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Interface Engineering of MOF Nanosheets for Accelerated Redox Kinetics in Lithium‐Sulfur Batteries

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Modifying the separator is considered as an effective strategy for achieving high performance lithium‐sulfur (Li‐S) batteries. However, most modification layers are excessively thick, with catalytic active sites primarily located within the material′s interior. This configuration severely impacts Li⁺ transport and the efficient catalytic conversion of polysulfides. Therefore, there is an urgent need to develop a multifunctional separator that integrates ultrathin design, catalytic activity, and ion sieving capabilities. Herein, we successfully linked TCPP(Ni) as a secondary ligand with Zr‐BTB nanosheets to create an ultra‐thin separator modification layer (Zr‐TCPP(Ni)) with efficient ion sieving and catalytic properties. The resultant multifunctional separators provide robust ion sieving capabilities that promote rapid Li⁺ transport and intercept polysulfides shuttling. Therefore, The Zr‐TCPP(Ni)@PP cell maintains 70.0 % of its initial capacity after 600 cycles at a high rate of 3 C, while achieving an impressive areal capacity of 4.55 mA h cm⁻² even with high sulfur content of 80 wt% at 0.5 C. This work provides valuable insights for rational design of MOF interface engineering in high energy density Li‐S batteries.
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Lithium-Sulfur Batteries
Interface Engineering of MOF Nanosheets for Accelerated Redox
Kinetics in Lithium-Sulfur Batteries
Zhibin Cheng,* Yiyang Chen, Jie Lian, Xingli Chen, Shengchang Xiang, Banglin Chen, and
Zhangjing Zhang*
Abstract: Modifying the separator is considered as an
effective strategy for achieving high performance lith-
ium-sulfur (Li-S) batteries. However, most modification
layers are excessively thick, with catalytic active sites
primarily located within the materials interior. This
configuration severely impacts Li+transport and the
efficient catalytic conversion of polysulfides. Therefore,
there is an urgent need to develop a multifunctional
separator that integrates ultrathin design, catalytic
activity, and ion sieving capabilities. Herein, we success-
fully linked TCPP(Ni) as a secondary ligand with Zr-
BTB nanosheets to create an ultra-thin separator
modification layer (Zr-TCPP(Ni)) with efficient ion
sieving and catalytic properties. The resultant multifunc-
tional separators provide robust ion sieving capabilities
that promote rapid Li+transport and intercept poly-
sulfides shuttling. Therefore, The Zr-TCPP(Ni)@PP cell
maintains 70.0% of its initial capacity after 600 cycles at
a high rate of 3 C, while achieving an impressive areal
capacity of 4.55 mAh cm2even with high sulfur content
of 80 wt% at 0.5 C. This work provides valuable insights
for rational design of MOF interface engineering in high
energy density Li-S batteries.
1. Introduction
With the widespread adoption of new energy vehicles and
large-scale energy storage devices, traditional Li+batteries
are approaching their limits in the energy storage
capacity.[1–4] Lithium-sulfur (Li-S) batteries, with their high
theoretical energy density (2600 W hkg1) and low cost, are
emerging as promising candidates for the next generation of
energy storage system.[5] However, the real-world applica-
tion of LiS batteries has encountered significant obstacles,
primarily due to limited practical energy density, low
coulombic efficiency, and poor cycling stability.[6–8] These
challenges are largely attributed to the notorious shuttle
effects, in which soluble lithium polysulfides formed during
charge and discharge migrate between the cathode and
anode.[9–11] This phenomenon results in active sulfur loss and
lithium metal corrosion, ultimately impairing battery ca-
pacity and stability.[12–14]
To address these issues, modifying the separator is
considered as an effective strategy. This approach not only
regulates the electrochemical behavior of polysulfides on the
cathode side, but also helps uniformly control Li+transport,
even facilitating the stripping and plating of lithium metal
on the anode side.[15,16] Various functional materials have
been utilized for separator modification, including porous
carbon materials[17], graphene,[18] metal oxides,[19] metal
sulfides[20], and metal-organic frameworks (MOFs).[21]
Among these, MOFs stand out as unique porous materials
with high specific surface area and uniform pore size
distribution. Their pore channels can be tailored for
specialized ion transport and efficient ion sieving.[22–24] More-
over, studies have shown that traditional functional MOFs
used as separator modification layers can effectively adsorb
polysulfides and catalyze their conversion[25–27], thereby
enhancing the electrochemical performance of Li-S bat-
teries. Hu et al.[28] combined porphyrin-based MOF with
CNT to prepare a PCN@CNT composite as a novel func-
tional separator coating, leveraging the catalytic activity of
PCN-222(Co) to significantly enhance the cycling stability of
Li-S batteries. Razaq et al.[29] introduced Fe doped metal
sites to synthesize a bimetallic MOF (Fe-ZIF-8) with nano-
structured pores, which served as a functional coating for
the separator, enabling efficient polysulfides interception
and promoting the transformation of polysulfides in Li-S
batteries. However, most modification layers are excessively
thick, with catalytic active sites primarily located within the
materials interior.[10,30] This configuration severely impacts
Li+transport and the efficient catalytic conversion of
polysulfides.[31,32] Therefore, there is an urgent need to
develop a multifunctional separator that integrates ultrathin
design, catalytic activity, and ion sieving capabilities.
To satisfy the demands of an ideal separator modifica-
tion layer, two-dimensional (2D) MOF nanosheets have
been chosen due to their substantial application potential.
Compared to three-dimensional (3D) MOFs, 2D MOFs,
characterized by nanometer-scale thickness and extensive
lateral dimensions, provide a high specific surface area,
thereby exposing a greater number of electrocatalytic active
[*] Prof. Z. Cheng, Y. Chen, Dr. J. Lian, X. Chen, Prof. S. Xiang,
Prof. B. Chen, Prof. Z. Zhang
Fujian Key Laboratory of Pcolymer Materials, College of Materials
Science and Engineering, Fujian Normal University, Fuzhou
350007, China
E-mail: chengzhibin@fjnu.edu.cn
zzhang@fjnu.edu.cn
Prof. Z. Cheng, Dr. J. Lian, Prof. Z. Zhang
State Key Laboratory of Structural Chemistry, Fujian Institute of
Research on the Structure of Matter, Chinese Academy of Sciences,
Fuzhou 350002, China
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How to cite: Angew. Chem. Int. Ed. 2024, e202421726
doi.org/10.1002/anie.202421726
Angew. Chem. Int. Ed. 2024, e202421726 (1 of 11) © 2024 Wiley-VCH GmbH
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