueous solution of ions and Ti-containing solution 4+ Mixing the ionic complex solution, stirring and mixing at 30 ℃ under normal pressure for 15 minutes, and standing for 40 minutes to obtain stable CaCu 3 Ti 3.4 Al 0.3 Y 0.3 O 12 A precursor solution.
(4) Adding monomer and cross-linking agent
Adding monomer acrylamide and cross-linking agent N, N' -methylene bisacrylamide to the CaCu 3 Ti 3.4 Al 0.3 Y 0.3 O 12 Stirring and mixing the precursor solution until the precursor solution is completely dissolved to obtain a transparent solution, wherein the volume of the solution and the amount of monomer acrylamide and cross-linking agent N, N' -methylene bisacrylamide contained in the solution are 100ml of CaCu 3 Ti 3.4 Al 0.3 Y 0.3 O 12 The mass of N, N '-methylene-bisacrylamide in the precursor solution is 2.03g, and the molar ratio of N, N' -methylene-bisacrylamide to acrylamide is 1:4.
(5) Initiator is added to initiate polymerization
Adding azobisisobutyronitrile as the initiator for polymerization, heating in oil bath to 70 deg.c under normal pressure, and stirring. After 10 minutes the polymerization was complete to give a blue gel. The amount of the initiator azobisisobutyronitrile is as follows: 100mL of CaCu 3 Ti 3.4 Al 0.3 Y 0.3 O 12 The mass of the initiator azobisisobutyronitrile in the precursor solution of (b) is (mass of N, N' -methylenebisacrylamide + mass of acrylamide) × 15%.
(6)CaCu 3 Ti 3.4 Al 0.3 Y 0.3 O 12 Drying and firing of precursor wet gel
CaCu obtained in the step (5) 3 Ti 3.4 Al 0.3 Y 0.3 O 12 Drying the precursor wet gel to obtain dry gel, then putting the dry gel into a sintering furnace, heating from room temperature to 650 ℃ in the atmosphere of normal pressure and air, keeping the temperature 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 phase CaCu 3 Ti 3.4 Al 0.3 Y 0.3 O 12 And (4) nano micropowder.
(7) Preparation of thermistors
Adding CaCu 3 Ti 3.4 Al 0.3 Y 0.3 O 12 Grinding the nanometer powder, adding binder, granulating, and pressing under 20Mpa to obtain ceramic blank with diameter of 0.8cm and thickness of 0.5 cm. Removing plastic at 550 deg.C for 5 hr, and sintering at 1000 deg.C for 3 hr to obtain CaCu 3 Ti 3.4 Al 0.3 Y 0.3 O 12 A thermistor. And preparing silver electrodes on two surfaces of the sintered ceramic wafer respectively.
CaCu prepared in this example 3 Ti 3.4 Al 0.3 Y 0.3 O 12 The results of the resistance temperature characteristics of the thermistor are shown in table 1.
Example 4: caCu 3 Ti 3.95 Zr 0.05 O 12 Thermistor and its preparation
(1) According to CaCu 3 Ti 3.95 Zr 0.05 O 12 The water-soluble calcium salt, the water-soluble zirconium salt and the water-soluble copper salt are measured according to the stoichiometric ratio, the 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 clear and transparent to form Ca 2+ Concentration 0.02M, cu 2+ Calcium and Zr at a concentration of 0.06M 4+ 0.001M aqueous solution.
(2) Preparation of Metal-containing Ti 4+ Solutions of ionic complexes
Tetrabutyl titanate is used as a solute, a mixed solution of glacial ethanol and absolute ethanol is used as a solvent, the reaction is carried out 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. Reacting at normal temperature and normal pressure to form metal Ti 4+ Complex solution with ion concentration of 0.079M.
