CN112876238A - Stannate system negative temperature coefficient thermistor material and preparation method thereof - Google Patents

Stannate system negative temperature coefficient thermistor material and preparation method thereof Download PDF

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CN112876238A
CN112876238A CN202110212343.4A CN202110212343A CN112876238A CN 112876238 A CN112876238 A CN 112876238A CN 202110212343 A CN202110212343 A CN 202110212343A CN 112876238 A CN112876238 A CN 112876238A
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temperature coefficient
negative temperature
coefficient thermistor
thermistor material
oxide
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高博
李晓卉
常爱民
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Xinjiang Technical Institute of Physics and Chemistry of CAS
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Abstract

The invention relates to a stannate system negative temperature coefficient thermistor material, which takes tin dioxide, lanthanum oxide, neodymium oxide, samarium oxide and gadolinium oxide as raw materials, the tin dioxide is respectively mixed with the lanthanum oxide, the neodymium oxide, the samarium oxide or the gadolinium oxide, and the stannate system material can be obtained after ball milling, drying, grinding, calcining, regrinding, cold isostatic pressing and high-temperature sintering, and the electrical performance parameters of the system material are as follows: b is400℃/1000℃=12320‑15177K，ρ1000℃=0.650‑8.095×103Omega cm. The stannate negative temperature coefficient thermistor material system prepared by the invention has obvious negative temperature coefficient characteristics within a temperature range of 400-1100 ℃, has stable electrical property, good consistency, stable aging performance and insensitivity to oxygen partial pressure, and is suitable for manufacturing thermistor materials used in high-temperature and different oxygen partial pressure environments.

Description

Stannate system negative temperature coefficient thermistor material and preparation method thereof
Technical Field
The invention relates to a stannate system negative temperature coefficient thermistor material and a preparation method thereof, the thermistor material has obvious negative temperature coefficient characteristic in the temperature range of 400-1100 ℃, is a novel thermistor suitable for manufacturing a high-temperature thermistor, and belongs to the field of semiconductor sensors.
Background
With the rapid development of scientific and technical information technology, automotive electronics and aerospace industry, there is an increasing demand for negative temperature coefficient thermistors (NTCs) having high accuracy and being applicable to high-temperature and severe environments. In recent years, perovskite-based composite materials and spinel-based composite materials are used as hot materials of high-temperature NTC thermistor materials. Although great progress has been made, the maximum temperature upper limit for most reported materials is only 800 ℃ and a few materials reach 1000 ℃. Meanwhile, most NTC thermistor materials have a resistance of only tens of ohms at a high temperature upper limit, and the resistance change range is small, so that the practical application of the NTC thermistor materials in a high-temperature environment is limited. And the materials also have the defects of poor aging characteristics, susceptibility to oxygen environment influence on electrical properties and the like. In the face of high temperature environments and high pressures and severe oxidation or corrosion caused by high temperatures, such materials are required to have high chemical and thermal stability and to be insensitive to oxygen partial pressure. Currently, most high temperature NTC thermistor materials cannot meet such requirements.
Therefore, the invention discloses a stannate system negative temperature coefficient thermistor material, which has obvious negative temperature coefficient characteristics within the temperature of 400-1100 ℃, stable electrical property, good consistency, stable aging performance and insensitivity to oxygen partial pressure, and is a thermistor material suitable for manufacturing a thermistor used in a high-temperature environment.
Disclosure of Invention
The invention aims to provide a stannate system negative temperature coefficient thermistor material and a preparation method thereofMixing lanthanum oxide, neodymium oxide, samarium oxide or gadolinium oxide, and performing ball milling, drying, grinding, calcining, re-grinding, cold isostatic pressing and high-temperature sintering to obtain a stannate system material, wherein the electrical performance parameters of the system material are as follows: b is400℃/1000℃＝12320-15177K，ρ1000℃＝0.650-8.095×103Omega cm. The stannate system negative temperature coefficient thermistor material has obvious negative temperature coefficient characteristics within a temperature range of 400-1100 ℃, has stable electrical property, good consistency, stable aging performance and insensitivity to oxygen partial pressure, and is a thermistor material suitable for manufacturing thermistors in high-temperature environments.
