CN110218087B - Preparation method of negative temperature coefficient thermistor material - Google Patents

Preparation method of negative temperature coefficient thermistor material Download PDF

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CN110218087B
CN110218087B CN201910603573.6A CN201910603573A CN110218087B CN 110218087 B CN110218087 B CN 110218087B CN 201910603573 A CN201910603573 A CN 201910603573A CN 110218087 B CN110218087 B CN 110218087B
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廖园富
何鹏飞
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Weihai Kebole New Energy Technology Co ltd
Weihai Kebole Automotive Electronics Co ltd
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    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/04—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having negative temperature coefficient
    • H01C7/042—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having negative temperature coefficient mainly consisting of inorganic non-metallic substances
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
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Abstract

The invention discloses a preparation method of a negative temperature coefficient thermistor material, which solves the problem that the existing thermistor material inevitably introduces elements of iron, cobalt and nickel. The technical scheme is that the material is prepared from the following raw materials in parts by mole: la2O3 of 22.5-47.5, CaCO35 to 55, Mn 45 to 95, ZrO25-55, and controlling Fe in the raw materials to be less than 0.001, Co to be less than 0.001 and Ni to be less than 0.001. The invention has simple raw materials, does not add any element or compound of three elements of Fe, Co and Ni, can realize the adjustment of the room temperature resistance value and the material constant B value in a wide range by adjusting the contents of CaZrO3 and LaMn3, has stable performance and wide application temperature range.

Description

Preparation method of negative temperature coefficient thermistor material
Technical Field
The invention relates to the field of thermistor materials, in particular to a preparation method of a negative temperature coefficient thermistor material.
Background
In the new century, with the rapid development of the fields of communication and the like, the requirement on the electromagnetic anti-interference capability of terminal communication equipment is higher and higher particularly in recent years. These requirements bring great challenges to the design layout of weak current lines, and the large capacitive reactance may affect the reliability of communication. Under the circumstances, the development of components with high reliability, low capacitance and low inductance is more and more urgent. The traditional thermistor material generally consists of transition elements of manganese, cobalt and nickel and iron oxides, as is well known, due to the electronic arrangement of the elements of iron, cobalt and nickel, the magnetic properties of the elements are particularly outstanding, materials containing the elements are easy to magnetize and have higher magnetic permeability, and materials without the elements of iron, cobalt and nickel eliminate the influence.
For example, application No. 201910235582.4 discloses a material having a negative temperature coefficient of resistance (NTC) thermistor, characterized in that the composition of the material is Zn1-x-2yAlxCuyMoyO, wherein x is more than or equal to 0.001 and less than or equal to 0.03, and y is more than 0 and less than or equal to 0.01. The NTC thermistor material provided by the invention is mainly composed of zinc oxide, and the purpose of adjusting the room temperature resistivity and the material constant B value of the thermistor element is achieved by changing the content of each element in the composition, so that the adjustment of the room temperature resistivity and the material constant B value in a wide range is realized. Although this material does not contain fe, co, and ni, the material has a problem in consistency and the like due to the high volatility of Zn at high temperature.
Also disclosed are negative temperature coefficient thermistor materials and methods for making the same, such as patent No. 201410460757.9. The chemical general formula of the thermistor material is CexMnxSi1-xO2x +2, wherein x is more than 0.65 and less than 1; the material constant B100 ℃/200 ℃, (5400-5880) K + -10%, the resistivity rho 25 ℃, (3.6-97) x 105 omega cm + -10%, and rho 250 ℃, (250-8000) omega cm + -10%. The resistance-temperature relation curve of the thermistor material has good linearity in the whole temperature test interval, stable high-temperature performance and wide applicable temperature range, and the room temperature resistivity of the thermistor material can be continuously adjusted by adjusting the content of Si in the system. In the technical scheme, the problem of aging stability exists due to the SiO2 glass.
Disclosure of Invention
The invention aims to solve the technical problems and provides a preparation method of a negative temperature coefficient thermistor material, which is simple in raw material, free of any element or compound of three elements of Fe, Co and Ni, capable of realizing adjustment of room temperature resistance value and material constant B value in a wide range through content adjustment of CaZrO3 and LaMn3, stable in performance and wide in applicable temperature range.
The technical scheme is that the material is prepared from the following raw materials in parts by mole: 22.5-47.5 La2O3, 5-55 CaCO3, 45-95 Mn and 5-55 ZrO2, wherein Fe is less than 0.001, Co is less than 0.001 and Ni is less than 0.001 in the raw materials.
The raw materials are prepared by the following steps:
a. la2O3, MnCO3, CaCO3 and ZrO2 are used as raw materials, and are mixed according to the molar ratio of La2O3 to 22.5-47.5, CaCO3 to 5-55, Mn to 45-95 and ZrO2 to 5-55, and then water is added to the mixture to be ball-milled into slurry;
b. drying and calcining the slurry to obtain a solid powder material;
C. and adding water into the solid powder material again, ball-milling, drying, pressing, forming and sintering to obtain the negative temperature coefficient thermistor material.
In the steps a and c, the ball milling conditions are as follows: material preparation: ball: the water is 1:3:3, and the ball milling time is 8 hours.
In the step b, the drying temperature is 250 ℃, the calcination temperature is 900-1200 ℃, and the time is 2-8 hours, preferably 6 hours.
In the step c, the sintering temperature is 1100-1500 ℃ (preferably 1130 ℃) and the sintering time is 5 hours.
Aiming at the problems in the background art, the inventor carries out intensive research on raw materials and selects La2o3 and CaCO on the premise of not introducing three elements of Fe, Co and Ni3、MnCO3、 ZrO2The La2o3 can be synthesized into perovskite LaMnO3 with MnCO3 and CaCO3 can be synthesized into ZrO2The synthesized CaZrO3 has small LaMnO3 resistance and B value, can form solid solution with CaZrO3 with large resistance, realizes the adjustment of the room temperature resistance value and the material constant B value in a wide range by changing the content of the CaZrO3 and the LaMnO3, and solves the problem of stability when Fe, Co and Ni elements are not added in the background technology due to the rare earth element La.
Has the advantages that:
the invention has simple raw materials, does not add any element or compound of three elements of Fe, Co and Ni, can realize the resistance value at room temperature in a wide range and the value of the material constant B by adjusting the contents of CaZrO3 and LaMn3, has stable adjusting performance and wide application temperature range.
Detailed Description
The method comprises the following steps:
a. la2O3, MnCO3, CaCO3 and ZrO2 are used as raw materials, and are mixed according to the molar ratio of La2O3 being 22.5-47.5, CaCO3 being 5-55, Mn being 45-95 and ZrO2 being 5-55, and then water is added to the mixture to be ball-milled into slurry, wherein the ball-milling conditions are as follows: material preparation: ball: water is 1:3:3, and the ball milling time is 8 hours;
b. drying and calcining the slurry to obtain a solid powder material, wherein the drying temperature is 250 ℃, the calcining temperature is 900-1200 ℃, and the time is 2-8 hours;
C. adding water into the solid powder material again, ball-milling, drying, pressing, forming and sintering to obtain the negative temperature coefficient thermistor material, wherein the ball-milling conditions are as follows: material preparation: ball: the ratio of water to water is 1:3:3, the ball milling time is 8 hours, the drying temperature is 250 ℃, the calcining temperature is 900-1200 ℃, and the time is 2-8 hours;
for various examples and properties using the above process, see the following table:
Figure BDA0002119976840000041

