低温水浴法制备钾离子预嵌层状MnO2 及其储锌性能

doi:10.19799/j.cnki.2095-4239.2022.0612

摘要/Abstract

摘要：

本工作采用低温水浴法一步合成K⁺预插层δ-MnO₂(K-δ-MnO₂)，并应用于锌离子电池正极。一方面，K⁺嵌入δ-MnO₂层间结构形成层间支柱，加固其层状结构，增强Zn²⁺在MnO₂中的扩散能力，增大了储锌配位活性位点；另一方面，水浴法在MnO₂结构中引入结构水，能有效屏蔽MnO₂结构对于Zn²⁺的强静电排斥效应，从而使K-δ-MnO₂展现出良好的电化学性能。在0.3 A/g的电流密度下，放电比容量可达401.3 mAh/g；在3 A/g的电流密度下循环1200次后，容量保持率达到83.2%，循环性能优于同等条件下无预插层MnO₂(循环1200次后，容量保持率为55.4%)。进一步采用非原位XRD研究了K-δ-MnO₂充放电过程中电极结构的变化，揭示其储能机理为H⁺和Zn²⁺共插层机制。同时，利用碳纳米管(CNT)与K-δ-MnO₂复合，两者之间形成络合体，有效提高了导电性，进一步巩固层状结构。该复合材料展示了出色的循环性能，在3 A/g的电流密度下循环1200次后，仍有271.7 mAh/g的比容量，容量保持率高达98.6%。水浴法制备的K-δ-MnO₂展现了优秀的电化学性能，且该方法易于工业化生产，在水系锌离子电池正极材料的应用方面具备极大的潜力。

关键词: 预插层, δ-MnO₂, CNT, 锌离子电池

Abstract:

In this study, K⁺ incorporated into δ-MnO₂ (K-δ-MnO₂) are prepared by a facile redox method and applied as cathodes in aqueous zinc ion batteries (AZIBs). The pre-intercalated K⁺acting as structure stabilizing "pillars" allows the tune of the lattice space of MnO₂ and promotes the diffusion kinetics of Zn²⁺ in the tunnel structure. Additionally, cations introduce shallow donor levels that enhance hosts' electronic conductivity and activate additional active sites. Besides, the co-intercalating water screens the intercalation between the intercalated Zn ions and the MnO₂cathode, resulting in faster intercalation processes. The as-prepared K-δ-MnO₂ as cathode materials for AZIBs shows a relatively high capacity (401.3 mAh/g at 0.3 A/g) and an impressive cycling stability (83.2% retention after 1200 cycles at 3 A/g), while an inferior cyclability is observed for the pristine δ-MnO₂. The energy storage mechanism is clarified as H⁺/Zn²⁺ coinsertion/extraction via an ex-situ XRD characterization. With the combination of CNT, the composite electrode of K-?δ?-MnO₂/CNT displays better cycling stability (98.6% retention after 1200 cycles at 3 A/g). The K-δ-MnO₂ prepared by the facile redox method, which is simple and easy upscaling from the laboratory to industry, shows great potential as the cathode for AZIBs with good electrochemical performance.

Key words: pre-intercalation, δ-MnO₂, CNT, zinc ion batteries

中图分类号:

TM 911

刘起辉, 傅焰鹏, 罗京, 方桃, 施志聪. 低温水浴法制备钾离子预嵌层状MnO₂ 及其储锌性能[J]. 储能科学与技术, 2023, 12(3): 768-776.

Qihui LIU, Yanpeng FU, Jing LUO, Tao FANG, Zhicong SHI. Low-temperature solution synthesis of K⁺ preintercalated delta-MnO₂ for high performance Zn-ion battery[J]. Energy Storage Science and Technology, 2023, 12(3): 768-776.

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低温水浴法制备钾离子预嵌层状MnO₂ 及其储锌性能

Low-temperature solution synthesis of K⁺ preintercalated delta-MnO₂ for high performance Zn-ion battery

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