硅酸盐学报

Mn掺杂对热压烧结（K_0.5Na_0.5）NbO₃无铅压电陶瓷电学性能的影响

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钟子晴 ¹ , 张乾宇 ¹ , 徐泽 ¹ , 曾繁达 ¹ , 邢志鹏 ¹ , 刘亦轩 ¹^,² , 赵纯林 ³ , 王轲 ¹

硅酸盐学报 | 研究论文 2025,53(9): 2613-2621

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硅酸盐学报 |研究论文 2025 , 53 (9) : 2613 -2621

Mn掺杂对热压烧结（K_0.5Na_0.5）NbO₃无铅压电陶瓷电学性能的影响

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钟子晴¹, 张乾宇¹, 徐泽¹, 曾繁达¹, 邢志鹏¹, 刘亦轩¹^,², 赵纯林³, 王轲¹

作者信息

^1．清华大学材料学院，新型陶瓷材料全国重点实验室，北京 100084

^2．乌镇实验室先进功能陶瓷材料研究中心，浙江嘉兴 314500

^3．福州大学材料科学与工程学院，福州 350108

通讯作者:

徐泽（1995—），男，博士，助理研究员；

刘亦轩（1995—），男，博士，助理研究员；

赵纯林（1990—），男，博士，副研究员。

作者简介:

钟子晴（2000—），女，硕士研究生。

Effects of Mn Doping on Electrical Properties in Hot-Pressed (K_0.5Na_0.5)NbO₃ Lead-Free Piezoceramics

Ziqing ZHONG¹, Qianyu ZHANG¹, Ze XU¹, Fanda ZENG¹, Zhipeng XING¹, Yixuan LIU¹^,², Chunlin ZHAO³, Ke WANG¹

Affiliations

^1.State Key Laboratory of New Ceramic Materials, School of Materials Science and Engineering, Tsinghua University, Beijing 100084, China

^2.Research Center for Advanced Functional Ceramics, Wuzhen Laboratory, Zhejiang, Jiaxing 314500, China

^3.School of Materials Science and Engineering, Fuzhou University, Fuzhou 350108, China

Corresponding Author:

XU Ze (1995-), male, Ph.D., Research Associate. E-mail: xu-ze@mail.tsinghua.edu.cn;

LIU Yixuan (1995-), male, Ph.D., Research Associate. liuyx2022@mail.tsinghua.edu.cn;

ZHAO Chunlin (1990-), male, Ph.D., Associate Professorial Fellow. zhaochunlin@fzu.edu.cn

ZHONG Ziqing (2000-), female, Master candidate. E-mail: zhongzq23@mails.tsinghua.edu.cn

出版时间: 2025-09-20 doi: 10.14062/j.issn.0454-5648.20240851

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摘要

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（K, Na）NbO₃（KNN）基无铅压电陶瓷具有较高的居里温度和优异的综合性能，被认为是替代铅基压电陶瓷的重要候选材料之一。为进一步提升其性能，研究者们采用元素掺杂等方法进行优化。Mn元素的化学改性机理在常压烧结的KNN陶瓷中被广泛研究，然而，掺杂后的KNN陶瓷致密度差异明显，从而给解析Mn元素掺杂改性的物理化学机制带来挑战。本工作以热压烧结制备的KNN陶瓷为研究对象，系统探究Mn掺杂对热压烧结的KNN陶瓷微观结构及电学性能的影响。结果表明，所制备的陶瓷均具有高的致密度，相对密度超过98%，且Mn掺杂并未改变KNN的相结构。同时Mn掺杂后材料依然保持了较高的压电性能，当掺杂量为1.5%（摩尔分数）时，d₃₃达到106 pC/N，剩余极化提高至15 μC/cm²；而PFM微观畴翻转测试表明，随着Mn掺杂量的增加，铁电畴的局域翻转电压逐渐提升，陶瓷机械品质因数Q_m提高到175，表现出“硬性”掺杂效应。上述结果表明，Mn掺杂在热压烧结制备的KNN陶瓷中展现出与传统掺杂机制所不同的Q_m和P_r同时提升、d₃₃保持在较高值的非典型“硬性”掺杂效应。本研究为理解Mn掺杂对KNN的作用机制提供了新的视角，并为无铅压电陶瓷的设计与优化提供参考。

关键词

热压烧结 / 铌酸钾钠 / 锰掺杂 / 掺杂效应 / 电学性能

Abstract

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Introduction

(K, Na)NbO₃ (KNN)-based lead-free piezoelectric ceramics are considered to be one of the important candidates to replace lead-based piezoelectric ceramics due to their high Curie temperature and excellent comprehensive performance. To further improve its performance, the strategy of element doping is employed. The doping behavior of the Mn element in pressure-sintered KNN ceramics has been extensively studied. However, there are significant differences in the density of Mn-doped KNN ceramics in different works, which poses a challenge to the analysis of the underlying mechanism of Mn doping and its modification effect. Therefore, this study takes hot-pressed KNN ceramics as the research object due to their high densification, and systematically explores the impact of Mn doping on the microstructure and electrical properties of KNN ceramics.