The invention relates to a stannate system negative temperature coefficient thermistor material, wherein the chemical general formula of the system thermistor material is as follows: a. the2Sn2O7Wherein A is La, Nd, Sm or Gd, which is formed by mixing and burning raw material tin dioxide with lanthanum oxide, neodymium oxide, samarium oxide or gadolinium oxide respectively, and the specific operation is carried out according to the following steps:
a. according to A2Sn2O7Weighing tin dioxide, mixing the tin dioxide with lanthanum oxide, neodymium oxide, samarium oxide or gadolinium oxide respectively, placing the mixture in an agate ball milling tank, wet-milling the mixture for 6 to 8 hours by using analytically pure absolute ethyl alcohol as a dispersion medium, drying the slurry after the wet milling at the temperature of 120 ℃, taking out the slurry and milling the slurry for 1 hour to obtain powder;
b. calcining the powder obtained in the step a at the temperature of 1200-1250 ℃ for 3-5h, and then grinding for 2-4h to obtain thermistor powder;
c. c, mixing the powder obtained in the step b at a ratio of 15-25kg/cm2The pressure is pressed and molded, the pressure maintaining time is 1-2min, the molded block is subjected to cold isostatic pressing, the pressure is maintained at 250-300MPa for 1-3min, and then the block is sintered for 10h at the temperature of 1600-1650 ℃ to obtain the negative temperature coefficient thermistor material of the stannate system;
d. coating platinum slurry electrodes on the front and back surfaces of the negative temperature coefficient thermistor material of the stannate system obtained in the step c, and then annealing at 900 ℃ for 1-2 hours to obtain the negative temperature coefficient thermistor materialThe electrical property parameters were: b is400℃/1000℃＝12320-15177K，ρ1000℃＝0.650-8.095×103Omega cm stannate system negative temperature coefficient thermistor material.
A method for preparing a stannate system negative temperature coefficient thermistor material comprises the following steps:
a. according to A2Sn2O7Weighing tin dioxide, mixing the tin dioxide with lanthanum oxide, neodymium oxide, samarium oxide or gadolinium oxide respectively, placing the mixture in an agate ball milling tank, wet-milling the mixture for 6 to 8 hours by using analytically pure absolute ethyl alcohol as a dispersion medium, drying the slurry after the wet milling at the temperature of 120 ℃, taking out the slurry and milling the slurry for 1 hour to obtain powder;
b. calcining the powder obtained in the step a at the temperature of 1200-1250 ℃ for 3-5h, and then grinding for 2-4h to obtain thermistor powder;
c. c, mixing the powder obtained in the step b at a ratio of 15-25kg/cm2The pressure is pressed and molded, the pressure maintaining time is 1-2min, the molded block is subjected to cold isostatic pressing, the pressure is maintained at 250-300MPa for 1-3min, and then the block is sintered for 10h at the temperature of 1600-1650 ℃ to obtain the negative temperature coefficient thermistor material of the stannate system;
d. coating platinum slurry electrodes on the front and back surfaces of the negative temperature coefficient thermistor material of the stannate system obtained in the step c, and then annealing at 900 ℃ for 1-2h to obtain the negative temperature coefficient thermistor material with the following electrical performance parameters: b is400℃/1000℃＝12320-15177K，ρ1000℃＝0.650-8.095×103Omega cm stannate system negative temperature coefficient thermistor material.
The invention relates to a stannate system negative temperature coefficient thermistor material and a preparation method thereof, analytically pure tin dioxide is respectively mixed with analytically pure lanthanum oxide, analytically pure neodymium oxide, analytically pure samarium oxide or analytically pure gadolinium oxide by a ball milling method, ball milling, drying, grinding, calcining and re-grinding are carried out, then the powder is formed by sheet type cold isostatic pressing, platinum slurry electrodes are coated on the front and back surfaces after high-temperature sintering to obtain the thermistor, the system thermistor material is A2Sn2O7Stannate, the bodyThe series electrical property parameters are as follows: b is400℃/1000℃＝12320-15177K，ρ1000℃＝0.650-8.095×103Omega cm. By changing the cation at the A position, a series of A can be obtained2Sn2O7The high-temperature negative temperature coefficient thermistor material.
