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通过ZnF层的电化学活化来调控锂在铜集流体上的成核与生长

Taming Lithium Nucleation and Growth on Cu Current Collector by Electrochemical Activation of ZnF Layer.

作者信息

Nguyen Viet Phuong, Shim Hyung Cheoul, Byeon Young-Woon, Kim Jae-Hyun, Lee Seung-Mo

机构信息

Nanomechatronics, University of Science and Technology (UST), 217 Gajeong-ro, Daejeon, 34113, Republic of Korea.

Department of Nanomechanics, Korea Institute of Machinery & Materials (KIMM), 156 Gajeongbuk-ro, Daejeon, 34103, Republic of Korea.

出版信息

Adv Sci (Weinh). 2025 May;12(19):e2416426. doi: 10.1002/advs.202416426. Epub 2025 Mar 26.

DOI:10.1002/advs.202416426
PMID:40138201
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC12097123/
Abstract

Lithium-metal anodes are essential for the advancement of next-generation batteries. However, their practical use is largely hindered by the uncontrollable growth of dendrites and intricate problems associated with fabricating anodes that meet capacity requirements. Here, it is demonstrated that an ultrathin ZnF layer deposited on the copper foil can produce a novel and efficient current collector to address these challenges. It is observed that ZnF can be transformed into LiZn alloy and LiF salt in one step by simple electrochemical activation. The resulting LiZn alloy exhibits high lithiophilicity, which reduces overpotential and promotes uniform lithium nucleation, while the LiF salt enhances the solid electrolyte interphase, ensuring uniform lithium growth. This synergistic effect led to a dendrite-free, densely packed lithium anode with an extended lifespan, achieving over 900 h in symmetric cells at a high current density of 3 mA cm and a high cut-off capacity of 3 mAh cm. Furthermore, full cells utilizing the lithium anode (Li capacity of 6 mAh cm) paired with LiNiMnCoO cathodes (mass loading of 11.5 mg cm) demonstrates drastically improved rate capability and excellent cycling stability. This approach holds great promise for developing safer and more efficient lithium-metal-based batteries for future energy storage solutions.

摘要

锂金属阳极对于下一代电池的发展至关重要。然而,它们的实际应用在很大程度上受到枝晶不可控生长以及与制造满足容量要求的阳极相关的复杂问题的阻碍。在此,证明了沉积在铜箔上的超薄ZnF层可以产生一种新颖且高效的集流体来应对这些挑战。观察到通过简单的电化学活化,ZnF可以一步转化为LiZn合金和LiF盐。所得的LiZn合金表现出高亲锂性,这降低了过电位并促进均匀的锂成核,而LiF盐增强了固体电解质界面,确保锂的均匀生长。这种协同效应导致了一种无枝晶、紧密堆积的锂阳极,其寿命延长,在3 mA cm的高电流密度和3 mAh cm的高截止容量下,对称电池中实现了超过900小时的寿命。此外,使用锂阳极(Li容量为6 mAh cm)与LiNiMnCoO阴极(质量负载为11.5 mg cm)配对的全电池表现出显著提高的倍率性能和出色的循环稳定性。这种方法对于开发用于未来储能解决方案的更安全、更高效的锂金属基电池具有巨大的前景。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1697/12097123/443a8eb624a5/ADVS-12-2416426-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1697/12097123/4e7dd297647d/ADVS-12-2416426-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1697/12097123/09fb9b5b0989/ADVS-12-2416426-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1697/12097123/a7801c8bb49b/ADVS-12-2416426-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1697/12097123/a9a56e6758d0/ADVS-12-2416426-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1697/12097123/443a8eb624a5/ADVS-12-2416426-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1697/12097123/4e7dd297647d/ADVS-12-2416426-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1697/12097123/09fb9b5b0989/ADVS-12-2416426-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1697/12097123/a7801c8bb49b/ADVS-12-2416426-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1697/12097123/a9a56e6758d0/ADVS-12-2416426-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1697/12097123/443a8eb624a5/ADVS-12-2416426-g006.jpg

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本文引用的文献

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An Ultralight Composite Current Collector Enabling High-Energy-Density and High-Rate Anode-Free Lithium Metal Battery.一种实现高能量密度和高倍率无阳极锂金属电池的超轻复合集流体
Adv Mater. 2024 Aug;36(33):e2407648. doi: 10.1002/adma.202407648. Epub 2024 Jun 28.
2
Constructing Lithium-Free Anode/Separator Interface via 3D Carbon Fabric Scaffold for Ultrasafe Lithium Metal Batteries.通过3D碳纤维支架构建用于超安全锂金属电池的无锂负极/隔膜界面
Research (Wash D C). 2023 Nov 8;6:0267. doi: 10.34133/research.0267. eCollection 2023.
3
Copper Current Collector: The Cornerstones of Practical Lithium Metal and Anode-Free Batteries.
铜集流体:实用锂金属电池和无阳极电池的基石。
Chemphyschem. 2024 Apr 16;25(8):e202400007. doi: 10.1002/cphc.202400007. Epub 2024 Mar 11.
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Interfacial Manipulation via In Situ Constructed Fast Ion Transport Channels toward an Ultrahigh Rate and Practical Li Metal Anode.通过原位构建快速离子传输通道实现超高倍率及实用化锂金属负极的界面调控
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Zincophilic Interfacial Manipulation against Dendrite Growth and Side Reactions for Stable Zn Metal Anodes.用于稳定锌金属负极的亲锌界面调控以抑制枝晶生长和副反应
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Integrated Gradient Cu Current Collector Enables Bottom-Up Li Growth for Li Metal Anodes: Role of Interfacial Structure.集成梯度铜集流体实现锂金属负极的自下而上锂生长:界面结构的作用
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