CN110423112B - Double-perovskite phase composite thermistor material with adjustable temperature zone and B value and preparation method thereof - Google Patents

Double-perovskite phase composite thermistor material with adjustable temperature zone and B value and preparation method thereof Download PDF

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CN110423112B
CN110423112B CN201910728850.6A CN201910728850A CN110423112B CN 110423112 B CN110423112 B CN 110423112B CN 201910728850 A CN201910728850 A CN 201910728850A CN 110423112 B CN110423112 B CN 110423112B
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张惠敏
桑旭
常爱民
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Xinjiang Technical Institute of Physics and Chemistry of CAS
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Abstract

The invention discloses a double perovskite phase composite thermistor material with an adjustable temperature zone and B value and a preparation method thereof. Compared with the existing material, the composite thermistor material can accurately adjust the B value, the temperature measurement interval and the resistivity of a material system by adjusting X, Y, the molar ratio of the chemical general formula and the sintering temperature, and the electrical property parameters are as follows: b is25/50=4422.910 K‑2527.529 K，ρ25℃The temperature range is-100-550 ℃ and the temperature range is-26.02M omega-cm-234 omega-cm. The material solves the problem that the B value is difficult to adjust within 30K; the measurement temperature zone is difficult to change greatly; the repeatability of the material is poor; uneven distribution of manganese ions in crystal lattices and the like. The material has excellent linear relation and can be applied to the fields of temperature measurement and surge suppression.

Description

Double-perovskite phase composite thermistor material with adjustable temperature zone and B value and preparation method thereof
Technical Field
The invention relates to a double perovskite phase composite thermistor material with an adjustable temperature zone and B value and a preparation method thereof. The novel material relates to the field of semiconductor carrier transmission, and is applied to the fields of temperature measurement, surge suppression and the like.
Background
NTC thermistors have been studied and developed for a long time and are roughly classified into two types of structures, namely, a spinel structure and a perovskite structure. Co-Mn-Ni-O is the most common material system for spinel configurations, however, due to the non-uniform distribution of valence states of manganese ions in the spinel phase. The B value of NTC temperature measuring elements made of the same material in the market at present is difficult to be regulated within 30K, and the regulation range of the B value by doping the same material system is generally more than 50K. Most manufacturers adopt the following three methods in order to refine the adjustment of the B value: (1) altering the material system; (2) each link in the production is strictly controlled; (3) the relevant parameters were found by batch preparation. The three methods all increase the production cost of the NTC thermistor. Meanwhile, experiments show that part of manganese in the thermistor containing manganese is still precipitated under high-temperature sintering, in order to solve the problem, firstly, oxides which have higher melting points and are difficult to decompose, absorb moisture or volatilize are selected as sintering agents, and the oxides of the manganese are doped into the sintering agents to inhibit the precipitation of the manganese.
It is well known that perovskite structures are more stable than spinel structures, with fewer voids in the crystal structure. The stability of the perovskite structure can be obtained not only from the resistance drift rate (the resistance drift rate of the barium strontium titanate and lanthanum manganate calcium-doped double perovskite phase composite material can reach six parts per million), but also from the Alexandra Navrotsky article (Chemistry of Materials, 1998, 10[10 ]]2787-. Single-phase La0.8Ca0.2MnO3A tolerance factor of 1.07, 0.125 and 0.875 mol% La, respectively0.8Ca0.2MnO3And Ba0.5Sr0.5TiO3The tolerance factor after phase recombination is 1.05, and the tolerance factor after double perovskite phase recombination is closer to 1 than that of monocalcium phase, which shows that the stability of the material can be improved by double perovskite phase recombination. Compared with the perovskite phase and the spinel phase, the composite stability is higher. Meanwhile, the double perovskite phase composite material has the characteristic of widening the temperature measurement range, the room temperature resistance of lanthanum manganate is only dozens of ohms, the application range of a temperature zone is narrow, and barium strontium titanate has extremely high dielectric constant and room temperature resistivityThe biphase recombination (the forbidden band width range is 3.2eV-3.4eV) can greatly widen the lanthanum manganate temperature zone and expand the application of the lanthanum manganate in the temperature measurement field. Meanwhile, the material characteristics are compounded by utilizing the structure additive effect and the seepage principle, and the temperature measuring interval which cannot be obtained by a single material, the fine adjustment of the B value and the improvement of the repeatability of the material are achieved by utilizing the electrical characteristics of two different materials in the composite ceramic material to make up for the deficiencies. After the double perovskite phase composite NTC thermistor is calcined, the phase structure can be accurately controlled by strictly comparing the 2 theta angle of the traditional PDF card, and the repeatability of components is improved.
Disclosure of Invention
The invention aims to provide a double perovskite phase composite thermistor material with adjustable temperature zone and B value, which is prepared from BaCO3、SrCO3、La2O3、TiO2、CaCO3And MnO2The double perovskite phase composite thermistor material is synthesized by taking the double perovskite phase composite thermistor as a raw material, and the molar ratio of the chemical general formula is as follows: ba1-XSrXTiO3:La1-YCaYMnO3The temperature zone obtained by the preparation processes of ball milling, calcining, compounding, molding, high-temperature sintering and the like and the double perovskite phase composite NTC thermistor with the adjustable B value are 0.9:0.1-0.1:0.9, wherein X is more than or equal to 0.1 and less than or equal to 0.9, and Y is more than or equal to 0.1 and less than or equal to 0.9. Compared with the existing material, the double perovskite phase composite thermistor material with the temperature zone and the adjustable B value can accurately adjust the B value, the temperature measuring interval and the resistivity of a material system by adjusting X, Y, the molar ratio of the chemical general formula and the sintering temperature, and the electrical performance parameters are as follows: b is25/50＝4422.910K-2527.529K，ρ25℃The temperature range can be adjusted to-100-550 ℃ when the temperature is 26.02M omega cm-234 omega cm. The material system solves the problem that the B value is difficult to adjust within 30K; the measurement temperature zone is difficult to change greatly; the repeatability of the material is poor; uneven distribution of manganese ions in crystal lattices and the like. The material has excellent linear relation and can be applied to the fields of temperature measurement and surge suppression.
