硅酸盐学报

xCdWO₄-(1-x)CdSnO₃系线性负温度系数热敏电阻的制备与线性化机理

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张笑 ¹^,² , 张晓兰 ¹ , 杨光灿 ¹ , 王品一 ¹ , 肖一凡 ¹ , 陈赟 ¹ , 陆有军 ¹^,²

硅酸盐学报 | 研究论文 2026,54(6): 2027-2035

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硅酸盐学报 |研究论文 2026 , 54 (6) : 2027 -2035

xCdWO₄-(1-x)CdSnO₃系线性负温度系数热敏电阻的制备与线性化机理

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张笑¹^,², 张晓兰¹, 杨光灿¹, 王品一¹, 肖一凡¹, 陈赟¹, 陆有军¹^,²

作者信息

^1．北方民族大学材料科学与工程学院，银川 750021

^2．贺兰山实验室半导体晶体与陶瓷材料研究所，银川 750021

作者简介:

张笑（1982—），女，博士，副教授。

Preparation and Linearization Mechanism of xCdWO₄-(1-x)CdSnO₃ NTC Thermistors

Xiao ZHANG¹^,², Xiaolan ZHANG¹, Guangcan YANG¹, Pinyi WANG¹, Yifan XIAO¹, Yun CHEN¹, Youjun LU¹^,²

Affiliations

^1.School of Materials Science and Engineering, North Minzu University, Yinchuan 750021, China

^2.Institute of Semiconductor Crystals and Ceramic Materials, Helanshan Laboratory, Yinchuan 750021, China

ZHANG Xiao (1982-), female, Ph.D., Associate Professor. E-mail: smile_zhang@nun.edu.cn

出版时间: 2026-05-12 doi: 10.14062/j.issn.0454-5648.20250575

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摘要

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负温度系数（NTC）热敏电阻因具有高灵敏度和快速响应特性，在国民经济、军事及航空航天等领域应用广泛。为开发具有优异线性阻温特性的新型NTC材料，本工作采用固相法制备了xCdWO₄-（1-x）CdSnO₃（0.10≤x≤0.35）系线性NTC热敏材料。该体系通过高阻相CdWO₄与低阻热敏相CdSnO₃形成三维导电网络并诱导获得线性电性能，研究了组分比例与材料性能之间的内在规律。XRD分析证实所有样品均由CdWO₄和CdSnO₃两相组成，无其他杂相。在300~450 K温度范围内，材料的电阻率随温度升高呈线性下降趋势，表现出优异的线性NTC特性；其中，当x=0.10时，显示出最高的线性度（R²=0.996）。XPS分析进一步显示，随着x增加，Sn元素的特征峰向更高结合能方向移动，且Sn⁴⁺/Sn²⁺的比值显著减小，表明CdWO₄的引入促进了更多Sn⁴⁺向Sn²⁺的转化，该体系的导电机理主要由锡离子变价的跳跃导电理论主导。交流阻抗谱分析表明材料的电学弛豫过程主要受晶粒效应控制，晶界效应影响微弱。

关键词

线性负温度系数热敏电阻 / 线性度 / 线性化机理 / 钨酸镉 / 锡酸镉

Abstract

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Introduction

Negative temperature coefficient (NTC) thermistors are widely applied in various industries such as automotive electronics, communications, military, and medical fields due to their high sensitivity and fast response. Conventional nonlinear thermistors exhibit a resistivity that varies as an exponential function of temperature, thereby necessitating the use of complex circuitry to achieve linearized output. However, such compensation circuits increase the complexity of use and result in a decrease in the accuracy, limiting the applications. It is thus of great significance for the practical application of the materials to investigate linear NTC thermistors. In this study, the effect of the component ratio on the material properties was investigated via introducing the high-resistance phase CdWO₄ with the low-resistance phase CdSnO₃ to form a three-dimensional conductive network and inducing the acquisition of linear electrical properties. The prepared xCdWO₄-(1-x)CdSnO₃-based linear NTC thermosensitive materials could exhibit good negative temperature coefficient properties at 300-450 K, i.e., the resistivity of the samples could decrease linearly with increasing temperature.

Methods

The linear thermistor material of xCdWO₄-(1-x)CdSnO₃ (0.1≤x≤0.35) was synthesized by a solid-phase reaction method. CdCO₃, WO₃ and SnO₂ were used as raw materials and weighed according to the stoichiometric ratio. After grinding, drying and calcination, CdWO₄ and CdSnO₃ powders were obtained. The two powders were weighed according to a certain ratio, ground and dried to obtain the precursor powder. Based on the precursor powders prepared above, the precursor powders were pressed at 200 MPa by a molding method to obtain plain discs with a diameter of 10 mm and a thickness of approximately 3 mm, and sintered in a muffle furnace at 1423 K for 2 h to obtain the target ceramic samples.

