硅酸盐学报

柔性Pb_0.99Sm_0.01（Mg_1/3Nb_2/3）_0.68Ti_0.32O₃弛豫铁电薄膜储能特性

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吕盼盼 ¹ , 石长清 ¹ , 辛乐 ³ , 战行 ¹ , 张书志 ¹ , 王佳 ¹ , 李瑞航 ¹ , 李存成 ¹ , 任路超 ¹ , 杨长红 ⁴ , 张明伟 ¹^,² , 程新 ⁴

硅酸盐学报 | 电介质储能材料专刊—研究论文 2024,52(4): 1301-1309

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硅酸盐学报 |电介质储能材料专刊—研究论文 2024 , 52 (4) : 1301 -1309

柔性Pb_0.99Sm_0.01（Mg_1/3Nb_2/3）_0.68Ti_0.32O₃弛豫铁电薄膜储能特性

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吕盼盼¹, 石长清¹, 辛乐³, 战行¹, 张书志¹, 王佳¹, 李瑞航¹, 李存成¹, 任路超¹, 杨长红⁴, 张明伟¹^,², 程新⁴

作者信息

^1．山东理工大学材料科学与工程学院，山东淄博 255000

^2．山东理工大学分析测试中心，山东淄博 255000

^3．淄博师范高等专科学校数理系，山东淄博 255130

^4．济南大学，山东省建筑材料制备与测试技术重点实验室，济南 250022

通讯作者:

张明伟（1982—），男，博士，教授。

作者简介:

吕盼盼（1990—），女，博士，讲师。

Study on Energy Storage Performance of Flexible Pb_0.99Sm_0.01(Mg_1/3Nb_2/3)_0.68Ti_0.32O₃ Relaxor-Ferroelectric Film

Panpan LV¹, Changqing SHI¹, Le XIN³, Hang ZHAN¹, Shuzhi ZHANG¹, Jia WANG¹, Ruihang LI¹, Cuncheng LI¹, Luchao REN¹, Changhong YANG⁴, Mingwei ZHANG¹^,², Xin CHENG⁴

Affiliations

^1.School of Materials Science and Engineering, Shandong University of Technology, Zibo 255000, Shandong, China

^2.Analytical Texting Center, Shandong University of Technology, Zibo 255000, Shandong, China

^3.Department of Mathematics and Physics, Zibo Normal College, Zibo 255130, Shandong, China

^4.Shandong Provincial Key Laboratory of Preparation and Measurement of Building Materials, University of Jinan, Jinan 250022, Shandong, China

Corresponding Author:

ZHANG Mingwei (1982-), male, Ph.D., Professor. E-mail: zmwsdut@163.com

LV Panpan (1990-), female, Ph.D., Lecture. E-mail: lvpp@sdut.edu.cn

出版时间: 2024-04-20 doi: 10.14062/j.issn.0454-5648.20230758

文章导航

摘要

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弛豫铁电薄膜电容器因具有细长电滞回线和高能量转化效率成为介电储能应用的理想选择。本工作采用溶胶凝胶法在沉积有LaNiO₃缓冲层的云母基底上直接制备了柔性Pb_0.99Sm_0.01（Mg_1/3Nb_2/3）_0.68Ti_0.32O₃（PSMNT）薄膜，系统研究了柔性PSMNT膜的微观结构、介电、铁电和储能性能。X射线衍射结果表明薄膜样品为单一钙钛矿相。扫描电子显微镜结果显示薄膜的晶粒尺寸均匀且致密。在极化特性方面，所制备的柔性PSMNT薄膜因具有弛豫性，其电滞回线呈现出纤细束腰特征，在外加电场2 468 kV/cm下，其最大饱和极化为74.5 μC/cm²，剩余极化为16.4 μC/cm²。薄膜电容器击穿前最大可释放能量密度和储能效率分为40.7 J/cm³和70%，并且表现出较好的频率（1~20 kHz）和温度（25~120 ℃）稳定性。此外，样品借助云母衬底可实现优异的可弯折性，在弯曲半径R低至2 mm和弯曲疲劳循环1 000次（R=4 mm）后，其储能性能仍可保持。此研究表明以云母为基底的PSMNT弛豫薄膜在柔性储能领域具有很大的应用潜力。

