弛豫铁电陶瓷KNN-CZ的制备及储能性能研究

doi:10.16553/j.cnki.issn1000-985x.2024.0201

摘要/Abstract

摘要： 利用无铅介电材料进行机械能收集和能量储存是环境友好型储能设备的必然选择。本文采用固相反应法制备了(1-x)[(K_0.5Na_0.5)(Nb_0.9Sr_0.05Ta_0.08)O₃]-x(CaZrO₃) (KNN-CZ,x=0, 0.05, 0.07, 0.09)陶瓷,并对其相结构、微观形貌、介电及储能性能等进行了系统的研究。结果表明,KNN-CZ陶瓷表现出良好的弛豫性,且P-E电滞回线均较为“细瘦”,这是由于掺杂破坏了体系的长程有序性。其中,0.93KNN-0.07CZ的储能性能最优,有效储能密度为1.98 J/cm³,这是因为x=0.07时材料的储能效率(83.19%)和击穿场强较高(250 kV/cm)。本文研究结果提供了一种环保的、有前途的陶瓷电容器材料。

关键词: 弛豫铁电体, 无铅弛豫铁电陶瓷, KNN-CZ, 储能性能, 介电性能

Abstract: Utilizing lead-free dielectric materials for mechanical energy harvesting and energy storage is an inevitable choice for environmental friendly energy storage devices. In this paper, (1-x)[(K_0.5Na_0.5)(Nb_0.9Sr_0.05Ta_0.08)O₃]-x(CaZrO₃) (KNN-CZ, x=0, 0.05, 0.07, 0.09) ceramics were prepared by solid-state reaction method, and their phase structure, microscopic morphology, dielectric and energy-storage properties were systematically studied. The results show that the KNN-CZ ceramics exhibit good relaxation and the P-E hysteresis lines are “thin”, which is due to the long-range ordered structure of KNN is destroyed by doping. Among them, 0.93KNN-0.07CZ has the best energy storage performance with effective energy storage density of 1.98 J/cm³, which is due to the higher energy storage efficiency (83.19%) and breakdown field strength (250 kV/cm) at x=0.07. The above results provide an environmentally friendly and promising material for ceramic capacitors.

Key words: relaxor ferroelectric, lead-free relaxation ferroelectric ceramics, KNN-CZ, energy storage performance, dielectric property

中图分类号:

庞国旺, 张盼, 尹伟, 杨亚宏, 马亚斌, 杨菲宇, 马钧亮, 王平, 秦彦军, 李萍. 弛豫铁电陶瓷KNN-CZ的制备及储能性能研究[J]. 人工晶体学报, 2025, 54(1): 139-145.

PANG Guowang, ZHANG Pan, YIN Wei, YANG Yahong, MA Yabin, YANG Feiyu, MA Junliang, WANG Ping, QIN Yanjun, LI Ping. Preparation and Energy Storage Performance of KNN-CZ Relaxation Ferroelectric Ceramics[J]. Journal of Synthetic Crystals, 2025, 54(1): 139-145.

