Cation substitution enabled electron rearrangement in high-entropy perovskite oxides for enhanced supercapacitor performance

IF 9.1 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Progress in Solid State Chemistry Pub Date : 2025-06-24 DOI:10.1016/j.progsolidstchem.2025.100536

Xiaoying Hu, Bo Wang, Xiaotong Zhou, Junzhi Li

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Abstract

The controllable synthesis of high-entropy perovskite oxides and the modulation of their electronic structures are crucial for enhancing the electrochemical performance of supercapacitors. However, it remains challenging to regulate the electronic configuration of B-site elements via A-site doping. In this study, we have reconstructed the electron configuration of B-site elements in high-entropy perovskites through Sm doping, and obtained high-entropy perovskite oxides La_1-xSm_x (Mn_0·2Fe_0·2Co_0·2Ni_0·2Cr_0.2)O₃ (LaSmTMO₃−x) with abundant valence states. The fabricated LaSmTMO₃−0.2 exhibits high specific capacitance of 1367.3 F g⁻¹ at 0.5 A g⁻¹. Besides, the asymmetric supercapacitor (ASC) based on LaSmTMO₃−0.2 exhibits an impressive energy density of 41.2 Wh kg⁻¹ at a power density of 400 W kg⁻¹, with a specific capacity retention of 87.1 % after 10000 cycles. The experimental results demonstrate that superior supercapacitor performance can be attributed to electron rearrangement induced by Sm doping, leading to the formation of active metal species with multiple oxidation states. Simultaneously, Sm doping significantly improves structural integrity, electronic conductivity, and ion transfer kinetics. This work emphasizes the importance of A-site regulation of high entropy perovskite oxides for improving electrochemical performance and provides A new direction for the design of perovskite oxides in energy storage and conversion systems.

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阳离子取代使高熵钙钛矿氧化物中的电子重排增强了超级电容器的性能

高熵钙钛矿氧化物的可控合成及其电子结构的调制是提高超级电容器电化学性能的关键。然而，通过掺杂a位来调节b位元素的电子构型仍然具有挑战性。本研究通过Sm掺杂重建了高熵钙钛矿中b位元素的电子构型，得到了价态丰富的高熵钙钛矿氧化物La1-xSmx (Mn0·2Fe0·2Co0·2Ni0·2Cr0.2)O3 （LaSmTMO3−x）。制备的LaSmTMO3−0.2在0.5 A g−1时具有1367.3 F g−1的高比电容。此外，基于LaSmTMO3−0.2的非对称超级电容器（ASC）在功率密度为400 W kg−1时，能量密度为41.2 Wh kg−1，循环10000次后比容量保持率为87.1%。实验结果表明，优异的超级电容器性能可归因于Sm掺杂引起的电子重排，从而形成具有多种氧化态的活性金属。同时，Sm掺杂显著改善了结构完整性、电子导电性和离子转移动力学。本研究强调了高熵钙钛矿氧化物的A位调控对提高电化学性能的重要性，为钙钛矿氧化物在储能和转换系统中的设计提供了新的方向。

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来源期刊

Progress in Solid State Chemistry 化学-无机化学与核化学

CiteScore

14.10

自引率

3.30%

发文量

期刊介绍： Progress in Solid State Chemistry offers critical reviews and specialized articles written by leading experts in the field, providing a comprehensive view of solid-state chemistry. It addresses the challenge of dispersed literature by offering up-to-date assessments of research progress and recent developments. Emphasis is placed on the relationship between physical properties and structural chemistry, particularly imperfections like vacancies and dislocations. The reviews published in Progress in Solid State Chemistry emphasize critical evaluation of the field, along with indications of current problems and future directions. Papers are not intended to be bibliographic in nature but rather to inform a broad range of readers in an inherently multidisciplinary field by providing expert treatises oriented both towards specialists in different areas of the solid state and towards nonspecialists. The authorship is international, and the subject matter will be of interest to chemists, materials scientists, physicists, metallurgists, crystallographers, ceramists, and engineers interested in the solid state.