The invention relates to a stannate system negative temperature coefficient thermistor material and a preparation method thereof, and the innovation points of the material are as follows:
(1) the stannate system A of the invention2Sn2O7The negative temperature coefficient thermistor material has typical NTC characteristic in a higher temperature range of 400-1100 ℃, and is stable in performance in a high-temperature environment.
(2) The resistivity of the material is hardly influenced by oxygen partial pressure, and the material can keep higher resistivity in a high-temperature environment, can reach a kiloohm level, and is beneficial to the practical application in the high-temperature environment.
The material has obvious negative temperature coefficient characteristic, and the system material has stable electrical property, good consistency, stable aging performance and insensitivity to oxygen partial pressure, and is a thermistor material suitable for manufacturing high-temperature and different oxygen partial pressure environments.
Drawings
FIG. 1 shows the present invention A2Sn2O7Graph of resistivity versus temperature for (a ═ La, Nd, Sm, Gd) materials.
FIG. 2 shows the present invention A2Sn2O7Graph of resistivity versus oxygen partial pressure for (a ═ La, Nd, Sm, Gd) materials.
Detailed Description
Example 1
a. According to La2Sn2O7Weighing tin dioxide and lanthanum oxide, mixing, placing in an agate ball milling tank, wet milling for 8h by using analytically pure absolute ethyl alcohol as a dispersion medium, drying slurry after wet milling at the temperature of 120 ℃, taking out and grinding for 1h to obtain powder;
b. calcining the powder obtained in the step a at 1200 ℃ for 4h, and grinding for 4h to obtain thermistor powder;
c. b, mixing the powder obtained in the step b at a ratio of 25kg/cm2Pressing the block to form the block, keeping the pressure for 2min, carrying out cold isostatic pressing on the formed block, keeping the pressure for 1min at the pressure of 300MPa, and then sintering the block at the temperature of 1600 ℃ for 10h to obtain the negative temperature coefficient thermistor material of lanthanum stannate;
d. coating platinum slurry electrodes on the front and back surfaces of the negative temperature coefficient thermistor material of lanthanum stannate obtained in the step c, and then annealing at 900 ℃ for 2 hours to obtain the thermistor material with the following electrical performance parameters: b is400℃/1000℃＝15177K，ρ1000℃＝1.707×103Omega cm lanthanum stannate negative temperature coefficient thermistor material.
Example 2
a. According to La2Sn2O7Weighing tin dioxide and lanthanum oxide, mixing, placing in an agate ball milling tank, wet milling for 8h by using analytically pure absolute ethyl alcohol as a dispersion medium, drying slurry after wet milling at the temperature of 120 ℃, taking out and grinding for 1h to obtain powder;
b. calcining the powder obtained in the step a at 1250 ℃ for 5 hours, and grinding for 4 hours to obtain thermistor powder;
c. b, mixing the powder obtained in the step b at a ratio of 25kg/cm2Pressing the block to form the block, keeping the pressure for 2min, carrying out cold isostatic pressing on the formed block, keeping the pressure for 2min at the pressure of 300MPa, and then sintering the block at the temperature of 1650 ℃ for 10h to obtain the negative temperature coefficient thermistor material of lanthanum stannate;
d. coating platinum slurry electrodes on the front and back surfaces of the negative temperature coefficient thermistor material of lanthanum stannate obtained in the step c, and then annealing at 900 ℃ for 2 hours to obtain the thermistor material with the following electrical performance parameters: b is400℃/1000℃＝13643K，ρ1000℃＝0.650×103Omega cm lanthanum stannate negative temperature coefficient thermistor material.