The invention relates to a double perovskite phase composite thermistor material with adjustable temperature zone and B value, which is prepared from BaCO 3、SrCO3、La2O3、TiO2、CaCO3And MnO2The double perovskite phase composite thermistor material is synthesized by taking the double perovskite phase composite thermistor as a raw material, and the molar ratio of the chemical general formula is as follows: ba1-XSrXTiO3:La1-YCaYMnO30.9:0.1-0.1:0.9, wherein X is more than or equal to 0.1 and less than or equal to 0.9, and Y is more than or equal to 0.1 and less than or equal to 0.9.
The preparation method of the double perovskite phase composite thermistor material with the temperature zone and the B value adjustable comprises the following steps:
a. powder proportioning: according to the molar ratio of the chemical formula: ba1-XSrXTiO3:La1-YCaYMnO30.9:0.1-0.1:0.9, wherein X is more than or equal to 0.1 and less than or equal to 0.9, Y is more than or equal to 0.1 and less than or equal to 0.9, adding BaCO3-SrCO3-TiO2And La2O3-CaCO3-MnO2Respectively weighing the elements Ba-Sr-Ti and La-Ca-Mn according to the mol ratio, respectively placing the elements into polytetrafluoroethylene tanks, controlling the mixing mass ratio of agate balls, powder, dispersant absolute ethyl alcohol and acetone to be 1-4:1:1, carrying out ball milling for 8-12 h, and drying at the temperature of 100-150 ℃ to obtain BaCO3-SrCO3-TiO2Mixing the powder with La2O3-CaCO3-MnO2Mixing the powder, wherein the mixing volume ratio of the dispersant absolute ethyl alcohol to the acetone is 1:9-9: 1;
b. and (3) calcining: b, mixing the BaCO obtained in the step a3-SrCO3-TiO2Mixing the powder with La2O3-CaCO3-MnO2Mixing the powders, calcining at 800-1000 deg.C and 900-1100 deg.C for 1-4h to obtain Ba1-XSrXTiO3And La1- YCaYMnO3Powder;
c. mixing and grinding: b, calcining the powder Ba in the step b1-XSrXTiO3And La1-YCaYMnO3Regulating and controlling according to the molar ratio of 0.9:0.1-0.1:0.9 of the chemical general formula, performing two-phase compounding, adding 0.5-5 wt% of polyvinyl alcohol solution, and grinding for 2-5 h;
d. Molding: c, performing cold isostatic pressing on the powder compounded in the step c for 75-110 s under 150-220MP, and then molding;
e. and (3) sintering: putting the formed block in the step d into a material containing MnO and Mn2O3、Mn3O4、MnO2One or four kinds of Al2O3Or ZrO2Sintering the powder at the temperature of 1200-1400 ℃ for 2-6h to obtain the double perovskite phase composite thermistor material with adjustable temperature zone and B value.
The invention relates to a double perovskite phase composite thermistor material with an adjustable temperature zone and an adjustable B value, which has the following characteristics:
when X, Y, the molar ratio of the chemical formula is a certain value, the B value of the current chemical formula and the temperature measuring temperature zone can be changed by adjusting the sintering temperature. For the same chemical formula and the mixture ratio thereof, the sintering temperature is increased by 75 ℃, and the B value can be increased by 200K.
The invention has the advantages that: the double perovskite phase composition can avoid the uneven distribution of manganese ions in a crystal lattice structure, improve the stability of the crystal structure and simultaneously ensure that the B value regulation range is below 30K. The compounding of barium strontium titanate and lanthanum manganate widens the temperature range of lanthanum manganate-based phase NTC thermistor, so that the temperature reaches-100 ℃ to 550 ℃. By adjusting the molar ratio of the general chemical formula: ba1- XSrXTiO3：La1-YCaYMnO30.9: 0.1-0.1: 0.9, wherein X is more than or equal to 0.1 and less than or equal to 0.9, and Y is more than or equal to 0.1 and less than or equal to 0.9, so that the experimental precision is reduced, and the production cost is directly reduced. Meanwhile, the repeatability of the material is greatly improved, and the problem that the phase structure is difficult to control is solved.
Drawings
FIG. 1 is a graph of resistivity versus temperature for examples 5-8 of the present invention, wherein S1、S2、S3、S4Respectively and chemical formula 0.875Ba0.5Sr0.5TiO3-0.125La0.8Ca0.2MnO3、0.75Ba0.5Sr0.5TiO3-0.25La0.8Ca0.2MnO3、0.625Ba0.5Sr0.5TiO3-0.375La0.8Ca0.2MnO3、0.5Ba0.5Sr0.5TiO3-0.5La0.8Ca0.2MnO3And correspond to each other.
Detailed Description
The present invention will be described in further detail with reference to examples. Several modifications may be made without departing from the principles of the invention and these are considered to be within the scope of the invention.