Claims (4)

1. the preparation method of the negative temperature coefficient thermistor material is characterized in that the material is prepared by the following steps:
a. la2O3, MnCO3, CaCO3 and ZrO2 are used as raw materials, Fe is controlled to be less than 0.001, Co is controlled to be less than 0.001, Ni is controlled to be less than 0.001, the La2O3 is 22.5-47.5, CaCO3 is 5-55, MnCO3 is 45-95, and ZrO2 is 5-55 in molar parts, and water is added to the mixture to be ball-milled into slurry;
b. drying and calcining the slurry to obtain a solid powder material;
C. and adding water into the solid powder material again, ball-milling, drying, pressing, forming and sintering to obtain the negative temperature coefficient thermistor material.
2. The method of preparing a ntc thermistor material according to claim 1, wherein in steps a and c, the ball milling conditions are: material preparation: ball: the water is 1:3:3, and the ball milling time is 8 hours.
3. The method as claimed in claim 1 or 2, wherein in the step b, the drying temperature is 250 ℃, the calcination temperature is 900-1200 ℃, and the time is 2-8 hours.
4. The method of claim 3, wherein the sintering temperature is 1100-1500 ℃ and the sintering time is 5 hours in the step c.
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CN111548159A (en) * 2020-05-16 2020-08-18 中国科学院新疆理化技术研究所 Zirconate system negative temperature coefficient thermistor material and preparation method thereof
CN112960979B (en) * 2021-02-25 2023-05-16 中国科学院新疆理化技术研究所 Zirconate system high-temperature negative temperature coefficient thermistor material and preparation method thereof
CN114920555A (en) * 2022-05-16 2022-08-19 中国科学院新疆理化技术研究所 Preparation method of manganese-doped calcium zirconate high-temperature negative temperature coefficient thermistor material

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JPH08167501A (en) * 1994-12-12 1996-06-25 Matsushita Electric Ind Co Ltd Positive thermistor and its manufacture
CN1374667A (en) * 2001-03-07 2002-10-16 株式会社村田制作所 Multi-layer ceramic capacitor and its producing method
CN102249662A (en) * 2010-04-05 2011-11-23 Tdk株式会社 Nonlinear resistor ceramic composition and electronic component
CN107140982A (en) * 2017-05-18 2017-09-08 侯丹 A kind of preparation method of negative temperature coefficient heat-sensitive resistance material

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Publication number Priority date Publication date Assignee Title
JPH08167501A (en) * 1994-12-12 1996-06-25 Matsushita Electric Ind Co Ltd Positive thermistor and its manufacture
CN1374667A (en) * 2001-03-07 2002-10-16 株式会社村田制作所 Multi-layer ceramic capacitor and its producing method
CN102249662A (en) * 2010-04-05 2011-11-23 Tdk株式会社 Nonlinear resistor ceramic composition and electronic component
CN107140982A (en) * 2017-05-18 2017-09-08 侯丹 A kind of preparation method of negative temperature coefficient heat-sensitive resistance material

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