Example 3
a. According to La2Sn2O7Weighing tin dioxide and lanthanum oxide, mixing, placing in an agate ball milling tank, wet milling for 6h by using analytically pure absolute ethyl alcohol as a dispersion medium, and wet millingDrying the slurry at the temperature of 120 ℃, taking out and grinding for 1h to obtain powder;
b. calcining the powder obtained in the step a at 1200 ℃ for 3h, and grinding for 4h to obtain thermistor powder;
c. c, mixing the powder obtained in the step b at a ratio of 20kg/cm2Pressing the block body into a block under the pressure of 2min, carrying out cold isostatic pressing on the formed block body, keeping the pressure at 250MPa for 3min, and then sintering the block body at the temperature of 1600 ℃ for 10h to obtain the negative temperature coefficient thermistor material of lanthanum stannate;
d. coating platinum slurry electrodes on the front and back surfaces of the negative temperature coefficient thermistor material of lanthanum stannate obtained in the step c, and then annealing for 1h at 900 ℃ to obtain the thermistor material with the following electrical performance parameters: b is400℃/1000℃＝14982K，ρ1000℃＝1.638×103Omega cm lanthanum stannate negative temperature coefficient thermistor material.
Example 4
a. According to Nd2Sn2O7Weighing tin dioxide and neodymium oxide, mixing, placing in an agate ball milling tank, wet milling for 7h by using analytically pure absolute ethyl alcohol as a dispersion medium, drying slurry after wet milling at the temperature of 120 ℃, taking out and grinding for 1h to obtain powder;
b. calcining the powder obtained in the step a at 1200 ℃ for 3h, and grinding for 3h to obtain thermistor powder;
c. c, mixing the powder obtained in the step b at a ratio of 15kg/cm2The pressure is pressed into blocks for molding, the pressure maintaining time is 2min, the molded blocks are subjected to cold isostatic pressing, the pressure is maintained at 300MPa for 1min, and then the blocks are sintered for 10h at the temperature of 1600 ℃ to obtain the negative temperature coefficient thermistor material of neodymium stannate;
d. coating platinum slurry electrodes on the front and back surfaces of the neodymium stannate negative temperature coefficient thermistor material obtained in the step c, and then annealing at 900 ℃ for 1h to obtain the material with the following electrical performance parameters: b is400℃/1000℃＝13705K，ρ1000℃＝8.095×103Omega cm neodymium stannate negative temperature coefficient thermistor material.
Example 5
a. According to Nd2Sn2O7Weighing tin dioxide and neodymium oxide, mixing, placing in an agate ball milling tank, wet milling for 8h by using analytically pure absolute ethyl alcohol as a dispersion medium, drying slurry after wet milling at the temperature of 120 ℃, taking out and grinding for 2h to obtain powder;
b. calcining the powder obtained in the step a at 1200 ℃ for 3h, and grinding for 4h to obtain thermistor powder;
c. c, mixing the powder obtained in the step b at a ratio of 20kg/cm2The pressure is pressed into blocks for molding, the pressure maintaining time is 1min, the molded blocks are subjected to cold isostatic pressing, the pressure is maintained at 250MPa for 2min, and then the blocks are sintered for 10h at the temperature of 1600 ℃ to obtain the negative temperature coefficient thermistor material of neodymium stannate;
d. coating platinum slurry electrodes on the front and back surfaces of the neodymium stannate negative temperature coefficient thermistor material obtained in the step c, and then annealing at 900 ℃ for 1h to obtain the material with the following electrical performance parameters: b is400℃/1000℃＝13324K，ρ1000℃＝7.895×103Omega cm neodymium stannate negative temperature coefficient thermistor material.