参考文献

[1] GOMASU S, SAHA S, GHOSH S, et al. High energy density achieved in novel lead-free BiFeO₃-CaTiO₃ ferroelectric ceramics for high-temperature energy storage applications[J]. ACS Applied Materials & Interfaces, 2024, 16(3): 3654-3664.
[2] XIANG L, YUAN H L, YANG F, et al. Lowered ferromagnetic resonance linewidth and enhanced spin wave linewidth of nickel-based ferrite ceramics using hot-pressing method[J]. Ceramics International, 2024, 50(5): 8277-8283.
[3] PENG X W, YANG B, DENG D J, et al. Lead-free KNN-based ceramics incorporated with Bi(Zn_2/3Nb_1/3)O₃ possessing excellent optical transmittance and superior energy storage density[J]. Materials Research Bulletin, 2023, 165: 112294.
[4] 苗健, 邵辉, 曹瑞龙. K_0.5Na_0.5NbO₃掺杂对0.94Bi_0.5Na_0.5TiO₃-0.06BaTiO₃陶瓷储能性能的影响[J]. 人工晶体学报, 2024, 53(5): 882-888.
MIAO J, SHAO H, CAO R L. Effect of K_0.5Na_0.5NbO₃ doping on the energy storage performance of 0.94Bi_0.5Na_0.5TiO₃-0.06BaTiO₃ ceramics[J]. Journal of Synthetic Crystals, 2024, 53(5): 882-888 (in Chinese).
[5] MA Y M, YANG S X, ZHAO C L, et al. Photochromic and electric field-regulating luminescence in high-transparent (K, Na)NbO₃-based ferroelectric ceramics with two-phase coexistence[J]. ACS Applied Materials & Interfaces, 2022, 14(31): 35940-35948.
[6] ZHANG M, YANG H B, YU Y W, et al. Energy storage performance of K_0.5Na_0.5NbO₃-based ceramics modified by Bi(Zn_2/3(Nb_0.85Ta_0.15)_1/3)O₃[J]. Chemical Engineering Journal, 2021, 425: 131465.
[7] AN Z X, YAO Y, WANG J, et al. Energy storage performance and piezoelectric response of silver niobate antiferroelectric thin film[J]. Ceramics International, 2024, 50(7): 12427-12433.
[8] GOYAL R K, CHANDRASEKHAR M, SAHOO S. Structural, dielectric and electrical transport properties of thermal stable (1-x)K_0.5Bi_0.5TiO₃-xBaTiO₃ ceramics[J]. Ceramics International, 2024, 50(5): 7978-7987.
[9] XIE A W, FU J, ZUO R Z, et al. Supercritical relaxor nanograined ferroelectrics for ultrahigh-energy-storage capacitors[J]. Advanced Materials, 2022, 34(34): e2204356.
[10] XIAO S B, SUI H T, WU F L, et al. Optimizing energy storage performance of 0.9(Na_0.5Bi_0.5)(Fe_0.02Ti_0.98)O₃-0.1SrTiO₃ flexible capacitor via relaxation strategy[J]. Ceramics International, 2024, 50(5): 7713-7722.
[11] WANG W, ZHANG L Y, LI C, et al. Effective strategy to improve energy storage properties in lead-free (Ba_0.8Sr_0.2)TiO₃-Bi(Mg_0.5Zr_0.5)O₃ relaxor ferroelectric ceramics[J]. Chemical Engineering Journal, 2022, 446: 137389.
[12] WANG M Q, LIN Y, YUAN Q B, et al. Significantly improved energy storage performances of K_0.5Na_0.5NbO₃ lead-free ceramics via a composition optimization strategy[J]. Inorganic Chemistry Frontiers, 2023, 10(15): 4578-4586.
[13] XIAO W R, LIU Z, ZHANG C, et al. Free energy regulation and domain engineering of BaTiO₃-NaNbO₃ ceramics for superior dielectric energy storage performance[J]. Chemical Engineering Journal, 2023, 461: 142070.
[14] 任香, 李筱, 郭中秋, 等. 稀土Ce⁴⁺掺杂对BCT-BZNT陶瓷结构和储能性能的影响[J]. 硅酸盐学报, 2024, 52(4): 1355-1364.
REN X, LI X, GUO Z Q, et al. Effect of rare-earth Ce⁴⁺ doping on structure and energy storage properties of BCT-BZNT ceramics[J]. Journal of the Chinese Ceramic Society, 2024, 52(4): 1355-1364 (in Chinese).
[15] DAI Z H, ZHANG F B, RAFIQ M N, et al. Design of a KNN-BZT ceramic with high energy storage properties and transmittance under low electric fields[J]. ACS Omega, 2023, 8(8): 7883-7890.
[16] LIU C X, DAI Z H, FENG Y, et al. High energy storage characteristics for Ba_0.9Sr_0.1TiO₃ (BST) doped Na_0.7Bi_0.1NbO₃ (NBN) ceramics[J]. Journal of Energy Storage, 2023, 73: 109044.