Example 1
a. Powder proportioning: according to the chemical formula 0.9Ba0.9Sr0.1TiO3-0.1La0.1Ca0.9MnO3Molar ratio 0.9:0.1, X ═ 0.1, Y ═ 0.9:
mixing BaCO3-SrCO3-TiO2And La2O3-CaCO3-MnO2Respectively weighing the elements Ba-Sr-Ti and La-Ca-Mn according to the mol ratio, respectively placing the elements into polytetrafluoroethylene tanks, controlling the mixing mass ratio of agate balls to powder to the dispersing agent absolute ethyl alcohol to acetone to be 1:1:1, carrying out ball milling for 8h, and drying at the temperature of 100 ℃ to obtain BaCO3-SrCO3-TiO2Mixing the powder with La2O3-CaCO3-MnO2Mixing the powder, wherein the volume ratio of the dispersant absolute ethyl alcohol to the acetone is 1: 9;
b. and (3) calcining: b, mixing the BaCO obtained in the step a3-SrCO3-TiO2Mixing the powder with La2O3-CaCO3-MnO2Mixing the powders, calcining at 800 deg.C and 900 deg.C for 1 hr to obtain 0.9Ba0.9Sr0.1TiO3-0.1La0.1Ca0.9MnO3Powder;
c. mixing and grinding: b, calcining the powder of 0.9Ba in the step b0.9Sr0.1TiO3-0.1La0.1Ca0.9MnO3Regulating and controlling according to the molar ratio of the chemical general formula of 0.9:0.1, performing two-phase compounding, adding 0.5 wt% of polyvinyl alcohol solution, and grinding for 2 hours;
d. Molding: c, performing cold isostatic pressing on the powder compounded in the step c for 110s at 150MP, and then forming;
e. and (3) sintering: d, placing the formed block in the step d into Al containing MnO2O3Sintering the powder at 1200 ℃ for 2h to obtain a double perovskite phase composite thermistor material with an adjustable temperature zone and an adjustable B value;
preparing an electrode: coating silver paste on the front and back surfaces of the temperature zone and the double perovskite phase composite thermistor material with the adjustable B value, and sintering the material in a bell jar furnace at 800 ℃ for 60 min; the double perovskite phase negative temperature coefficient thermistor material prepared by the electrode is subjected to electrical property test, and the result is as follows: b is25/50＝4282.860K，ρ25℃＝17.48MΩ.cm。
Example 2
a. Powder proportioning: according to the chemical formula 0.8Ba0.9Sr0.1TiO3-0.2La0.1Ca0.9MnO3Molar ratio 0.8:0.2, X ═ 0.1, Y ═ 0.9:
mixing BaCO3-SrCO3-TiO2And La2O3-CaCO3-MnO2Respectively weighing the elements Ba-Sr-Ti and La-Ca-Mn according to the mol ratio, respectively placing the elements into polytetrafluoroethylene tanks, controlling the mixing mass ratio of agate balls to powder to the dispersing agent absolute ethyl alcohol to acetone to be 2:1:1, carrying out ball milling for 8h, and drying at the temperature of 100 ℃ to obtain BaCO3-SrCO3-TiO2Mixing the powder with La2O3-CaCO3-MnO2Mixing the powder, wherein the volume ratio of the dispersant absolute ethyl alcohol to the acetone is 2: 8;
b. and (3) calcining: b, mixing the BaCO obtained in the step a3-SrCO3-TiO2Mixing the powder with La2O3-CaCO3-MnO2Mixing the powders, calcining at 800 deg.C and 900 deg.C for 2 hr to obtain 0.8Ba 0.9Sr0.1TiO3-0.2La0.1Ca0.9MnO3Powder;
c. mixing and grinding: b, calcining the powder of 0.8Ba in the step b0.9Sr0.1TiO3-0.2La0.1Ca0.9MnO3Regulating and controlling according to the molar ratio of 0.8:0.2 of the chemical general formula to perform biphaseCompounding and adding 1 wt% of polyvinyl alcohol solution for grinding for 3 hours;
d. molding: c, performing cold isostatic pressing on the powder compounded in the step c for 90s under 180MP, and then forming;
e. and (3) sintering: placing the shaped block in step d into a container containing MnO and MnO2ZrO of2Sintering the powder at 1200 ℃ for 4h to obtain a double perovskite phase composite thermistor material with an adjustable temperature zone and an adjustable B value;
preparing an electrode: coating silver paste on the front and back surfaces of the temperature zone and the double perovskite phase composite thermistor material with the adjustable B value, and sintering the material in a bell jar furnace at 800 ℃ for 60 min; the double perovskite phase negative temperature coefficient thermistor material prepared by the electrode is subjected to electrical property test, and the result is as follows: b is25/50＝4079.289K，ρ25℃＝365.69KΩ.cm。
Example 3
a. Powder proportioning: according to the chemical formula 0.7Ba0.9Sr0.1TiO3-0.3La0.1Ca0.9MnO3Molar ratio 0.7:0.3, X ═ 0.1, Y ═ 0.9:
mixing BaCO3-SrCO3-TiO2And La2O3-CaCO3-MnO2Respectively weighing the elements Ba-Sr-Ti and La-Ca-Mn according to the mol ratio, respectively placing the elements into polytetrafluoroethylene tanks, controlling the mixing mass ratio of agate balls to powder to the dispersing agent absolute ethyl alcohol to acetone to be 3:1:1, carrying out ball milling for 8.5h, and drying at the temperature of 110 ℃ to obtain BaCO 3-SrCO3-TiO2Mixing the powder with La2O3-CaCO3-MnO2Mixing the powder, wherein the mixing volume ratio of the dispersant absolute ethyl alcohol to the acetone is 3: 7;