Example 6
a. According to Sm2Sn2O7Weighing tin dioxide and samarium sesquioxide, mixing, placing in an agate ball milling tank, wet milling for 6 hours by using analytically pure absolute ethyl alcohol as a dispersion medium, drying slurry after the wet milling at the temperature of 120 ℃, taking out and grinding for 1 hour to obtain powder;
b. calcining the powder obtained in the step a at 1250 ℃ for 5 hours, and grinding for 2 hours to obtain thermistor powder;
c. c, mixing the powder obtained in the step b at a ratio of 20kg/cm2Pressing the blocks into blocks under the pressure of 2min, performing cold isostatic pressing on the formed blocks, maintaining the pressure at 250MPa for 2min, and sintering the blocks at 1600 ℃ for 10h to obtain the samarium stannate negative temperature coefficient thermistor material;
d. coating platinum slurry electrodes on the front and back surfaces of the samarium stannate negative temperature coefficient thermistor material obtained in the step c, and annealing at 900 ℃ for 1h to obtain the electrical propertyThe energy parameters are as follows: b is400℃/1000℃＝12897K，ρ1000℃＝1.739×103Omega cm samarium stannate negative temperature coefficient thermistor material.
Example 7
a. According to Sm2Sn2O7Weighing tin dioxide and samarium sesquioxide, mixing, placing in an agate ball milling tank, wet milling for 8h by using analytically pure absolute ethyl alcohol as a dispersion medium, drying slurry after the wet milling at the temperature of 120 ℃, taking out and grinding for 1h to obtain powder;
b. calcining the powder obtained in the step a at 1200 ℃ for 3h, and grinding for 3h to obtain thermistor powder;
c. c, mixing the powder obtained in the step b at a ratio of 20kg/cm2Pressing the blocks into blocks under the pressure of 2min, carrying out cold isostatic pressing on the formed blocks, keeping the pressure at 300MPa for 3min, and then sintering the blocks at 1600 ℃ for 10h to obtain the samarium stannate negative temperature coefficient thermistor material;
d. coating platinum slurry electrodes on the front surface and the back surface of the samarium stannate negative temperature coefficient thermistor material obtained in the step c, and then annealing at 900 ℃ for 1h to obtain the thermistor material with the following electrical performance parameters: b is400℃/1000℃＝12320K，ρ1000℃＝1.654×103Omega cm samarium stannate negative temperature coefficient thermistor material.
Example 8
a. According to Gd2Sn2O7Weighing tin dioxide and gadolinium oxide, mixing, placing in an agate ball milling tank, wet milling for 6h by using analytically pure absolute ethyl alcohol as a dispersion medium, drying slurry after wet milling at the temperature of 120 ℃, taking out and grinding for 1h to obtain powder;
b. calcining the powder obtained in the step a at 1250 ℃ for 5 hours, and grinding for 3 hours to obtain thermistor powder;
c. b, mixing the powder obtained in the step b at a ratio of 25kg/cm2Pressing the mixture into a block under the pressure of 1min, performing cold isostatic pressing on the formed block, maintaining the pressure at 250MPa for 2min, and sintering the block at 1600 ℃ for 10h to obtain the negative temperature of gadolinium stannateA coefficient thermistor material;
d. coating platinum slurry electrodes on the front surface and the back surface of the gadolinium stannate negative temperature coefficient thermistor material obtained in the step c, and then annealing for 2 hours at 900 ℃ to obtain the gadolinium stannate negative temperature coefficient thermistor material with the following electrical performance parameters: b is400℃/1000℃＝13604K，ρ1000℃＝2.812×103Omega cm gadolinium stannate negative temperature coefficient thermistor material.
Example 9
a. According to Gd2Sn2O7Weighing tin dioxide and gadolinium oxide, mixing, placing in an agate ball milling tank, wet milling for 8h by using analytically pure absolute ethyl alcohol as a dispersion medium, drying slurry after wet milling at the temperature of 120 ℃, taking out and grinding for 1h to obtain powder;
b. calcining the powder obtained in the step a at 1200 ℃ for 5 hours, and grinding for 4 hours to obtain thermistor powder;
c. c, mixing the powder obtained in the step b at a ratio of 20kg/cm2Pressing the block to form the block, keeping the pressure for 1min, carrying out cold isostatic pressing on the formed block, keeping the pressure at 300MPa for 3min, and then sintering the block at 1600 ℃ for 10h to obtain the gadolinium stannate negative temperature coefficient thermistor material;
d. coating platinum slurry electrodes on the front surface and the back surface of the gadolinium stannate negative temperature coefficient thermistor material obtained in the step c, and then annealing for 2 hours at 900 ℃ to obtain the gadolinium stannate negative temperature coefficient thermistor material with the following electrical performance parameters: b is400℃/1000℃＝13256K，ρ1000℃＝2.342×103Omega cm gadolinium stannate negative temperature coefficient thermistor material.
