NiMn layered double hydroxides with promoted surface defects as bifunctional electrocatalysts for rechargeable zinc–air batteries

IF 5.9 3区材料科学 Q2 CHEMISTRY, PHYSICAL

FlatChem Pub Date : 2024-04-24 DOI:10.1016/j.flatc.2024.100664

Oscar Ambriz-Peláez , José Béjar , Anabel D. Delgado , Claramaría Rodríguez-González , C.M. Ramos-Castillo , Lorena Álvarez-Contreras , Minerva Guerra-Balcázar , Noé Arjona

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Abstract

Layered double hydroxides (LDHs) are attractive bidimensional materials for electrochemical applications because of their high activity in the oxygen evolution reaction (OER). However, their limited bifunctionality due to the slow kinetics of the oxygen reduction reaction (ORR) is a bottleneck for their use in secondary Zn-air batteries (ZABs). In this work, cobalt-free NiMn LDHs were rationally designed by optimizing the Ni composition and incorporating surface defects onto the LDH (oxygen vacancies, Ov) while performing interface engineering using a carbonaceous support enriched with nitrogen heteroatoms. The LDHs without induced defects presented the optimal activity for the OER at a 3:1 Ni/Mn atomic ratio (onset potential 1.47 V vs. 1.45 V for IrO₂/C), while the ORR was unfavorable. However, the further optimization by introducing Ov and N–heteroatoms (labeled as Ov-NiMn LDH/NCNTG) allowed bifunctionality by improving the onset potential to 0.90 V while decreasing the half-wave potential difference from 180 mV for the material without induced defects to 100 mV, and by improving the limiting current density by a factor of two. In this regard, density of states (DOS) calculations suggested that surface defects improved the electronic transfer while decreasing the oxygen adsorption energy. ZAB tests indicated that the interface-engineered material allowed a battery voltage of 1.47 V, and a power density of 64 mW cm⁻². The battery also maintained stability over 180 charge/discharge cycles at 10 mA cm⁻² (50 h), with ΔV below 150 mV between the initial and final cycles.

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具有促进表面缺陷的镍锰层状双氢氧化物作为可充电锌-空气电池的双功能电催化剂

层状双氢氧化物（LDHs）因其在氧进化反应（OER）中的高活性而成为电化学应用中极具吸引力的二维材料。然而，由于氧还原反应（ORR）的动力学速度较慢，它们的双功能性受到限制，这是它们用于二次锌-空气电池（ZAB）的瓶颈。在这项工作中，通过优化镍的成分，并在 LDH 上加入表面缺陷（氧空位，Ov），同时使用富含氮杂质原子的碳质支撑进行界面工程，合理地设计了无钴镍锰 LDH。在镍/锰原子比为 3:1 时，无诱导缺陷的 LDH 具有最佳的 OER 活性（起始电位为 1.47 V，IrO2/C 为 1.45 V），而 ORR 则不理想。然而，通过引入 Ov 原子和 N 原子（标记为 Ov-NiMn LDH/NCNTG）进一步优化后，起始电位提高到了 0.90 V，同时半波电位差从无诱导缺陷材料的 180 mV 降到了 100 mV，极限电流密度提高了 2 倍，从而实现了双功能性。在这方面，状态密度（DOS）计算表明，表面缺陷改善了电子转移，同时降低了氧气吸附能。ZAB 测试表明，界面工程材料可使电池电压达到 1.47 V，功率密度达到 64 mW cm-2。在 10 mA cm-2 的条件下，该电池还能在 180 个充放电循环（50 小时）中保持稳定，初始循环和最终循环之间的ΔV 低于 150 mV。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

FlatChem Multiple-

CiteScore

8.40

自引率

6.50%

发文量

104

审稿时长

26 days

期刊介绍： FlatChem - Chemistry of Flat Materials, a new voice in the community, publishes original and significant, cutting-edge research related to the chemistry of graphene and related 2D & layered materials. The overall aim of the journal is to combine the chemistry and applications of these materials, where the submission of communications, full papers, and concepts should contain chemistry in a materials context, which can be both experimental and/or theoretical. In addition to original research articles, FlatChem also offers reviews, minireviews, highlights and perspectives on the future of this research area with the scientific leaders in fields related to Flat Materials. Topics of interest include, but are not limited to, the following: -Design, synthesis, applications and investigation of graphene, graphene related materials and other 2D & layered materials (for example Silicene, Germanene, Phosphorene, MXenes, Boron nitride, Transition metal dichalcogenides) -Characterization of these materials using all forms of spectroscopy and microscopy techniques -Chemical modification or functionalization and dispersion of these materials, as well as interactions with other materials -Exploring the surface chemistry of these materials for applications in: Sensors or detectors in electrochemical/Lab on a Chip devices, Composite materials, Membranes, Environment technology, Catalysis for energy storage and conversion (for example fuel cells, supercapacitors, batteries, hydrogen storage), Biomedical technology (drug delivery, biosensing, bioimaging)