Wu Dirui, Dong Wen, Yang Ying, Chen Long, Xiao Wenrong, Zhang Chao, Zou Kailun, Zhou Wenjing, Luo Wei, Zhang Guangzu, Fu Qiuyun, Jiang Shenglin
School of Integrated Circuits & Wuhan National Lab for Optoelectronics Laboratory & Engineering Research Center for Functional Ceramics of the Ministry of Education, Huazhong University of Science and Technology, Wuhan 430074, P. R. China.
ACS Appl Mater Interfaces. 2023 Mar 22;15(11):14495-14501. doi: 10.1021/acsami.2c12300. Epub 2023 Mar 13.
Antiferroelectric materials are promising to be used for power capacitive devices. To improve the energy storage performance, solid-solution and defect engineering are widely used to suppress the long-range order by introducing local heterogeneities. However, both methods generally deteriorate either the maximum polarization or breakdown electric field due to damaged intrinsic polarization or increased leakage. Here, we show that forming defect-dipole clusters by A-B site acceptor-donor co-doping in antiferroelectrics can comprehensively enhance the energy storage performance. We took the La-Mn co-doped (PbBaLa)(ZrSnTi)O (PBLZST) as an example. For co-doping with unequal amounts, high dielectric loss, impurity phase, and decreased polarization were observed. By contrast, La and Mn in an equal amount of co-doping can significantly improve the overall energy storage performance. An over 48% increasement in both the maximum polarization (62.7 μC/cm) and breakdown electric field (242.6 kV/cm) was obtained in 1 mol % La and 1 mol % Mn equally co-doped PBLZST, followed by a nearly two-time enhancement in (6.52 J/cm) compared with that of the pure matrix. Moreover, a high energy storage efficiency of 86.3% with an enhanced temperature stability over a wide temperature range can be achieved. The defect-dipole clusters associated with charge-compensated co-doping are suggested to contribute to an enhanced dielectric permittivity, linear polarization behavior, and maximum polarization strength compared with that of the unequal co-doping cases. The defect-dipole clusters are suggested to couple with the host, leading to a high energy storage performance. The proposed strategy is believed to be applicable to modify the energy storage behavior of antiferroelectrics.
反铁电材料有望用于功率电容器件。为了提高储能性能，固溶体和缺陷工程被广泛用于通过引入局部不均匀性来抑制长程有序。然而，由于本征极化受损或泄漏增加，这两种方法通常都会降低最大极化强度或击穿电场。在此，我们表明在反铁电体中通过A-B位受主-施主共掺杂形成缺陷偶极子簇可以全面提高储能性能。我们以La-Mn共掺杂的(PbBaLa)(ZrSnTi)O（PBLZST）为例。对于不等量的共掺杂，观察到高介电损耗、杂质相和极化强度降低。相比之下，等量的La和Mn共掺杂可以显著提高整体储能性能。在1 mol% La和1 mol% Mn等量共掺杂的PBLZST中，最大极化强度（62.7 μC/cm²）和击穿电场（242.6 kV/cm）均提高了48%以上，随后其储能密度（6.52 J/cm³）相比纯基体提高了近两倍。此外，还可实现高达86.3%的高储能效率，且在很宽的温度范围内具有增强的温度稳定性。与不等量共掺杂情况相比，与电荷补偿共掺杂相关的缺陷偶极子簇被认为有助于提高介电常数、线性极化行为和最大极化强度。缺陷偶极子簇被认为与主体耦合，从而导致高储能性能。所提出的策略被认为适用于改变反铁电体的储能行为。