关键词

铌镁酸铅钛酸铅基薄膜 / 弛豫铁电体 / 介电储能 / 柔性

Abstract

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Introduction

Global energy crisis has sparked unprecedented momentum for renewable energy sources. Energy storage systems such as electrochemical capacitors, batteries, fuel cells, and dielectric capacitors are considered as the most important technologies to address rapidly growing energy demands and environmental concerns. In comparison with batteries or fuel cells, dielectric capacitors possess high power density resulting from their faster charging/discharging characteristics, which are advantageous for power electronics and pulse power applications. The majority of materials used for fabrication of dielectric capacitors consist of linear dielectrics, ferroelectrics, relaxor ferroelectrics, and anti-ferroelectrics. Among these materials, relaxor ferroelectrics are the most popular choice for capacitor applications because of their lack of long-range order ferroelectric domains. (1-x)Pb(Mg_1/3Nb_2/3)O₃-xPbTiO₃ (PMNT) as the typical representative of relaxor ferroelectrics, which possesses small remanent polarization and low coercive electric field, enjoys promising prospects in dielectric capacitor application. Nevertheless, limited by its low E_b, the energy storage density and efficiency for pure PMNT film are not yet ideal. Moreover, it is difficult for traditional PMNT film to be bendable due to limitations of rigid substrates, which lead to descend of flexibility and cannot meet modern flexible electronic production requirements. In this paper, to overcoming the bottlenecks of inflexibility and inferior energy storage performance of the pure PMNT films, rare-earth element of Sm and promising LaNiO₃ (LNO) buffer layer were introduced into PMNT thin film. To obtain extraordinary flexibility, two-dimensional mica substrate was used to prepare the modified PMNT film via a simple sol-gel method. The microstructure, dielectric, ferroelectric and energy storage properties of the flexible Pb_0.99Sm_0.01(Mg_1/3Nb_2/3)_0.68Ti_0.32O₃ (PSMNT) film were studied systematically.

Methods

The PSMNT and LNO films were prepared using a sol-gel method. First, niobium ethoxide (Nb(OC₂H₅)₅) was dissolved in 2-methoxyethanol at room temperature. And tetrabutyl titanate (Ti(OC₄H₉)₄) was stabilized in acetylacetone. Second, lead (Ⅱ) acetate trihydrate (Pb(CH₃COO)₂·3H₂O) with 10% excess Pb, samarium (Ⅲ) nitrate hexahydrate (Sm(NO₃)₃·6H₂O), and magnesium (Ⅱ) acetate tetrahydrate (Mg(CH₃COO)₂·4H₂O) were dissolved together in a mixed solvent of glacial acetic acid and 2-methoxyethanol (volume ratio of 2∶1) at room temperature. Then, the solutions above were mixed to obtain the PSMNT precursor. To prepare the LNO precursor, the lanthanum (Ⅲ) nitrate hexahydrate (La(NO₃)₃·6H₂O) and nickel (Ⅱ) acetate tetrahydrate (Ni(CH₃COO)₂·4H₂O) were dissolved in 2-methoxyethanol. The concentration of the PSMNT and LNO precursors were 0.2 mol·L^-1 and 0.1 mol·L^-1, respectively.

The flexible mica substrate was separated from the bulk fluorphlogopite mica crystal by mechanical exfoliation using a razor blade in deionized water. When the thickness of the mica substrate was reduced to ~15 μm, good flexibility could be realized. The LNO precursor solution was firstly spin-coated onto the mica substrate, followed by an annealing process at 750 ℃ for 2 min. Then, the PSMNT precursor was spin-coated on the surface of the freshly prepared LNO layer and then the wet film was annealed at 700 ℃. The spin-coating and annealing process was repeated to achieve a desirable film thickness. Finally, Au top electrodes, ~200 μm in diameter, were sputtered on the film surface through a shadow mask for electrical properties measurements.

