CN112321298B - Perovskite-like thermistor material and preparation method thereof - Google Patents

Perovskite-like thermistor material and preparation method thereof Download PDF

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CN112321298B
CN112321298B CN202011229554.0A CN202011229554A CN112321298B CN 112321298 B CN112321298 B CN 112321298B CN 202011229554 A CN202011229554 A CN 202011229554A CN 112321298 B CN112321298 B CN 112321298B
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张博
魏亚鑫
付志龙
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 perovskite-like thermistor material which is prepared by a Pechini method, wherein yttrium nitrate hexahydrate, copper nitrate trihydrate, tetrabutyl titanate and manganese nitrate tetrahydrate are used as raw materials, ethylene glycol is used as a polymerization agent, citric acid is used as a chelating agent, a complex coordination reaction is carried out, and Y with a perovskite-like structure can be obtained by mixing, stirring, heating, drying, grinding, calcining, re-grinding, cold isostatic pressing, high-temperature sintering and electrode coating and sintering2/3Cu3Ti4‑xMnxO12(x is more than or equal to 0.1 and less than or equal to 1) thermal sensitive ceramic material with the material constant ofB ‑50/250= 3579K-4302K, 25 ℃ resistivity of 1.70X 104Ω•cm‑2.20×107Ω. cm. The perovskite-like thermistor material prepared by the method has stable performance and high sensitivity, has an obvious negative temperature coefficient characteristic in the temperature range of-50-250 ℃, has stable electrical performance and high sensitivity, and is suitable for manufacturing thermistors.

Description

Perovskite-like thermistor material and preparation method thereof
Technical Field
The invention relates to a perovskite-like thermistor material and a preparation method thereof, the thermistor material has obvious negative temperature coefficient characteristic in the temperature range of minus 50 ℃ to 250 ℃, and is a novel thermistor material suitable for manufacturing thermistors.
Background
The monitoring and control of temperature is closely related to our daily life, and temperature sensors are ubiquitous in both homes, industry, and laboratories and medicine. Negative Temperature Coefficient (NTC) thermistors are widely used in various industries due to their multiple advantages of high reliability, small size, fast response time, low cost, etc. Negative Temperature Coefficient (NTC) thermistors can be classified into low-temperature (less than or equal to 60 ℃) thermistors, normal-temperature (minus 60 ℃ -300 ℃) thermistors and high-temperature (more than or equal to 300 ℃) thermistors according to the use temperature region. In recent years, perovskite-like negative temperature coefficient thermistors show excellent performances of high sensitivity and good stability in a high temperature region (not less than 300 ℃), and arouse great interest. But the application of the nano-silver powder in a normal temperature zone (60 ℃ below zero to 300 ℃) has not been researched and paid attention. The research work of the filling perovskite type NTC thermistor in the application range of the normal temperature region is significant, and a new challenging subject is provided for the development of novel normal temperature thermistor materials.
Many approaches have been devoted to tuning electrical properties by ion doping, introducing binary phases, or varying the fabrication process. The invention relates to Y prepared by the Pechini method2/3Cu3Ti3.5Mn0.5O12The electrical properties of the thermistor material are preliminarily researched, and the material constant is 3820K, so that the thermistor material is expected to be used for manufacturing thermistors. Taking Mn into account4+With Ti4+Both are valence-changing ions and have similar ionic radii, Mn4+Substituted Ti4+Adjustable Y2/3Cu3Ti3.5Mn0.5O12The thermistor material has electrical properties, and thermistors with different electrical property parameters are manufactured.
The invention is from Y2/3Cu3Ti3.5Mn0.5O12Based on the semiconductor characteristics, the perovskite-like Y is synthesized by doping manganese nitrate tetrahydrate2/3Cu3Ti3.5Mn0.5O12(x is more than or equal to 0.1 and less than or equal to 1) thermistor material.