(3) Preparation of CaCu 3 Ti 3.95 Zr 0.05 O 12 Precursor solution
Adding the above Ca 2+ 、Cu 2+ 、Zr 4+ Aqueous solution of ions and Ti-containing solution 4+ Mixing the ionic complex solution, stirring and mixing at 40 ℃ under normal pressure for 20 minutes, and standing for 40 minutes to obtain stable CaCu 3 Ti 3.95 Zr 0.05 O 12 A precursor solution.
(4) Adding monomer and cross-linking agent
Then monomer acrylamide and cross-linking agent N, N' -methylene bisacrylamide are added into the CaCu 3 Ti 3.95 Zr 0.05 O 12 Stirring and mixing the precursor solution until the precursor solution is completely dissolved to obtain a transparent solution, wherein the volume of the solution and the amount of monomer acrylamide and cross-linking agent N, N' -methylene bisacrylamide contained in the solution are 100ml of CaCu 3 Ti 3.95 Zr 0.05 O 12 The mass of N, N '-methylene-bisacrylamide in the precursor solution is 2.13g, and the molar ratio of N, N' -methylene-bisacrylamide to acrylamide is 1:3.
(5) Initiator is added to initiate polymerization
Adding azobisisobutyronitrile as the initiator for polymerization, heating in oil bath to 60 deg.c under normal pressure and stirring. After 10 minutes the polymerization was complete to give a blue gel. The amount of the initiator azobisisobutyronitrile is as follows: 100ml of CaCu 3 Ti 3.95 Zr 0.05 O 12 The mass of the initiator azobisisobutyronitrile in the precursor solution is (mass of N, N' -methylenebisacrylamide + mass of acrylamide) × 10%.
(6)CaCu 3 Ti 3.95 Zr 0.05 O 12 Drying and firing of precursor wet gel
CaCu obtained in the step (5) 3 Ti 4 O 12 Drying the precursor wet gel to obtain dry gel, then putting the dry gel into a sintering furnace, heating the dry gel from room temperature to 750 ℃ in the atmosphere of normal pressure and air, keeping the temperature and roasting for 3 hours, and cooling the dried gel to room temperature along with the furnace after roasting is finished to obtain the pure body core cubic perovskite phase CaCu 3 Ti 3.95 Zr 0.05 O 12 And (4) nano micropowder.
(7) Preparation of thermistor
Adding CaCu 3 Ti 3.95 Zr 0.05 O 12 Grinding the nanometer powder, adding binder, granulating, and pressing under 15Mpa to obtain ceramic blank with diameter of 0.8cm and thickness of 0.5 cm. Removing plastic at 550 deg.C for 5 hr, and sintering at 1050 deg.C for 3 hr to obtain CaCu 3 Ti 3.95 Zr 0.05 O 12 A thermistor. And preparing silver electrodes on two surfaces of the sintered ceramic wafer respectively.
CaCu prepared in this example 3 Ti 3.95 Zr 0.05 O 12 The results of the resistance temperature characteristics of the thermistor are shown in table 1.
Example 5: caCu 3 Ti 3.95 Mn 0.05 O 12 Thermistor and its preparation
(1) According to CaCu 3 Ti 3.95 Mn 0.05 O 12 The water-soluble calcium salt, the water-soluble manganese salt and the water-soluble copper salt are metered in a stoichiometric ratio, and the water-soluble calcium salt, the water-soluble manganese salt and the water-soluble copper salt are metered inDissolving in deionized water, mixing at normal pressure and 25 deg.C, and stirring to obtain clear and transparent mixture containing Ca 2+ Concentration 0.02M, cu 2+ Concentration 0.06M and Mn 2+ 0.01M aqueous solution.
(2) Preparation of Metal-containing Ti 4+ Solutions of ionic complexes
Reacting tetrabutyl titanate serving as a solute with a mixed solution of glacial ethanol and absolute ethanol serving as a solvent at normal temperature and normal pressure to form a clear and transparent solution, and adding a proper amount of acetylacetone to stabilize the solution; reacting at normal temperature and normal pressure to form metal Ti 4+ Complex solution with ion concentration of 0.079M.