Example 10
Any of the negative temperature coefficient thermistor materials of stannate systems obtained in examples 1 to 9 was subjected to a cation change at the A site to obtain a pyrochlore-structured high-temperature negative temperature coefficient thermistor material. The material has the advantages of simple preparation process, good consistency, stable aging performance and insensitivity to oxygen partial pressure, and is suitable for manufacturing thermistor materials used in high-temperature and different oxygen partial pressure environments.

Claims (2)

1. Negative temperature of stannate systemThe coefficient thermistor material is characterized in that the chemical general formula of the thermistor material is as follows: a. the2Sn2O7Wherein A = La, Nd, Sm or Gd, is formed by mixing and burning raw material tin dioxide with lanthanum oxide, neodymium oxide, samarium oxide or gadolinium oxide respectively, and the specific operation is carried out according to the following steps:
a. according to A2Sn2O7Weighing tin dioxide, mixing the tin dioxide with lanthanum oxide, neodymium oxide, samarium oxide or gadolinium oxide respectively, placing the mixture in an agate ball milling tank, wet-milling the mixture for 6 to 8 hours by using analytically pure absolute ethyl alcohol as a dispersion medium, drying the slurry after the wet milling at the temperature of 120 ℃, taking out the slurry and milling the slurry for 1 hour to obtain powder;
b. calcining the powder obtained in the step a at the temperature of 1200-1250 ℃ for 3-5h, and then grinding for 2-4h to obtain thermistor powder;
c. c, mixing the powder obtained in the step b at a ratio of 15-25kg/cm2The pressure is pressed and molded, the pressure maintaining time is 1-2min, the molded block is subjected to cold isostatic pressing, the pressure is maintained at 250-300MPa for 1-3min, and then the block is sintered for 10h at the temperature of 1600-1650 ℃ to obtain the negative temperature coefficient thermistor material of the stannate system;
d. coating platinum slurry electrodes on the front and back surfaces of the negative temperature coefficient thermistor material of the stannate system obtained in the step c, and then annealing at 900 ℃ for 1-2h to obtain the negative temperature coefficient thermistor material with the following electrical performance parameters: b is400℃/1000℃=12320-15177K，ρ1000℃=0.650-8.095×103Omega cm stannate system negative temperature coefficient thermistor material.
2. A method for preparing a stannate system negative temperature coefficient thermistor material is characterized by comprising the following steps:
a. according to A2Sn2O7Weighing tin dioxide, mixing with lanthanum oxide, neodymium oxide, samarium oxide or gadolinium oxide, placing in an agate ball milling tank, wet milling for 6-8h with analytically pure absolute ethyl alcohol as a dispersion medium, drying the slurry after wet milling at 120 ℃, taking the slurry, and drying the slurryGrinding for 1h to obtain powder;
b. calcining the powder obtained in the step a at the temperature of 1200-1250 ℃ for 3-5h, and then grinding for 2-4h to obtain thermistor powder;
c. c, mixing the powder obtained in the step b at a ratio of 15-25kg/cm2The pressure is pressed and molded, the pressure maintaining time is 1-2min, the molded block is subjected to cold isostatic pressing, the pressure is maintained at 250-300MPa for 1-3min, and then the block is sintered for 10h at the temperature of 1600-1650 ℃ to obtain the negative temperature coefficient thermistor material of the stannate system;
d. coating platinum slurry electrodes on the front and back surfaces of the negative temperature coefficient thermistor material of the stannate system obtained in the step c, and then annealing at 900 ℃ for 1-2h to obtain the negative temperature coefficient thermistor material with the following electrical performance parameters: b is400℃/1000℃=12320-15177K，ρ1000℃=0.650-8.095×103Omega cm stannate system negative temperature coefficient thermistor material.
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