Disclosure of Invention
The invention aims to provide a perovskite-like thermistor material and a preparation method thereof, the material is prepared by a Pechini method, yttrium nitrate hexahydrate, copper nitrate trihydrate, tetrabutyl titanate and manganese nitrate tetrahydrate are used as raw materials, ethylene glycol is used as a polymerization agent, citric acid is used as a chelating agent, a complex coordination reaction is carried out, and the perovskite-like thermistor material can be obtained by mixing, stirring, heating, drying, grinding, calcining and regrinding, cold isostatic pressing, high-temperature sintering and electrode coating and sintering, wherein the material constant is B-50/2503579K-4302K, 25 deg.C, and 1.70 × 104Ω·cm-2.20×107Omega cm. The perovskite-like thermistor material prepared by the method has stable performance and good consistency, has obvious negative temperature coefficient characteristic at the temperature of minus 50-250 ℃, has stable electrical performance and good consistency of a material system, and is suitable for manufacturing thermistors.
The invention relates to a perovskite-like thermistor material, which is prepared by taking yttrium nitrate hexahydrate, copper nitrate trihydrate, tetrabutyl titanate and manganese nitrate tetrahydrate as raw materials, taking ethylene glycol as a polymerization agent and taking citric acid as a chelating agent to perform complex coordination reaction to obtain a body-centered cubic perovskite-like structure with a chemical composition of Y2/3Cu3Ti4-xMnxO12Wherein x is more than or equal to 0.1 and less than or equal to 1, and is prepared by a Pechini method.
The preparation method of the perovskite-like thermistor material adopts a Pechini method, and the specific operation is carried out according to the following steps:
a. according to Y2/3Cu3Ti4-xMnxO12Respectively weighing yttrium nitrate hexahydrate, copper nitrate trihydrate, tetrabutyl titanate and manganese nitrate tetrahydrate, dissolving in 99% ethanol to form a mixed solution, adding ethylene glycol and citric acid, and magnetically stirring for 1-3 hours to obtain blue hydrosol;
b. b, heating the blue hydrosol obtained in the step a on a heating plate at the temperature of 120 ℃ to dehydrate the blue hydrosol until gel is formed, and drying the gel at the temperature of 150 ℃ to obtain loose brown ash powder;
c. grinding the powder obtained in the step b in a mortar and decomposing the powder at the temperature of 350 ℃ for 1 to 3 hours, then grinding the powder again and calcining the powder at the temperature of 600 ℃ and 800 ℃ for 5 to 7 hours to obtain Y2/3Cu3Ti4-xMnxO12Powder;
d. c, mixing the powder material obtained in the step c at a ratio of 10-18Kg/cm2The pressure is pressed into blocks for molding for 0.5 to 2.5 minutes, the molded block material is subjected to cold isostatic pressing, pressure is maintained for 1 to 3 minutes under the pressure of 200 and 400MPa, and then sintering is carried out for 4 to 8 hours at the temperature of 950 to 1150 ℃ to obtain the high-temperature thermosensitive ceramic material;
e. coating silver paste electrodes on the front surface and the back surface of the ceramic material sintered in the step d, and annealing at the temperature of 650 ℃ for 30 minutes to obtain the ceramic material with the temperature range of-50-250 ℃ and the material constant of B-50/2503579K-4302K, 25 deg.C, and 1.70 × 104Ω·cm-2.20×107Omega cm perovskite-like thermistor material.
The perovskite-like thermistor material is prepared by dissolving nitrates of yttrium, copper, titanium and manganese in ethanol with the concentration of 99% by adopting a Pechini method, sequentially adding polymerization agent ethylene glycol and chelating agent citric acid, and carrying out a complex coordination reaction by stirring and heatingDrying the gel to obtain brown ash powder, grinding, calcining and grinding again to obtain powder material, then carrying out sheet-type cold isostatic pressing on the powder material, coating silver paste electrodes on the front and back surfaces after high-temperature sintering to obtain the perovskite-like thermistor material, wherein the material constant is B-50/2503579K-4302K, 25 deg.C, and 1.70 × 104Ω·cm-2.20×107Omega cm. The perovskite-like thermistor material prepared by the method has stable performance and good consistency, has obvious negative temperature coefficient characteristic at the temperature of minus 50-250 ℃, and is suitable for manufacturing thermistors.