b. and (3) calcining: b, mixing the BaCO obtained in the step a3-SrCO3-TiO2Mixing the powder with La2O3-CaCO3-MnO2Mixing the powders, calcining at 800 deg.C and 900 deg.C for 4 hr to obtain 0.7Ba0.9Sr0.1TiO3-0.3La0.1Ca0.9MnO3Powder;
c. mixing and grinding: b, calcining the powder of 0.7Ba in the step b0.9Sr0.1TiO3-0.3La0.1Ca0.9MnO3Regulating and controlling according to the molar ratio of the chemical general formula of 0.7:0.3, performing two-phase compounding, adding 2 wt% of polyvinyl alcohol solution, and grinding for 4 hours;
d. molding: c, performing cold isostatic pressing on the powder compounded in the step c for 80s at 160MP, and then forming;
e. and (3) sintering: putting the formed block in the step d into a material containing MnO and Mn2O3And Mn3O4ZrO of2Sintering the powder at 1200 ℃ for 5h to obtain a double perovskite phase composite thermistor material with an adjustable temperature zone and an adjustable B value;
preparing an electrode: coating silver paste on the front and back surfaces of the temperature zone and the double perovskite phase composite thermistor material with the adjustable B value, and sintering the material in a bell jar furnace at 800 ℃ for 60 min; the double perovskite phase negative temperature coefficient thermistor material prepared by the electrode is subjected to electrical property test, and the result is as follows: b is25/50＝3222.495K，ρ25℃＝4.85KΩ.cm。
Example 4
a. Powder proportioning: according to the chemical formula 0.6Ba0.9Sr0.1TiO3-0.4La0.1Ca0.9MnO3Molar ratio 0.6:0.4, X ═ 0.1, Y ═ 0.9:
Mixing BaCO3-SrCO3-TiO2And La2O3-CaCO3-MnO2Respectively weighing the elements Ba-Sr-Ti and La-Ca-Mn according to the mol ratio, respectively placing the elements into polytetrafluoroethylene tanks, controlling the mixing mass ratio of agate balls to powder to the dispersing agent absolute ethyl alcohol to acetone to be 4:1:1, carrying out ball milling for 9h, and drying at the temperature of 110 ℃ to obtain BaCO3-SrCO3-TiO2Mixing the powder with La2O3-CaCO3-MnO2Mixing the powder, wherein the mixing volume ratio of the dispersant absolute ethyl alcohol to the acetone is 4: 6;
b. and (3) calcining: b, mixing the BaCO obtained in the step a3-SrCO3-TiO2Mixing the powder with La2O3-CaCO3-MnO2MixingCalcining the powder at 850 deg.C and 950 deg.C for 3 hr to obtain 0.6Ba0.9Sr0.1TiO3-0.4La0.1Ca0.9MnO3Powder;
c. mixing and grinding: b, calcining the powder of 0.6Ba in the step b0.9Sr0.1TiO3-0.4La0.1Ca0.9MnO3Regulating and controlling according to the molar ratio of 0.6:0.4 of the chemical general formula, performing two-phase compounding, adding 5 wt% of polyvinyl alcohol solution, and grinding for 5 hours;
d. molding: c, performing cold isostatic pressing on the powder compounded in the step c for 75s at 220MP, and then forming;
e. and (3) sintering: putting the formed block in the step d into a material containing MnO and Mn2O3、Mn3O4And MnO2Al of (2)2O3Sintering the powder at 1200 ℃ for 6h to obtain the double perovskite phase composite thermistor material with adjustable temperature zone and B value.
Preparing an electrode: coating silver paste on the front and back surfaces of the temperature zone and the double perovskite phase composite thermistor material with the adjustable B value, and sintering the material in a bell jar furnace at 800 ℃ for 60 min; the double perovskite phase negative temperature coefficient thermistor material prepared by the electrode is subjected to electrical property test, and the result is as follows: b is 25/50＝2593.082K，ρ25℃＝382.1Ω.cm。
Example 5
a. Powder proportioning: according to the chemical formula 0.875Ba0.5Sr0.5TiO3-0.125La0.8Ca0.2MnO3Molar ratio 0.875:0.125, X ═ 0.5, Y ═ 0.2:
mixing BaCO3-SrCO3-TiO2And La2O3-CaCO3-MnO2Respectively weighing the elements Ba-Sr-Ti and La-Ca-Mn according to the mol ratio, respectively placing the elements into polytetrafluoroethylene tanks, controlling the mixing mass ratio of agate balls to powder to the dispersing agent absolute ethyl alcohol to acetone to be 1:1:1, carrying out ball milling for 9.5h, and drying at the temperature of 125 ℃ to obtain BaCO3-SrCO3-TiO2Mixing the powder with La2O3-CaCO3-MnO2MixingPowder, wherein the volume ratio of the dispersant absolute ethyl alcohol to the acetone is 5: 5;
b. and (3) calcining: b, mixing the BaCO obtained in the step a3-SrCO3-TiO2Mixing the powder with La2O3-CaCO3-MnO2Mixing the powders, calcining at 850 deg.C and 950 deg.C for 1.5 hr to obtain 0.875Ba0.5Sr0.5TiO3-0.125La0.8Ca0.2MnO3Powder;
c. mixing and grinding: b, calcining the powder of 0.875Ba in the step b0.5Sr0.5TiO3-0.125La0.8Ca0.2MnO3Regulating and controlling according to the molar ratio of the chemical general formula of 0.875:0.125, performing two-phase compounding, adding 0.5 wt% of polyvinyl alcohol solution, and grinding for 5 hours;