Methods

In this study, KNN ceramics with MnO₂ doping were prepared by hot-pressed sintering. The specific composition is (K_0.5Na_0.5)NbO₃-x% MnO₂ (abbreviated as KNN-x% MnO₂, x = 0, 0.5, 1.0, 1.5). The raw materials include K₂CO₃ (99.0%), Na₂CO₃ (99.8%), Nb₂O₅ (99.99%), and MnO₂ (98.8%), all of which were purchased from Sinopharm Chemical Reagent Co., Ltd. First, carbonate and Nb₂O₅ were placed in a nylon ball mill with zirconia balls according to the formula ratio, and ball milled for 24 h using anhydrous ethanol as the medium; the ball-milled slurry was dried and calcined at 730 ℃ for 4 h, and then ball-milled again and calcined again at 930 ℃ for 4 hours. Subsequently, different amounts of MnO₂ were added to the calcined powder, mixed and ball-milled for 24 h, and then dried and ground to obtain Mn-doped KNN ceramic powder. Finally, the ceramic block was prepared by hot pressing and sintering at 950 ℃ and 30 MPa for 2 h under argon atmosphere. After cutting, grinding, and annealing at different temperatures, the sample surfaces were subsequently coated with silver electrode for electrical measurements. The poling process was performed at 3.5 kV/mm in 120 ℃ silicone oil for 30 min.

The surface micromorphology of the ceramics was characterized by Merlin scanning electron microscope (SEM). The crystal structure was analyzed by D/Max 2500 X-ray diffractometer (XRD). The density of the samples was measured using the Archimedean drainage method. The dielectric properties were tested using a TH2827 impedance analyzer. The ferroelectric properties were obtained using a TF Analyzer 2000 ferroelectric analyzer. The piezoelectric constant d₃₃ was measured using a ZJ-3A quasi-static d₃₃ tester. The mechanical quality factor Q_m was measured using a TH2839 impedance analyzer. The local domain structure and domain switching behavior were tested and analyzed using an MFP-3D atomic force microscope with piezoelectric force microscopy (PFM).

Results and discussion

High-density (relative density > 98%) KNN-x% MnO₂ ceramics were successfully prepared by hot pressing sintering process. XRD results show that MnO₂ doping does not change the perovskite phase structure of KNN. With the increase of Mn doping amount, the P_r of the ceramic shows a trend of first increasing and then slightly decreasing. At x = 1.0-1.5%, P_r reaches 14.92-18.32 μC/cm², d₃₃ can reach up to 106 pC/N, and both positive and negative strains are improved, reflecting enhanced ferroelectric and piezoelectric responses after Mn doping. PFM test shows that the switching voltage of the local ferroelectric domain gradually increases from 5 V to 20 V, indicating that Mn doping enhances the domain wall pinning effect. At the same time, the mechanical quality factor Q_m of the ceramic is significantly improved, with the highest value reaching 175, reflecting the typical "hard" doping behavior.

Conclusions

This study found that Mn-doped KNN ceramics exhibit an atypical "hard" doping effect for the high-density hot-pressed ceramics that is different from the traditional doping mechanism in lead-based ceramics, in which Q_m and P_r are simultaneously improved and d₃₃ is maintained at a high value. This atypical "hard" doping effect induced by Mn doping provides a new perspective for understanding the mechanism of element doping in the KNN system, and also provides significant guidance for the optimized design of high-performance lead-free piezoelectric ceramics.

Key words

hot-pressed sintering / potassium-sodium niobate / manganese doping / doping effect / electrical property

引用本文

钟子晴, 张乾宇, 徐泽, 曾繁达, 邢志鹏, 刘亦轩, 赵纯林, 王轲. Mn掺杂对热压烧结（K_0.5Na_0.5）NbO₃无铅压电陶瓷电学性能的影响. 硅酸盐学报, 2025 , 53 (9) : 2613 -2621 . DOI: 10.14062/j.issn.0454-5648.20240851

Ziqing ZHONG, Qianyu ZHANG, Ze XU, Fanda ZENG, Zhipeng XING, Yixuan LIU, Chunlin ZHAO, Ke WANG. Effects of Mn Doping on Electrical Properties in Hot-Pressed (K_0.5Na_0.5)NbO₃ Lead-Free Piezoceramics[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (9) : 2613 -2621 . DOI: 10.14062/j.issn.0454-5648.20240851

基金

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国家自然科学基金(52421001; 52325204)

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2025年第53卷第9期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240851

接收时间：2024-12-31
首发时间：2026-10-21
出版时间：2025-09-20

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收稿日期：2024-12-31
修回日期：2025-01-31

基金

国家自然科学基金(52421001; 52325204)

作者信息

^1．清华大学材料学院，新型陶瓷材料全国重点实验室，北京 100084

^2．乌镇实验室先进功能陶瓷材料研究中心，浙江嘉兴 314500

^3．福州大学材料科学与工程学院，福州 350108

通讯作者:

徐泽（1995—），男，博士，助理研究员；

刘亦轩（1995—），男，博士，助理研究员；

赵纯林（1990—），男，博士，副研究员。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240851

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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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