Drawings
FIG. 1 is an X-ray diffraction pattern of a heat-sensitive ceramic material of the present invention.
Detailed Description
Example 1
a. According to Y2/3Cu3Ti3.9Mn0.1O12Weighing 2.1622g of yttrium nitrate hexahydrate, 6.1934g of copper nitrate trihydrate, 11.3414g of tetrabutyl titanate and 0.30227g of manganese nitrate tetrahydrate in 99% ethanol to form a mixed solution, adding 250ml of ethylene glycol and 20g of citric acid, and stirring for 1 hour by magnetic force to obtain blue hydrosol;
b. b, heating the blue hydrosol obtained in the step a on a heating plate at the temperature of 120 ℃ to dehydrate the blue hydrosol until gel is formed, and drying the gel at the temperature of 150 ℃ to obtain loose brown ash powder;
c. grinding the powder obtained in the step b in a mortar and decomposing the powder at the temperature of 350 ℃ for 1 hour, then grinding the powder again and calcining the powder at the temperature of 600 ℃ for 5 hours to obtain Y2/3Cu3Ti3.9Mn0.1O12Powder;
d. c, mixing the powder material obtained in the step c at a ratio of 10Kg/cm2The pressure of the raw material is pressed into blocks for molding for 0.5 minute, the molded block material is subjected to cold isostatic pressing, the pressure is maintained for 1 minute under the pressure of 200MPa, and then the block material is sintered for 4 hours at the temperature of 950 ℃ to prepare the high-temperature thermosensitive ceramic material;
e. coating silver paste electrodes on the front surface and the back surface of the ceramic material sintered in the step c, and annealing at 650 ℃ for 30 minutes to obtain the ceramic material with the temperature range of-50-250 ℃ and the material constant of B-50/2503579K-4302K, 25 deg.C, and 1.70 × 104Ω·cm-2.20×107Omega cm perovskite-like thermistor material.
Example 2
a. According to Y2/3Cu3Ti3.7Mn0.3O12Weighing 2.1596g of yttrium nitrate hexahydrate, 6.1860g of copper nitrate trihydrate, 10.7407g of tetrabutyl titanate and 0.90722g of manganese nitrate tetrahydrate in 99% ethanol to form a mixed solution, adding 250ml of ethylene glycol and 20g of citric acid, and stirring for 1.5 hours by magnetic force to obtain blue hydrosol;
b. b, heating the blue hydrosol obtained in the step a on a heating plate at the temperature of 120 ℃ to dehydrate the blue hydrosol until gel is formed, and drying the gel at the temperature of 150 ℃ to obtain loose brown ash powder;
c. grinding the powder obtained in step b in a mortar and decomposing at 350 ℃ for 1.5 hours, then grinding the powder again and calcining at 650 ℃ for 5.5 hours to obtain Y2/3Cu3Ti3.7Mn0.3O12Powder;
d. c, mixing the powder material obtained in the step c with 12Kg/cm2The pressure of the raw material is pressed into blocks for forming for 1.0 minute, the formed block material is subjected to cold isostatic pressing, the pressure is maintained for 1.5 minutes under the pressure of 250MPa, and then the block material is sintered for 5 hours at the temperature of 1000 ℃ to prepare the high-temperature thermosensitive ceramic material;
e. coating silver paste electrodes on the front surface and the back surface of the ceramic material sintered in the step d, and annealing at the temperature of 650 ℃ for 30 minutes to obtain the ceramic material with the temperature range of-50-250 ℃ and the material constant of B-50/2503579K-4302K, 25 deg.C, and 1.70 × 104Ω·cm-2.20×107Omega cm perovskite-like thermistor material.