d. molding: c, performing cold isostatic pressing on the powder compounded in the step c for 85s at 170MP, and then forming;
e. and (3) sintering: putting the formed block in the step d into a container containing Mn2O3And MnO2ZrO of2Sintering the powder at 1300 ℃ for 2h to obtain a double perovskite phase composite thermistor material with an adjustable temperature zone and an adjustable B value;
Preparing an electrode: coating silver paste on the front and back surfaces of a temperature zone and the double perovskite phase composite thermistor material with adjustable B value, and sintering in a bell jar furnace at 800 ℃ for 10 min; the double perovskite phase negative temperature coefficient thermistor material prepared by the electrode is subjected to electrical property test, and the result is B25/50＝4388.716K，ρ25℃＝26.02MΩ.cm。
Example 6
a. Powder proportioning: according to the chemical formula 0.75Ba0.5Sr0.5TiO3-0.25La0.8Ca0.2MnO3Molar ratio 0.75:0.25, X ═ 0.5, Y ═ 0.2:
mixing BaCO3-SrCO3-TiO2And La2O3-CaCO3-MnO2Respectively weighing the elements according to the mole ratio of Ba-Sr-Ti to La-Ca-Mn, respectively placing the elements into a polytetrafluoroethylene tank, and controlling agate balls, powder and dispersionMixing absolute ethyl alcohol and acetone in a mass ratio of 1.5:1:1, performing ball milling for 10 hours, and drying at the temperature of 125 ℃ to obtain BaCO3-SrCO3-TiO2Mixing the powder with La2O3-CaCO3-MnO2Mixing the powder, wherein the mixing volume ratio of the dispersant absolute ethyl alcohol to the acetone is 5: 5;
b. and (3) calcining: b, mixing the BaCO obtained in the step a3-SrCO3-TiO2Mixing the powder with La2O3-CaCO3-MnO2Mixing the powders, calcining at 900 deg.C and 1000 deg.C for 2.5 hr to obtain 0.75Ba0.5Sr0.5TiO3-0.25La0.8Ca0.2MnO3Powder;
c. mixing and grinding: b, calcining the powder of 0.75Ba in the step b0.5Sr0.5TiO3-0.25La0.8Ca0.2MnO3Regulating and controlling according to the molar ratio of the chemical general formula of 0.75:0.25, performing two-phase compounding, adding 1.5 wt% of polyvinyl alcohol solution, and grinding for 3 hours;
d. Molding: c, performing cold isostatic pressing on the powder compounded in the step c for 90s under 180MP, and then forming;
e. and (3) sintering: putting the formed block in the step d into a material containing MnO and Mn2O3And MnO2ZrO of2Sintering the powder at 1300 ℃ for 3h to obtain the double perovskite phase composite thermistor material with adjustable temperature zone and B value.
Preparing an electrode: coating silver paste on the front and back surfaces of a temperature zone and the double perovskite phase composite thermistor material with adjustable B value, and sintering in a bell jar furnace at the temperature of 830 ℃ for 30 min; the double perovskite phase negative temperature coefficient thermistor material prepared by the electrode is subjected to electrical property test, and the result is as follows: b is25/50＝4086.1858K，ρ25℃＝303.53KΩ.cm。
Example 7
a. Powder proportioning: according to the chemical formula 0.625Ba0.5Sr0.5TiO3-0.375La0.8Ca0.2MnO3Molar ratio 0.625:0.375, X ═ 0.5, Y ═ 0.2:
mixing BaCO3-SrCO3-TiO2And La2O3-CaCO3-MnO2Respectively weighing the elements Ba-Sr-Ti and La-Ca-Mn according to the mol ratio, respectively placing the elements into polytetrafluoroethylene tanks, controlling the mixing mass ratio of agate balls to powder to the dispersing agent absolute ethyl alcohol to acetone to be 2.5:1:1, carrying out ball milling for 10.5h, and drying at the temperature of 130 ℃ to obtain BaCO3-SrCO3-TiO2Mixing the powder with La2O3-CaCO3-MnO2Mixing the powder, wherein the mixing volume ratio of the dispersant absolute ethyl alcohol to the acetone is 6: 4;
b. and (3) calcining: b, mixing the BaCO obtained in the step a3-SrCO3-TiO2Mixing the powder with La 2O3-CaCO3-MnO2Mixing the powders, calcining at 900 deg.C and 1000 deg.C for 3.5 hr to obtain 0.625Ba0.5Sr0.5TiO3-0.375La0.8Ca0.2MnO3Powder;
c. mixing and grinding: b, calcining the powder of 0.625Ba in the step b0.5Sr0.5TiO3-0.375La0.8Ca0.2MnO3Regulating and controlling according to the molar ratio of the chemical general formula of 0.625:0.375, performing two-phase compounding, adding 5 wt% of polyvinyl alcohol solution, and grinding for 5 hours;
d. molding: c, performing cold isostatic pressing on the powder compounded in the step c for 110s at 220MP, and then forming;
e. and (3) sintering: putting the formed block in the step d into a container containing Mn2O3、Mn3O4And MnO2Al of (2)2O3Sintering the powder at 1300 ℃ for 5h to obtain the double-perovskite-phase composite thermistor material with adjustable temperature zone and B value.