The phase structure of the sintered samples was determined by a model XRD-6000 X-ray diffractometer (Shimadzu Co., Japan). The microscopic morphology and grain size of the powders and ceramic block sections were characterized by a model SIGMA500 scanning electron microscope (SEM, Zeiss Co., Germany), and the elemental characterization and distribution of the sections were analyzed by an energy dispersive spectroscope (EDS). The elemental content and valence were determined by a model K-Alpha X-ray photoelectron spectroscope (XPS, Thermo Fisher Co., USA). After the silver electrodes were prepared via applying silver paste on the upper and lower surfaces of the ceramic disc specimens, the temperature characteristics of the resistance were measured by a model MS2008-10T thermistor R/T test system (Weihong Technology Co., Shenzhen, China) at 300-450 K. The impedance spectra of the ceramic disc specimens at 300-450 K and 100-20 MHz were determined by a model WK6500B impedance analyzer (Wayne Kerr Co., UK).

Results and discussion

The thermosensitive ceramics of xCdWO₄-(1-x)CdSnO₃ (0.1≤x≤0.35) system are prepared by a solid-phase method. The XRD patterns show that the samples consist of two main crystalline phases in the precursor powders, and no other phases occur. The peak intensity of the crystalline plane CdSnO₃ (121) gradually decreases and shifts to a low angle as CdWO₄ addition increases, indicating that the cell parameters of the phase CdSnO₃ increase and the cell volume increases. The SEM images and EDS spectra show that all the samples have the coexistence of two phases CdWO₄ and CdSnO₃. The XPS analysis shows that the Sn peaks move toward a higher binding energy with the increase of CdWO₄ addition, and the value of Sn⁴⁺/Sn²⁺ decreases with the increase of x, which is due to the fact that there is more Sn⁴⁺ converted to Sn²⁺ in CdSnO₃ alone. According to the curves of resistivity ρ versus temperature (T), the resistivity of all the samples exhibits a linear decrease with increasing temperature at 300-450 K, showing the typical NTC characteristics. When x = 0.1, the linearity is the optimum, and R² reaches 0.996. The Cole-Cole plots show a single quarter-circle arc, and the diameter decreases with increasing temperature, indicating that it is dominated by the grain effect, and the relaxation of grain boundaries is not obvious. The R_g and R_gb in the equivalent circuits both decrease with increasing temperature, further confirming the NTC characteristics.

Conclusions

xCdWO₄-(1-x)CdSnO₃ (0.1≤x≤0.35) linear thermistors were prepared by a solid-phase reaction method, having good linear resistance-temperature characteristics at 300-450 K. The room temperature resistivity and resistance temperature coefficient of the composite thermosensitive ceramics decreased, while the material constant B and activation energy increased as CdWO₄ doping increased. When x = 0.1, the thermistor had the optimal resistance-temperature linearization with R² of 0.996. Based on the impedance spectroscopy analysis, the conductive behavior of the xCdWO₄-(1-x)CdSnO₃ system was mainly dominated by the mechanism of the valence jump of Sn ion. The resistance-temperature linearized conductive mechanism originated from the unique microstructure formed by the composite of the high-resistance phase CdWO₄ and the low-resistance phase CdSnO₃. The microstructural units consisting of grain resistance, grain boundary resistance, and grain boundary capacitance could function through synergistic effects.

Key words

linear negative temperature coefficient thermistor / linearity / linearization mechanism / cadmium tungstate / cadmium stannate

引用本文

张笑, 张晓兰, 杨光灿, 王品一, 肖一凡, 陈赟, 陆有军. xCdWO₄-(1-x)CdSnO₃系线性负温度系数热敏电阻的制备与线性化机理. 硅酸盐学报, 2026 , 54 (6) : 2027 -2035 . DOI: 10.14062/j.issn.0454-5648.20250575

Xiao ZHANG, Xiaolan ZHANG, Guangcan YANG, Pinyi WANG, Yifan XIAO, Yun CHEN, Youjun LU. Preparation and Linearization Mechanism of xCdWO₄-(1-x)CdSnO₃ NTC Thermistors[J]. Journal of the Chinese Ceramic Society, 2026 , 54 (6) : 2027 -2035 . DOI: 10.14062/j.issn.0454-5648.20250575

基金

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国家自然科学基金(52372112)
北方民族大学研究生创新项目(CYX25170)

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2026年第54卷第6期

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文章信息

doi: 10.14062/j.issn.0454-5648.20250575

接收时间：2025-07-25
首发时间：2026-10-22
出版时间：2026-05-12

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收稿日期：2025-07-25
修回日期：2025-08-19

基金

国家自然科学基金(52372112)

北方民族大学研究生创新项目(CYX25170)

作者信息

^1．北方民族大学材料科学与工程学院，银川 750021

^2．贺兰山实验室半导体晶体与陶瓷材料研究所，银川 750021

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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