(3) Preparation of CaCu 3 Ti 3.95 Mn 0.05 O 12 Precursor solution
Adding the above Ca 2+ 、Cu 2+ Aqueous solution of ions and Ti-containing solution 4+ Mixing the ionic complex solution, stirring and mixing at 25 ℃ under normal pressure for 15 minutes, and standing for 40 minutes to obtain stable CaCu 3 Ti 3.95 Mn 0.05 O 12 A precursor solution.
(4) Adding monomer and cross-linking agent
Adding monomer acrylamide and cross-linking agent N, N' -methylene-bisacrylamide to the CaCu 3 Ti 3.95 Mn 0.05 O 12 Stirring and mixing the precursor solution until the precursor solution is completely dissolved to obtain a transparent solution, wherein the volume of the solution and the amount of monomer acrylamide and cross-linking agent N, N' -methylene bisacrylamide in the solution are 100mL of CaCu 3 Ti 3.95 Mn 0.05 O 12 The mass of N, N '-methylene-bisacrylamide in the precursor solution is 2.13g, and the molar ratio of N, N' -methylene-bisacrylamide to acrylamide is 1:4.
(5) Initiator is added to initiate polymerization
Adding azobisisobutyronitrile as the initiator for polymerization, heating in oil bath to 60 deg.c under normal pressure and stirring. After 10 minutes the polymerization was complete to give a blue gel. The amount of the initiator azobisisobutyronitrile is as follows: 100mL of CaCu 3 Ti 3.95 Mn 0.05 O 12 The mass of the initiator azobisisobutyronitrile in the precursor solution is (mass of N, N' -methylenebisacrylamide + mass of acrylamide) × 15%.
(6)CaCu 3 Ti 3.95 Mn 0.05 O 12 Drying and firing of precursor wet gel
CaCu obtained in the step (5) 3 Ti 3.95 Mn 0.05 O 12 Drying the precursor wet gel to obtain dry gel, then putting the dry gel into a sintering furnace, heating the dry gel from room temperature to 850 ℃ in the atmosphere of normal pressure and air, carrying out heat preservation roasting for at least 3h, and cooling the dried gel to room temperature along with the furnace after roasting is finished to obtain the pure body core cubic perovskite phase CaCu 3 Ti 3.95 Mn 0.05 O 12 And (4) nano micropowder.
(7) Preparation of thermistor
Adding CaCu 3 Ti 3.95 Mn 0.05 O 12 Grinding the nanometer powder, adding binder, granulating, and pressing under 15Mpa to obtain ceramic blank with diameter of 0.8cm and thickness of 0.5 cm. Removing plastic at 550 deg.C for 5 hr, and sintering at 1050 deg.C for 3 hr to obtain CaCu 3 Ti 3.95 Mn 0.05 O 12 A thermistor. And preparing silver electrodes on two surfaces of the sintered ceramic wafer respectively.
CaCu prepared in this example 3 Ti 3.95 Mn 0.05 O 12 The results of the resistance temperature characteristics of the thermistor are shown in table 1.
TABLE 1
As can be seen from examples 1 to 5, caCu of the present application 3 Ti 4-x M x O 12 The thermistor has a high room temperature resistivity of 10 7 Omega cm or more, and has a high B constant of 5000 or more.
It should be noted that, the above are only specific embodiments of the present application, but the protection scope of the present application is not limited thereto, and any person skilled in the art can easily think of the changes or substitutions within the technical scope of the present application, and shall cover the protection scope of the present application; in the present invention, the embodiments and features of the embodiments may be combined with each other without conflict. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.
Claims (15)
1. The thermal sensitive ceramic material is characterized by being a CaCu with a body-centered cubic perovskite structure doped with metal M 3 Ti 4 O 12 Molecular formula of CaCu 3 Ti 4-x M x O 12 Wherein M is at least one selected from Y, al, zr and Mn, and is 0<x≤0.6。
2. A heat-sensitive ceramic material according to claim 1, characterized in that it has a negative temperature coefficient characteristic in the temperature range-50 ℃ to 300 ℃.