Preparing an electrode: coating silver paste on the front and back surfaces of a temperature zone and the double perovskite phase composite thermistor material with adjustable B value, and sintering in a bell jar furnace at 860 ℃ for 10 min; the double perovskite phase negative temperature coefficient thermistor material prepared by the electrode is subjected to electrical property test, and the result is as follows: b is25/50＝3223.042K，ρ25℃＝3.21KΩ.cm。
Example 8
a. Powder proportioning: according to the chemical formula 0.5Ba0.5Sr0.5TiO3-0.5La0.8Ca0.2MnO3Molar ratio 0.5:0.5, X ═ 0.5, Y ═ 0.2:
mixing BaCO3-SrCO3-TiO2And La2O3-CaCO3-MnO2Respectively weighing the elements Ba-Sr-Ti and La-Ca-Mn according to the mol ratio, respectively placing the elements into polytetrafluoroethylene tanks, controlling the mixing mass ratio of agate balls to powder to the dispersing agent absolute ethyl alcohol to acetone to be 3.5:1:1, carrying out ball milling for 10.5h, and drying at the temperature of 130 ℃ to obtain BaCO 3-SrCO3-TiO2Mixing the powder with La2O3-CaCO3-MnO2Mixing the powder, wherein the mixing volume ratio of the dispersant absolute ethyl alcohol to the acetone is 6: 4;
b. and (3) calcining: b, mixing the BaCO obtained in the step a3-SrCO3-TiO2Mixing the powder with La2O3-CaCO3-MnO2Mixing the powders, calcining at 950 deg.C and 1050 deg.C for 4 hr to obtain 0.5Ba0.5Sr0.5TiO3-0.5La0.8Ca0.2MnO3Powder;
c. mixing and grinding: b, calcining the powder of 0.5Ba in the step b0.5Sr0.5TiO3-0.5La0.8Ca0.2MnO3Regulating and controlling according to the molar ratio of the chemical general formula of 0.5:0.5, performing two-phase compounding, adding 2.5 wt% of polyvinyl alcohol solution, and grinding for 2.5 h;
d. molding: c, performing cold isostatic pressing on the powder compounded in the step c for 95s under 190MP, and then forming;
e. and (3) sintering: placing the shaped block of step d in a container containing MnO2Al of (2)2O3Sintering the powder at 1300 ℃ for 6h to obtain the double perovskite phase composite thermistor material with adjustable temperature zone and B value.
Preparing an electrode: coating silver paste on the front and back surfaces of the double perovskite phase composite thermistor material with the temperature zone and the adjustable B value, and sintering the double perovskite phase composite thermistor material in a bell jar furnace at the temperature of 800 ℃ for 6 DEG C0 min; the double perovskite phase negative temperature coefficient thermistor material prepared by the electrode is subjected to electrical property test, and the result is as follows: b is25/50＝2627.124K，ρ25℃＝286.2Ω.cm。
Example 9
a. Powder proportioning: according to the chemical formula 0.4Ba0.1Sr0.9TiO3-0.6La0.9Ca0.1MnO3Molar ratio 0.4:0.6, X ═ 0.9, Y ═ 0.1:
Mixing BaCO3-SrCO3-TiO2And La2O3-CaCO3-MnO2Respectively weighing the elements Ba-Sr-Ti and La-Ca-Mn according to the mol ratio, respectively placing the elements into polytetrafluoroethylene tanks, controlling the mixing mass ratio of agate balls to powder to the dispersing agent absolute ethyl alcohol to acetone to be 4:1:1, carrying out ball milling for 11h, and drying at the temperature of 140 ℃ to obtain BaCO3-SrCO3-TiO2Mixing the powder with La2O3-CaCO3-MnO2Mixing the powder, wherein the mixing volume ratio of the dispersant absolute ethyl alcohol to the acetone is 7: 3;
b. and (3) calcining: b, mixing the BaCO obtained in the step a3-SrCO3-TiO2Mixing the powder with La2O3-CaCO3-MnO2Mixing the powders, calcining at 950 deg.C and 1050 deg.C for 1 hr to obtain 0.4Ba0.1Sr0.9TiO3-0.6La0.9Ca0.1MnO3Powder;
c. mixing and grinding: b, calcining the powder of 0.4Ba in the step b0.1Sr0.9TiO3-0.6La0.9Ca0.1MnO3Regulating and controlling according to the molar ratio of the chemical general formula of 0.4:0.6, performing two-phase compounding, adding 0.5 wt% of polyvinyl alcohol solution, and grinding for 2 hours;
d. molding: c, performing cold isostatic pressing on the powder compounded in the step c for 105s under 200MP, and then forming;
e. and (3) sintering: putting the formed block in the step d into a container containing Mn2O3And Mn3O4Al of (2)2O3Sintering the powder at 1400 deg.C for 2h to obtain a temperature zone and a temperature BThe value of the double perovskite phase composite thermistor material is adjustable.
Preparing an electrode: coating silver paste on the front and back surfaces of the temperature zone and the double perovskite phase composite thermistor material with the adjustable B value, and sintering the material in a bell jar furnace at the temperature of 830 ℃ for 60 min; the double perovskite phase negative temperature coefficient thermistor material prepared by the electrode is subjected to electrical property test, and the result is as follows: b is 25/50＝4422.910K，ρ25℃＝20.92MΩ.cm。
Example 10
a. Powder proportioning: according to the chemical formula 0.3Ba0.1Sr0.9TiO3-0.7La0.9Ca0.1MnO3The molar ratio is as follows: 0.3:0.7, X ═ 0.9, Y ═ 0.1:
mixing BaCO3-SrCO3-TiO2And La2O3-CaCO3-MnO2Respectively weighing the elements Ba-Sr-Ti and La-Ca-Mn according to the mol ratio, respectively placing the elements into polytetrafluoroethylene tanks, controlling the mixing mass ratio of agate balls to powder to the dispersing agent absolute ethyl alcohol to acetone to be 2.5:1:1, carrying out ball milling for 11.5h, and drying at the temperature of 150 ℃ to obtain BaCO3-SrCO3-TiO2Mixing the powder with La2O3-CaCO3-MnO2Mixing the powder, wherein the mixing volume ratio of the dispersant absolute ethyl alcohol to the acetone is 7: 3;