[17] ZHANG M, YANG H B, LIN Y, et al. Significant increase in comprehensive energy storage performance of potassium sodium niobate-based ceramics via synergistic optimization strategy[J]. Energy Storage Materials, 2022, 45: 861-868.
[18] FU H X, LI S, LIN Y C, et al. Enhancement of piezo-photocatalytic activity in perovskite (Bi_0.2Na_0.2Ba_0.2K_0.2La_0.2)TiO₃ oxides via high entropy induced lattice distortion and energy band reconfiguration[J]. Ceramics International, 2024, 50(6): 9159-9168.
[19] KHAN N U, YUN W S, ULLAH A, et al. Large electrostrictive response via tailoring ergodic relaxor state in Bi_1/2Na_1/2TiO₃- based ceramics with Bi(Mn_1/2Ce_1/2)O₃ end-member[J]. Ceramics International, 2024, 50(6): 8790-8799.
[20] LU J X, YAO Z H, HAO H, et al. Antiferroelectric ceramic capacitors with high energy-storage densities and reduced sintering temperature[J]. Ceramics International, 2024, 50(1): 1941-1946.
[21] LI W Q, WANG S B, LIN C L, et al. Enhanced energy-storage density in (Pb_0.98La_0.02)(Zr_0.45-xSn_0.55Hf_x)_0.995O₃ antiferroelectric ceramics[J]. Scripta Materialia, 2024, 242: 115959.
[22] DENG D, IRSHAD M S, KONG X, et al. Potassium sodium niobate-based transparent ceramics with high piezoelectricity and enhanced energy storage density[J]. Journal of Alloys and Compounds, 2023, 953: 170081.
[23] GAO X Y, CHENG Z X, CHEN Z B, et al. The mechanism for the enhanced piezoelectricity in multi-elements doped (K, Na)NbO₃ ceramics[J]. Nature Communications, 2021, 12(1): 881.
[24] CHEN Q F, GAO T T, LANG R, et al. Achieving outstanding temperature stability in KNN-based lead-free ceramics for energy storage behavior[J]. Journal of the European Ceramic Society, 2023, 43(6): 2442-2451.
[25] DAI Z H, LI D Y, ZHOU Z J, et al. A strategy for high performance of energy storage and transparency in KNN-based ferroelectric ceramics[J]. Chemical Engineering Journal, 2022, 427: 131959.
[26] YANG T H, YE W H, LIN J W, et al. Enhanced energy storage performance in Bi(Mg_1/3Zn_1/3Ta_1/3)O₃-doped (K_1/2Na_1/2)NbO₃ high-entropy ceramics[J]. Ceramics International, 2023, 49(22): 36173-36180.
[27] CHAI Q Z, PENG Z H, WU D, et al. Significant improvement of comprehensive energy storage performance and transparency in Sr_0.7La_0.2TiO₃-doped (K, Na)NbO₃ lead-free ceramics[J]. Journal of Alloys and Compounds, 2023, 968: 171908.
[28] DAI Z H, WANG S B, LIU Y, et al. Energy storage performance of SrSc_0.5Nb_0.5O₃ modified (Bi, Na)TiO₃-based ceramic under low electric fields[J]. Journal of the American Ceramic Society, 2023, 106(4): 2366-2374.
[29] 盛林生, 沈超, 姜梦琦, 等. (1-x)(0.75K_0.5Bi_0.5TiO₃-0.25BiFeO₃)-xNa_0.73Bi_0.09NbO₃电介质陶瓷的微观结构与储能性能[J]. 硅酸盐学报, 2024, 52(4): 1335-1344.
SHENG L S, SHEN C, JIANG M Q, et al. Microstructure and energy storage performance of (1-x)(0.75K_0.5Bi_0.5TiO₃-0.25BiFeO₃)-xNa_0.73Bi_0.09NbO₃ ceramics[J]. Journal of the Chinese Ceramic Society, 2024, 52(4): 1335-1344 (in Chinese).
[30] 肖齐龙, 王世宇, 蒋芮, 等. ZnNb₂O₆掺杂BNT基无铅弛豫铁电体陶瓷的性能研究[J]. 人工晶体学报, 2024, 53(1): 154-162.
XIAO Q L, WANG S Y, JIANG R, et al. Properties of ZnNb₂O₆ doped BNT-based lead-free relaxor ferroelectric ceramics[J]. Journal of Synthetic Crystals, 2024, 53(1): 154-162 (in Chinese).
[31] ZHU W, SHEN Z Y, DENG W, et al. A review: (Bi, Na)TiO₃ (BNT)-based energy storage ceramics[J]. Journal of Materiomics, 2024, 10(1): 86-123.
[32] NING Y T, PU Y P, WU C H, et al. Design strategy of high-entropy perovskite energy-storage ceramics: a review[J]. Journal of the European Ceramic Society, 2024, 44(8): 4831-4843.