3. The heat-sensitive ceramic material according to claim 1 or 2, wherein the B-constant of the heat-sensitive ceramic material is 5000 to 8000K.
4. The temperature-sensitive ceramic material according to any one of claims 1 to 3, wherein the temperature-sensitive ceramic material has a room temperature resistivity of 10 7 Ω·cm～10 9 Ω·cm。
5. A method for preparing a heat-sensitive ceramic material, which is characterized by comprising the following steps:
preparation of Ca-containing 2+ 、Cu 2+ And an aqueous solution of a dopant ion M selected from Y 3+ 、Al 3+ 、Zr 4+ 、Mn 2+ And is formulated to contain Ti 4+ A solution of an ionic complex;
mixing said aqueous solution with said Ti-containing solution 4+ Mixing and stirring the solution of the ionic 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 perform polymerization reaction to obtain blue gel;
drying the blue gel to obtain dry gel;
the xerogel is put into a sintering furnace for roasting, the temperature of the sintering furnace is raised from room temperature to 650-850 ℃ for heat preservation, and CaCu is obtained 3 Ti 4-x M x O 12 Powder of which 0<x≤0.6。
6. The method for preparing a heat-sensitive ceramic material according to claim 5, wherein Ca is formulated to contain 2+ 、Cu 2+ And doping the aqueous solution of ions and preparing Ti-containing solution 4+ The solution of ionic complexes comprises: according to CaCu 3 Ti 4-x M x O 12 In a stoichiometric ratio of water-soluble calcium salt, water-soluble copper salt, water-soluble salt of a dopant ion, ti 4+ An ionic complex, dissolving the water-soluble calcium salt, water-soluble copper salt and water-soluble doped ion salt in deionized water, and adding Ti 4+ The ionic complex is dissolved in an organic solvent.
7. The method for preparing a heat-sensitive ceramic material according to claim 6, wherein Ti is formulated to contain Ti 4+ In the step of preparing a solution of an ionic complex, the Ti 4+ The ionic complex adopts tetrabutyl titanate, the organic solvent adopts a mixed solution of glacial ethanol and absolute ethanol, and a proper amount of acetylacetone is added.
8. The method of any one of claims 5 to 7, wherein in the step of adding a monomer compound and a cross-linking agent to the precursor solution, the monomer compound is acrylamide and the cross-linking agent is N, N' -methylenebisacrylamide, and the amount of the cross-linking 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).
9. The method for preparing a heat-sensitive ceramic material according to any of claims 5 to 8, 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 cross-linking agent.
10. The method for preparing a heat-sensitive ceramic material according to any one of claims 5 to 9, wherein the sintering furnace is heated to 650 ℃ to 850 ℃ at a heating rate of 3 ℃/min to 6 ℃/min, and the roasting time is at least 3 hours at 650 ℃ to 850 ℃.
11. The method for preparing a heat-sensitive ceramic material according to any of claims 5 to 10, further comprising: subjecting the CaCu to 3 Ti 4-x M x O 12 Pressing the powder into a ceramic green body, and sintering the ceramic green body for 2-3 hours at 950-1100 ℃.
12. The method of claim 11, wherein forming the ceramic body comprises forming the CaCu 3 Ti 4-x M x O 12 Grinding the powder, adding a binder for granulation, and pressing the granulated powder under the pressure of 10-20 Mpa to form the ceramic blank.
13. The method for preparing a heat-sensitive ceramic material according to claim 12, wherein the binder in the ceramic body is removed by heating before sintering the ceramic body.
14. A heat-sensitive ceramic material, characterized in that it is produced by the production method according to any one of claims 5 to 13.
15. A thermistor comprising a ceramic plate and electrodes connecting the ceramic plate, characterized in that the ceramic plate comprises a temperature-sensitive ceramic material according to any of claims 1 to 4 and 14.
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