Example 3
a. According to Y2/3Cu3Ti3.5Mn0.5O12Weighing 2.1570g of yttrium nitrate hexahydrate, 6.1787g of copper nitrate trihydrate, 10.1539g of tetrabutyl titanate and 1.5102g of manganese nitrate tetrahydrate in 99% ethanol to form a mixed solution, adding 250ml of ethylene glycol and 20g of citric acid, and stirring for 2 hours by magnetic force to obtain blue hydrosol;
b. b, heating the blue hydrosol obtained in the step a on a heating plate at the temperature of 120 ℃ to dehydrate the blue hydrosol until gel is formed, and drying the gel at the temperature of 150 ℃ to obtain loose brown ash powder;
c. grinding the powder obtained in the step b in a mortar and decomposing the powder at the temperature of 350 ℃ for 2 hours, then grinding the powder again and calcining the powder at the temperature of 700 ℃ for 6 hours to obtain Y2/3Cu3Ti3.5Mn0.5O12Powder;
d. c, mixing the powder material obtained in the step c with 14Kg/cm2The pressure of the raw material is pressed into a block for molding for 1.5 minutes, the molded block material is subjected to cold isostatic pressing, pressure is maintained for 2 minutes under the pressure of 300MPa, and then the block material is sintered for 6 hours at the temperature of 1050 ℃ to prepare a high-temperature thermal sensitive ceramic material;
e. coating silver paste electrodes on the front surface and the back surface of the ceramic material sintered in the step d, and annealing at the temperature of 650 ℃ for 30 minutes to obtain the ceramic material with the temperature range of-50-250 ℃ and the material constant of B-50/2503579K-4302K, 25 deg.C, and 1.70 × 104Ω·cm-2.20×107Omega cm perovskite-like thermistor material.
Example 4
a. According to Y2/3Cu3Ti3.3Mn0.7O12Weighing 2.1545g of yttrium nitrate hexahydrate, 6.1713g of copper nitrate trihydrate, 9.5623g of tetrabutyl titanate and 2.1118g of manganese nitrate tetrahydrate in 99% ethanol to form a mixed solution, adding 250ml of ethylene glycol and 20g of citric acid, and stirring for 2.5 hours by magnetic force to obtain blue hydrosol;
b. b, heating the blue hydrosol obtained in the step a on a heating plate at the temperature of 120 ℃ to dehydrate the blue hydrosol until gel is formed, and drying the gel at the temperature of 150 ℃ to obtain loose brown ash powder;
c. grinding the powder obtained in the step b in a mortar and decomposing the powder at the temperature of 350 ℃ for 2.5 hours, then grinding the powder again and calcining the powder at the temperature of 750 ℃ for 6.5 hours to obtain Y2/3Cu3Ti3.3Mn0.7O12Powder;
d. c, mixing the powder material obtained in the step c with 16Kg/cm2The pressure of the raw material is pressed into a block for molding for 2.0 minutes, the molded block material is subjected to cold isostatic pressing, the pressure is maintained for 2.5 minutes under the pressure of 350MPa, and then the block material is sintered for 7 hours at the temperature of 1100 ℃ to prepare the high-temperature thermal sensitive ceramic material;
e. coating silver paste electrodes on the front surface and the back surface of the ceramic material sintered in the step d, and annealing at the temperature of 650 ℃ for 30 minutes to obtain the ceramic material with the temperature range of-50-250 ℃ and the material constant of B-50/2503579K-4302K, 25 deg.C, and 1.70 × 104Ω·cm-2.20×107Omega cm perovskite-like thermistor material.
