香港城市大学李扬扬开发了含氟的高价高熵层状双氢氧化物，用于高效、持久的锌空气电池。相关研究成果发表在2024年9月17日出版的《德国应用化学》。

目前迫切需要高效稳定的双功能析氧反应（OER）和氧还原反应（ORR）催化剂，来释放锌空气电池（ZABs）的全部潜力。高价氧化物（HVO）和高熵氧化物（HEO），因其最佳的电子结构和稳定性而成为合适的候选者，但合成要求很高。

该文中，研究人员通过多离子共沉淀方便地制备了，一种低成本的含氟高价高熵层状双氢氧化物（HV-HE-LDH）（FeCoNi₂F₄(OH)₄），其中F-牢固地嵌入到各个氢氧化物层中。光谱检测和理论模拟表明，在FeCoNi₂F₄(OH)₄中获得了高价金属阳离子，这扩大了金属3d和O2p之间的能带重叠，增强了电子电导率和电荷转移，从而提供了高的本征OER催化活性。

更重要的是，FeCoNi₂F₄(OH)₄中强化的金属氧（M-O）键和稳定的八面体几何结构（M-O（F）6）阻止了结构重组，从而提供了长期的催化稳定性。此外，构建了一个高效的能够进行快速氧气输送的三相反应界面，显著提高了ORR活性。用FeCoNi₂F₄(OH)₄@HCC（疏水碳布）阴极组装的ZABs，具有高往返能量效率（在10mA cm^-2下为60.6%）和长期稳定性（在1050次充放电循环后效率保持在58.8%）的卓越性能。

附：英文原文

Title: Fluorine-lodged high-valent high-entropy layered double hydroxide for efficient, long-lasting zinc-air batteries

Author: Bo Li, Jing Zhong, Hao Wang, Jialun Gu, Fucong Lyu, Shengmei Chen, Haikun Wu, Lanxi Li, Chunyi Zhi, Jian Lu, Yang Yang Li

Issue&Volume: 2024-09-17

Abstract: Efficient and stable bifunctional oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) catalysts are urgently needed to unlock the full potential of zinc-air batteries (ZABs). High-valence oxides (HVOs) and high entropy oxides (HEOs) are suitable candidates for their optimal electronic structures and stability but suffer from demanding synthesis. Here, a low-cost fluorine-lodged high-valent high-entropy layered double hydroxide (HV-HE-LDH) (FeCoNi2F4(OH)4) is conveniently prepared through multi-ions co-precipitation, where F- are firmly embedded into the individual hydroxide layers. Spectroscopic detections and theoretical simulations reveal high valent metal cations are obtained in FeCoNi2F4(OH)4, which enlarge the energy band overlap between metal 3d and O 2p, enhancing the electronic conductivity and charge transfer, thus affording high intrinsic OER catalytic activity. More importantly, the strengthened metal-oxygen (M-O) bonds and stable octahedral geometry (M-O(F)6) in FeCoNi2F4(OH)4 prevent structural reorganization, rendering long-term catalytic stability. Furthermore, an efficient three-phase reaction interface with fast oxygen transportation was constructed, significantly improving the ORR activity. ZABs assembled with FeCoNi2F4(OH)4@HCC (hydrophobic carbon cloth) cathodes deliver a top performance with high round-trip energy efficiency (60.6% at 10 mA cm-2) and long-term stability (efficiency remains at 58.8% after 1050 charge-discharge cycles).

DOI: 10.1002/anie.202410978

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202410978