Cathode-Electrolyte Interface Modification by Binder Engineering for High-Performance Aqueous Zinc-Ion Batteries.
Cathode-Electrolyte Interface Modification by Binder Engineering for High-Performance Aqueous Zinc-Ion Batteries.
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DOI：
10.1002/advs.202205084
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发表时间：
2023-02
期刊：
影响因子：
15.1
通讯作者：
Parkin, Ivan P. P.
中科院分区：
文献类型：
--
作者：
Dong, Haobo;Liu, Ruirui;Hu, Xueying;Zhao, Fangjia;Kang, Liqun;Liu, Longxiang;Li, Jianwei;Tan, Yeshu;Zhou, Yongquan;Brett, Dan J. L.;He, Guanjie;Parkin, Ivan P. P.
稳定的阴极-电解质界面（CEI）对于水性锌离子电池（AZIB）至关重要，但研究较少。商业粘合剂聚（偏二氟乙烯）（PVDF）在AZIB中被广泛使用，而没有仔细检查其适用性和阴极-电解质界面（CEI）。开发了一种水溶性粘合剂，其有助于原位形成CEI保护层，从而调节界面形态。通过将多糖海藻酸钠（SA）与疏水性聚四氟乙烯（PTFE）组合，可以将表面形态和电荷存储动力学从扩散主导限制为电容控制过程。从动力学和热力学角度对支撑机理进行了实验研究，结果表明，SA中的COO-作为阴离子载体促进了对Zn 2+的吸附;同时PTFE骨架上的氟原子提供了疏水性，打破了去溶剂化惩罚。混合粘合剂有利于在CEI下提供更高的Zn 2+面积通量，其中具有混合粘合剂的Zn-Birnessite MnO 2电池表现出比常规PVDF粘合剂高45.6%的平均比容量;此外，获得的降低的界面活化能促进了优异的上级倍率性能和1000次循环中99.1%的容量保持率。与PVDF/NMP相比，混合粘合剂还降低了成本，这是改变界面形态的通用策略。人们在阴极、阳极和电解质方面做了大量的工作，但对界面机理仍缺乏全面的了解。在此，提出了一种通用的策略，用于稳定阴极直接从界面改性的粘结剂界面工程。在粘合剂中引入阴离子型阴离子后，电池界面机制可以在扩散控制和电容主导之间调节。
A stable cathode–electrolyte interface (CEI) is crucial for aqueous zinc‐ion batteries (AZIBs), but it is less investigated. Commercial binder poly(vinylidene fluoride) (PVDF) is widely used without scrutinizing its suitability and cathode‐electrolyte interface (CEI) in AZIBs. A water‐soluble binder is developed that facilitated the in situ formation of a CEI protecting layer tuning the interfacial morphology. By combining a polysaccharide sodium alginate (SA) with a hydrophobic polytetrafluoroethylene (PTFE), the surface morphology, and charge storage kinetics can be confined from diffusion‐dominated to capacitance‐controlled processes. The underpinning mechanism investigates experimentally in both kinetic and thermodynamic perspectives demonstrate that the COO− from SA acts as an anionic polyelectrolyte facilitating the adsorption of Zn2+; meanwhile fluoride atoms on PTFE backbone provide hydrophobicity to break desolvation penalty. The hybrid binder is beneficial in providing a higher areal flux of Zn2+ at the CEI, where the Zn‐Birnessite MnO2 battery with the hybrid binder exhibits an average specific capacity 45.6% higher than that with conventional PVDF binders; moreover, a reduced interface activation energy attained fosters a superior rate capability and a capacity retention of 99.1% in 1000 cycles. The hybrid binder also reduces the cost compared to the PVDF/NMP, which is a universal strategy to modify interface morphology. Intensive efforts are applied to cathode, anode, and electrolyte, while it still lacks a comprehensive understanding of the interface mechanisms. Herein, a universal strategy is proposed for stabilizing the cathode directly from interface modification by the binder interface engineering. After introducing anionic polyelectrolyte in the binder, the battery interface mechanism can be tuned between diffusion control and capacitive dominance.
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