Example 5
a. According to Y2/3Cu3Ti3Mn1O12Weighing 2.1506g of yttrium nitrate hexahydrate, 6.1603g of copper nitrate trihydrate, 8.6774g of tetrabutyl titanate and 3.0115g of manganese nitrate tetrahydrate in 99% ethanol to form a mixed solution, adding 250ml of ethylene glycol and 20g of citric acid, and stirring for 3 hours by magnetic force to obtain blue hydrosol;
b. b, heating the blue hydrosol obtained in the step a on a heating plate at the temperature of 120 ℃ to dehydrate the blue hydrosol until gel is formed, and drying the gel at the temperature of 150 ℃ to obtain loose brown ash powder;
c. grinding the powder obtained in the step b in a mortar and decomposing the powder at the temperature of 350 ℃ for 3 hours, then grinding the powder again and calcining the powder at the temperature of 800 ℃ for 7 hours to obtain Y2/3Cu3Ti3Mn1O12Powder;
d. c, mixing the powder material obtained in the step c at a ratio of 18Kg/cm2Is pressed into blocks under the pressure for 2.5 minutesPerforming cold isostatic pressing on the formed block material, maintaining the pressure for 3 minutes under the pressure of 400MPa, and then sintering for 8 hours at the temperature of 1150 ℃ to prepare a high-temperature thermosensitive ceramic material;
e. coating silver paste electrodes on the front surface and the back surface of the ceramic material sintered in the step d, and annealing at the temperature of 650 ℃ for 30 minutes to obtain the ceramic material with the temperature range of-50-250 ℃ and the material constant of B-50/2503579K-4302K, 25 deg.C, and 1.70 × 104Ω·cm-2.20×107Omega cm perovskite-like thermistor material.

Claims (2)

1. The perovskite-like thermistor material is characterized in that yttrium nitrate hexahydrate, copper nitrate trihydrate, tetrabutyl titanate and manganese nitrate tetrahydrate are used as raw materials, ethylene glycol is used as a polymerization agent, citric acid is used as a chelating agent, and a complex coordination reaction is carried out to obtain a body-centered cubic perovskite-like structure with a chemical composition of Y2/3Cu3Ti4-xMnxO12Wherein x is more than or equal to 0.1 and less than or equal to 1, and is prepared by a Pechini method.
2. The method for preparing a perovskite-like thermistor material according to claim 1, characterized in that the perovskite-like thermistor material is prepared by a Pechini method, and the specific operation is carried out by the following steps:
a. according to Y2/3Cu3Ti4-xMnxO12Respectively weighing yttrium nitrate hexahydrate, copper nitrate trihydrate, tetrabutyl titanate and manganese nitrate tetrahydrate, dissolving in 99% ethanol to form a mixed solution, adding ethylene glycol and citric acid, and magnetically stirring for 1-3 hours to obtain blue hydrosol;
b. b, heating the blue hydrosol obtained in the step a on a heating plate at the temperature of 120 ℃ to dehydrate the blue hydrosol until gel is formed, and drying the gel at the temperature of 150 ℃ to obtain loose brown ash powder;
c. grinding the powder obtained in the step b in a mortar and decomposing the powder at the temperature of 350 ℃ for 1 to 3 hours, then grinding the powder again and calcining the powder at the temperature of 600 ℃ and 800 ℃ for 5 to 7 hours to obtain Y2/3Cu3Ti4-xMnxO12Powder;
d. c, mixing the powder material obtained in the step c with 10-18kg/cm2The pressure is pressed into blocks for molding for 0.5 to 2.5 minutes, the molded block material is subjected to cold isostatic pressing, pressure is maintained for 1 to 3 minutes under the pressure of 200 and 400MPa, and then sintering is carried out for 4 to 8 hours at the temperature of 950 to 1150 ℃ to obtain the high-temperature thermosensitive ceramic material;
e. coating silver paste electrodes on the front surface and the back surface of the ceramic material sintered in the step c, and annealing at the temperature of 650 ℃ for 30 minutes to obtain the ceramic material with the temperature range of-50-250 ℃ and the material constant ofB -50/250= 3579K-4302K, 25 ℃ resistivity of 1.70X 104 Ω•cm-2.20×107Ω · cm perovskite-like thermistor material.
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