Results and discussion

PSMNT and PMNT thin films were directly deposited on LaNiO₃ buffered mica substrate via simple one-step fabrication process. X-ray diffraction (XRD) results indicated that the crystal structure of PSMNT film was pure perovskite phase without detectable secondary phases. Scanning electron microscope (SEM) measurement revealed that the film exhibited compact microstructure with uniform crystal grain distribution, indicating that the PSMNT film can be successfully grown on the LaNiO₃ buffered mica substrate. In terms of polarization characteristics, slim hysteresis loop with a large maximum polarization P_max (~74.5 μC/cm²) and a small remnant polarization P_r (~16.4 μC/cm²) was observed in the PSMNT film under the electric field of 2 468 kV/cm, while fatted P-E loop was observed in the PMNT film. The leakage current density in the PSMNT film is almost an order of magnitude lower than the pure PMNT sample, indicating the success of the introduction of Sm in improving of electric resistance. The recoverable energy storage density for the PSMNT film capacitor at the maximum electric field was 40.7 J/cm³, and the corresponding energy-storage efficiency was 70% due to its high breakdown strength and strong relaxor dispersion. The PSMNT film capacitor also exhibits excellent stability in energy storage performance in a wide operating frequency (1-20 kHz) and broad temperature (25-120 ℃) ranges. With the assistance of a mica substrate, the all-inorganic PSMNT/LNO/mica capacitor possesses an outstanding mechanical-bending resistance without obvious deterioration in its energy storage performance even down to a bending radius of 2 mm or repeated bending for 10³ cycles.

Conclusions

The main conclusions of this paper are summarized as following. Flexible Pb_0.99Sm_0.01(Mg_1/3Nb_2/3)_0.68Ti_0.32O₃ (PSMNT) film was successfully deposited on LaNiO₃ buffered mica substrate by a simple sol-gel method. A high recoverable energy density of 40.7 J/cm³ and efficiency of 70% were realized in the fabricated film capacitor. The energy storage performance was quite stable in a wide temperature (25-120 ℃) and frequency (1-20 kHz) ranges. Meanwhile, the designed PSMNT film capacitor exhibited superior mechanical-bending resistance since it is attached on the bendable mica substrate, and its energy storage behavior did not show obvious deterioration even under a small bending radius of R=2 mm and 1 000 mechanical bending cycles (R=4 mm). This study showed that flexible PSMNT thin film on mica platform has bright prospects in future flexible electronics application for energy storage.

Key words

lead magnesium niobate-lead titanate thin film / relaxor ferroelectrics / dielectric energy storage / flexibility

引用本文

吕盼盼, 石长清, 辛乐, 战行, 张书志, 王佳, 李瑞航, 李存成, 任路超, 杨长红, 张明伟, 程新. 柔性Pb_0.99Sm_0.01（Mg_1/3Nb_2/3）_0.68Ti_0.32O₃弛豫铁电薄膜储能特性. 硅酸盐学报, 2024 , 52 (4) : 1301 -1309 . DOI: 10.14062/j.issn.0454-5648.20230758

Panpan LV, Changqing SHI, Le XIN, Hang ZHAN, Shuzhi ZHANG, Jia WANG, Ruihang LI, Cuncheng LI, Luchao REN, Changhong YANG, Mingwei ZHANG, Xin CHENG. Study on Energy Storage Performance of Flexible Pb_0.99Sm_0.01(Mg_1/3Nb_2/3)_0.68Ti_0.32O₃ Relaxor-Ferroelectric Film[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (4) : 1301 -1309 . DOI: 10.14062/j.issn.0454-5648.20230758

基金

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国家自然科学基金青年科学基金(52302145)
山东省自然科学基金青年基金(ZR2023QE126)
国家自然科学基金面上项目(51972144)

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2024年第52卷第4期

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文章信息

doi: 10.14062/j.issn.0454-5648.20230758

接收时间：2023-09-29
首发时间：2026-10-22
出版时间：2024-04-20

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收稿日期：2023-09-29
修回日期：2023-11-03

基金

国家自然科学基金青年科学基金(52302145)

山东省自然科学基金青年基金(ZR2023QE126)

国家自然科学基金面上项目(51972144)

作者信息

^1．山东理工大学材料科学与工程学院，山东淄博 255000

^2．山东理工大学分析测试中心，山东淄博 255000

^3．淄博师范高等专科学校数理系，山东淄博 255130

^4．济南大学，山东省建筑材料制备与测试技术重点实验室，济南 250022

通讯作者:

张明伟（1982—），男，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20230758

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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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