b. and (3) calcining: b, mixing the BaCO obtained in the step a3-SrCO3-TiO2Mixing the powder with La2O3-CaCO3-MnO2Mixing the powders, calcining at 1000 deg.C and 1100 deg.C for 2 hr to obtain 0.3Ba0.1Sr0.9TiO3-0.7La0.9Ca0.1MnO3Powder;
c. mixing and grinding: b, calcining the powder of 0.3Ba in the step b0.1Sr0.9TiO3-0.7La0.9Ca0.1MnO3Regulating and controlling according to the molar ratio of the chemical general formula of 0.3:0.7, performing two-phase compounding, adding 2 wt% of polyvinyl alcohol solution, and grinding for 3 hours;
d. molding: c, performing cold isostatic pressing on the powder compounded in the step c for 105s under 210MP, and then forming;
e. and (3) sintering: putting the formed block in the step d into a material containing MnO and Mn3O4And MnO2Al of (2)2O3Sintering the powder at 1400 ℃ for 3h to obtain a double perovskite phase composite thermistor material with an adjustable temperature zone and an adjustable B value;
Preparing an electrode: coating silver paste on the front and back surfaces of a temperature zone and the double perovskite phase composite thermistor material with adjustable B value, and sintering in a bell jar furnace at 800 ℃ for 20 min; the double perovskite phase negative temperature coefficient thermistor material prepared by the electrode is subjected to electrical property test, and the result is as follows: b is25/50＝4377.288K，ρ25℃＝602.83KΩ.cm。
Example 11
a. Powder proportioning: according to the chemical formula 0.2Ba0.1Sr0.9TiO3-0.8La0.9Ca0.1MnO3Molar ratio 0.2:0.8, X ═ 0.9, Y ═ 0.1:
mixing BaCO3-SrCO3-TiO2And La2O3-CaCO3-MnO2Respectively weighing the elements Ba-Sr-Ti and La-Ca-Mn according to the mol ratio, respectively placing the elements into polytetrafluoroethylene tanks, controlling the mixing mass ratio of agate balls to powder to the dispersing agent absolute ethyl alcohol to acetone to be 1.5:1:1, carrying out ball milling for 12h, and drying at the temperature of 100 ℃ to obtain BaCO3-SrCO3-TiO2Mixing the powder with La2O3-CaCO3-MnO2Mixing the powder, wherein the mixing volume ratio of the dispersant absolute ethyl alcohol to the acetone is 8: 2;
b. and (3) calcining: b, mixing the BaCO obtained in the step a3-SrCO3-TiO2Mixing the powder with La2O3-CaCO3-MnO2Mixing the powders, calcining at 1000 deg.C and 1100 deg.C for 3 hr to obtain 0.2Ba0.1Sr0.9TiO3-0.8La0.9Ca0.1MnO3Powder;
c. mixing and grinding: b, calcining the powder of 0.2Ba in the step b0.1Sr0.9TiO3-0.8La0.9Ca0.1MnO3Regulating and controlling according to the molar ratio of the chemical general formula of 0.2:0.8, performing two-phase compounding, adding 4.5 wt% of polyvinyl alcohol solution, and grinding for 3 hours;
d. Molding: c, performing cold isostatic pressing on the powder compounded in the step c for 75s at 150MP, and then forming;
e. and (3) sintering: putting the formed block in the step d into a material containing MnO and Mn2O3、Mn3O4And MnO2ZrO of2Sintering the powder at 1400 ℃ for 4h to obtain the double perovskite phase composite thermistor material with adjustable temperature zone and B value.
Preparing an electrode: coating silver paste on the front and back surfaces of the temperature zone and the double-perovskite-phase composite thermistor material with adjustable B value, sintering the double-perovskite-phase composite thermistor material in a bell jar furnace at 860 ℃ for 15min, and testing the electrical properties of the double-perovskite-phase negative temperature coefficient thermistor material prepared by the electrode to obtain the following parameter B25/50＝3700.293K，ρ25℃＝5.50KΩ.cm。
Example 12
a. Powder proportioning: according to the chemical formula 0.1Ba0.1Sr0.9TiO3-0.9La0.9Ca0.1MnO3Molar ratio 0.1:0.9.X ═ 0.9, Y ═ 0.1:
mixing BaCO3-SrCO3-TiO2And La2O3-CaCO3-MnO2Respectively weighing the elements Ba-Sr-Ti and La-Ca-Mn according to the mol ratio, respectively placing the elements into polytetrafluoroethylene tanks, controlling the mixing mass ratio of agate balls to powder to the dispersing agent absolute ethyl alcohol to acetone to be 1:1:1, carrying out ball milling for 12h, and drying at the temperature of 150 ℃ to obtain BaCO3-SrCO3-TiO2Mixing the powder with La2O3-CaCO3-MnO2Mixing the powder, wherein the mixing volume ratio of the dispersant absolute ethyl alcohol to the acetone is 9: 1;
b. and (3) calcining: b, mixing the BaCO obtained in the step a3-SrCO3-TiO2Mixing the powder with La 2O3-CaCO3-MnO2Mixing the powders, calcining at 1000 deg.C and 1100 deg.C for 4 hr to obtain 0.1Ba0.1Sr0.9TiO3-0.9La0.9Ca0.1MnO3Powder;
c. mixing and grinding: b, calcining the powder of 0.1Ba in the step b0.1Sr0.9TiO3-0.9La0.9Ca0.1MnO3Regulating and controlling according to the molar ratio of 0.1:0.9 of the chemical general formula, performing two-phase compounding, adding 5 wt% of polyvinyl alcohol solution, and grinding for 5 hours;
d. molding: c, performing cold isostatic pressing on the powder compounded in the step c for 110s at 220MP, and then forming;
e. and (3) sintering: putting the formed block in the step d into a container containing Mn2O3ZrO of2Sintering the powder at 1400 ℃ for 6h to obtain the double perovskite phase composite thermistor material with adjustable temperature zone and B value.
