Porphyrinic N4 channels of zinc ions for the electrochemical reversibility of zinc plating/stripping†

IF 12.2 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Hyun-Woo Kim, Eunyoung Cho, Myung-Jun Kwak, Jeongin Lee, Hosik Lee, Chihyun Hwang and Hyun-Kon Song
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Abstract

A Zn2+-coordinated porphyrinic artificial solid–electrolyte interphase (αSEI) layer, named [Zn]PP-4COO-(Zn), was developed to improve the reversibility of zinc metal plating/stripping in aqueous zinc-ion batteries (ZIBs). Inspired by nitrogen-terminating sites of biological molecules coordinating and transporting zinc in zinc metabolic processes, the αSEI layer was designed with zinc ions connecting porphyrinic building blocks to form two-dimensional clathrate sheets and stacking xy-plane sheets along the z-axis to allow N4 cages to align and form porphyrinic N4 channels for zinc transport. The [Zn]PP-4COO-(Zn) αSEI layer was Zn2+-conductive and structurally durable during repeated stripping/plating. Zinc ions traveled through the porphyrinic αSEI layer along the N4 channels via (1) desolvation, (2) coordination to two nitrogens of the first clathrate sheet, (3) passing through distorted N4 cages, (4) moving to inter-plane N4 (two nitrogens from the first sheet and two nitrogens from the second sheet), (5) consecutive transport to next inter-plane N4, and (6) metal nucleation on zinc metal foil during plating. Zinc ions coming from electrolytes along the N4 channels were plated preferentially along the (002) plane, ensuring the non-dendritic growth of zinc metal for supporting plating/stripping reversibility to guarantee cycling durability. The porphyrinic N4 zinc-ion channels kept the zinc symmetric cells healthy even after 1500 times repeated plating/stripping during 3000 h operation.

Abstract Image

锌离子卟啉N4通道对锌电镀/剥离电化学可逆性的影响。
为了提高锌离子电池(zbs)中锌金属电镀/剥离的可逆性,制备了一种Zn2+配位卟啉人工固-电解质间相(αSEI)层,命名为[Zn]PP-4COO-(Zn)。受生物分子在锌代谢过程中协调和运输锌的氮终止位点的启发,设计了αSEI层,锌离子连接卟啉基构建块形成二维笼形物片,并沿z轴堆叠xy平面片,使N4笼对齐并形成卟啉型N4通道以运输锌。[Zn]PP-4COO-(Zn) αSEI层具有Zn2+导电性,且在反复剥离/电镀过程中结构耐用。锌离子沿N4通道穿过卟啉α - sei层,通过(1)脱溶,(2)与第一个笼形物片上的两个氮配位,(3)通过扭曲的N4笼,(4)移动到平面间的N4(第一个和第二个片上的两个氮),(5)连续迁移到下一个平面间的N4,(6)电镀时锌金属箔上的金属成核。来自电解液的锌离子沿着N4通道优先沿(002)平面镀,确保金属锌的非枝晶生长,以支持镀/剥离的可逆性,从而保证循环耐久性。在3000 h内反复镀/剥离1500次后,卟啉型N4锌离子通道仍能保持锌对称细胞的健康。
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来源期刊
Materials Horizons
Materials Horizons CHEMISTRY, MULTIDISCIPLINARY-MATERIALS SCIENCE, MULTIDISCIPLINARY
CiteScore
18.90
自引率
2.30%
发文量
306
审稿时长
1.3 months
期刊介绍: Materials Horizons is a leading journal in materials science that focuses on publishing exceptionally high-quality and innovative research. The journal prioritizes original research that introduces new concepts or ways of thinking, rather than solely reporting technological advancements. However, groundbreaking articles featuring record-breaking material performance may also be published. To be considered for publication, the work must be of significant interest to our community-spanning readership. Starting from 2021, all articles published in Materials Horizons will be indexed in MEDLINE©. The journal publishes various types of articles, including Communications, Reviews, Opinion pieces, Focus articles, and Comments. It serves as a core journal for researchers from academia, government, and industry across all areas of materials research. Materials Horizons is a Transformative Journal and compliant with Plan S. It has an impact factor of 13.3 and is indexed in MEDLINE.
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