Preparing an electrode: coating silver paste on the front and back surfaces of the temperature zone and the double-perovskite-phase composite thermistor material with adjustable B value, sintering the double-perovskite-phase composite thermistor material in a bell jar furnace at 860 ℃ for 10min, and testing the electrical properties of the double-perovskite-phase negative temperature coefficient thermistor material prepared by the electrode to obtain the following parameter B25/50＝2527.529K，ρ25℃＝234Ω.cm。
The image structures of any one of the double perovskite phase composite thermistor materials with the adjustable temperature zone and the adjustable B value obtained in the embodiments 1 to 12 are all perovskite phases, the micro-morphologies of all ceramic plates show good compactness, the ceramic formation is good, the testing temperature zone is adjustable, and the B value is adjustable, and the specific expression is as follows: FIG. 1 is a graph of the relationship obtained by resistance testing and formula calculation in examples 5-8, and the temperature measurement interval can be roughly judged to be within the range of-100 deg.C to 550 deg.C by extrapolation according to the relationship curve in the process.

Claims (2)

1. A dual-perovskite phase composite thermistor material with adjustable temperature region and B value is characterized in that the material is prepared from BaCO3、SrCO3、La2O3、TiO2、CaCO3And MnO2The double perovskite phase composite thermistor material is synthesized by taking the double perovskite phase composite thermistor as a raw material, and the molar ratio of the chemical general formula is as follows: ba1-XSrXTiO3:La1-YCaYMnO30.1-0.1:0.9, wherein X is more than or equal to 0.1 and less than or equal to 0.9, and Y is more than or equal to 0.1 and less than or equal to 0.9, and the specific operation is carried out according to the following steps:
a. powder proportioning: mixing BaCO3-SrCO3-TiO2And La2O3-CaCO3-MnO2Respectively weighing the elements Ba-Sr-Ti and La-Ca-Mn according to the mol ratio, respectively placing the elements into polytetrafluoroethylene tanks, controlling the mixing mass ratio of agate balls, powder, dispersant absolute ethyl alcohol and acetone to be 1-4:1:1, carrying out ball milling for 8-12 h, and drying at the temperature of 100-150 ℃ to obtain BaCO3-SrCO3-TiO2Mixing the powder with La2O3-CaCO3-MnO2Mixing the powder, wherein the mixing volume ratio of the dispersant absolute ethyl alcohol to the acetone is 1:9-9: 1;
b. and (3) calcining: b, mixing the BaCO obtained in the step a3-SrCO3-TiO2Mixing the powder with La2O3-CaCO3-MnO2Mixing the powders, calcining at 800-1000 deg.C and 900-1100 deg.C for 1-4h to obtain Ba1-XSrXTiO3And La1-YCaYMnO3Powder;
c. mixing and grinding: b, calcining the powder Ba in the step b1-XSrXTiO3And La1-YCaYMnO3Regulating and controlling according to the molar ratio of 0.9:0.1-0.1:0.9 of the chemical general formula, performing two-phase compounding, adding 0.5-5 wt% of polyvinyl alcohol solution, and grinding for 2-5 h;
d. Molding: c, performing cold isostatic pressing on the powder compounded in the step c at the pressure of 150-220MPa for 75-110 s, and then molding;
e. and (3) sintering: putting the formed block in the step d into a material containing MnO and Mn2O3、Mn3O4、MnO2One or four kinds of Al2O3Or ZrO2Sintering the powder at the temperature of 1200-1400 ℃ for 2-6h to obtain the double perovskite phase composite thermistor material with adjustable temperature zone and B value.
2. A preparation method of a double perovskite phase composite thermistor material with an adjustable temperature zone and B value is characterized by comprising the following steps:
a. powder proportioning: according to the molar ratio of the chemical formula: ba1-XSrXTiO3:La1-YCaYMnO30.1-0.1:0.9, wherein X is more than or equal to 0.1 and less than or equal to 0.9, Y is more than or equal to 0.1 and less than or equal to 0.9, and BaCO is added3-SrCO3-TiO2And La2O3-CaCO3-MnO2Respectively weighing the elements Ba-Sr-Ti and La-Ca-Mn according to the mol ratio, respectively placing the elements into polytetrafluoroethylene tanks, controlling the mixing mass ratio of agate balls, powder, dispersant absolute ethyl alcohol and acetone to be 1-4:1:1, carrying out ball milling for 8-12 h, and drying at the temperature of 100-150 ℃ to obtain BaCO3-SrCO3-TiO2Mixing the powder with La2O3-CaCO3-MnO2Mixing the powder, wherein the mixing volume ratio of the dispersant absolute ethyl alcohol to the acetone is 1:9-9: 1;
b. and (3) calcining: b, mixing the BaCO obtained in the step a3-SrCO3-TiO2Mixing the powder with La2O3-CaCO3-MnO2Mixing the powders, calcining at 800-1000 deg.C and 900-1100 deg.C for 1-4h to obtain Ba 1-XSrXTiO3And La1-YCaYMnO3Powder;
c. mixing and grinding: b, calcining the powder Ba in the step b1-XSrXTiO3And La1-YCaYMnO3Regulating and controlling according to the molar ratio of 0.9:0.1-0.1:0.9 of the chemical general formula, performing two-phase compounding, adding 0.5-5 wt% of polyvinyl alcohol solution, and grinding for 2-5 h;
d. molding: c, performing cold isostatic pressing on the powder compounded in the step c at the pressure of 150-220MPa for 75-110 s, and then molding;
e. and (3) sintering: putting the formed block in the step d into a material containing MnO and Mn2O3、Mn3O4、MnO2One or four kinds of Al2O3Or ZrO2Sintering the powder at the temperature of 1200-1400 ℃ for 2-6h to obtain the double perovskite phase composite thermistor material with adjustable temperature zone and B value.
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