物理化学学报

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聚吡咯@二氧化锰/碳纳米管薄膜电极的制备及在高性能锌离子电池中的应用

沈晓帆1,2, 王晓娜1, 俞能晟1,2, 杨薇1, 周雨融1,2, 石艳红1, 王玉莲1,3, 董立忠1,3, 邸江涛1,3, 李清文1,3   

  1. 1 中国科学院苏州纳米技术与纳米仿生研究所, 先进材料部, 中国科学院多功能材料与轻巧系统重点实验室, 江苏 苏州 215123;
    2 中国科学技术大学纳米科学技术学院, 江苏 苏州 215123;
    3 中国科学技术大学纳米技术与纳米仿生学院, 合肥 230026
  • 收稿日期:2020-06-23 修回日期:2020-07-28 录用日期:2020-08-12 发布日期:2020-08-17
  • 通讯作者: 邸江涛, 李清文 E-mail:jtdi2009@sinano.ac.cn;qwli2007@sinano.ac.cn
  • 基金资助:
    国家自然科学基金(21975281, 21773293, 21603264), 国家重点研发计划(2016YFA0203301), 江苏省博士后基金(2019K048), 苏州市科技计划项目(SYG201926)资助

A Polypyrrole-Coated MnO2/Carbon Nanotube Film Cathode for Rechargeable Aqueous Zn-Ion Batteries

Xiaofan Shen1,2, Xiaona Wang1, Nengsheng Yu1,2, Wei Yang1, Yurong Zhou1,2, Yanhong Shi1, Yulian Wang1,3, Lizhong Dong1,3, Jiangtao Di1,3, Qingwen Li1,3   

  1. 1 Key Laboratory of Multifunctional Nanomaterials and Smart Systems, Advanced Materials Division, Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Suzhou 215123, Jiangsu Province, China;
    2 Nano Science and Technology Institute, University of Science and Technology of China, Suzhou 215123, Jiangsu Province, China;
    3 School of Nano-Tech and Nano-Bionics, University of Science and Technology of China, Hefei 230026, China
  • Received:2020-06-23 Revised:2020-07-28 Accepted:2020-08-12 Published:2020-08-17
  • Supported by:
    The project was supported by the National Natural Science Foundation of China (21975281, 21773293, 21603264), the National Key Research and Development Program of China (2016YFA0203301), the Jiangsu Planned Projects for Postdoctoral Research Funds, China (2019K048), and the Suzhou Science and Technology Plan Project, China (SYG201926).

摘要: 中性/弱酸性水系锌锰电池因其能量密度高、价格低廉、环境友好等优势受到广泛关注。然而,现有的二氧化锰正极材料存在导电性能差,在充放电过程中易于溶解等问题。这严重影响了电池的倍率性能和循环稳定性,阻碍了中性锌锰电池的应用。为了解决上述问题,本文设计了以碳纳米管(CNT)网络薄膜为导电基底沉积聚吡咯(PPy)包覆二氧化锰(PPy@MnO2/CNT)的多级结构电极。碳纳米管和聚吡咯组装形成高比表面积的三维交联导电网络,为活性材料提供了快速的电子、离子传输通道;聚吡咯包覆纳米级二氧化锰能够有效地抑制二氧化锰的溶解,进而提升电池的倍率特性和循环稳定性。以PPy@MnO2/CNT作为正极材料组装的水系锌锰电池在1 A·g−1的电流密度下,比容量达到210 mAh·g−1,循环1000圈后,电池依然具有较高的容量保持率(85.7%)。本工作的导电聚合物包覆活性物质的策略可为发展高稳定柔性储能器件提供新思路。

关键词: 锌离子电池, 聚吡咯@二氧化锰, 碳纳米管, 柔性电池, 长循环

Abstract: Rechargeable aqueous Zinc-ion batteries (ZIBs) have emerged as potential energy storage devices due to their high energy density, low cost, and safety. To date, numerous cathodes based on manganese dioxide, vanadium dioxide, and polyanionic compounds have been reported. Among them, MnO2 cathodes are particularly desirable candidates for commercialization owing to their tunnel structure and affordability. In particular, the parasitic reaction of Mn-based cathodes in alkaline batteries can be suppressed in mild aqueous electrolytes, resulting in enthusiasm for the development of rechargeable Zn||MnO2 batteries. Even though various MnO2phases have been reported as hosts for Zn2+/H+ insertion, MnO2 crystal structures undergo significant, irreversible transformations during cycling, which is a major challenge in Zn||MnO2 batteries. In addition, the tunnel structure can collapse under the insertion of the hydrated cation resulting in Mn2+ dissolution into the electrolyte and significant loss in capacity over long cycling periods. The MnO2 cathode also has low intrinsic electronic conductivity due to the large charge transfer resistance, which limits the diffusivity of divalent ions. Despite the achievements made in the field of ZIBs so far, designing active materials and ZIBs systems to meet commercial requirements is a significant challenge. In this study, we report the preparation of polypyrrole-wrapped MnO2/carbon nanotubes (PPy@MnO2/CNT) as composite cathodes for aqueous ZIBs. A combination of design strategies was used to increase structural stability and improve electronic conductivity, including increased electrode/electrolyte interaction by using nano-sized structures, shortened diffusion pathways through multistage composites, and enhanced electrical conductivity with conductive composites. The three-dimensional (3D) structured PPy/CNT network can facilitate mass and charge transport during the charge and discharge processes. The structure of MnO2 wrapped by polypyrrole effectively prevents the dissolution of MnO2. Thus, the assembled Zn||MnO2 batteries, using PPy@MnO2/CNT composite cathodes, exhibit a high capacity of 210 mAh·g−1 at 1 A·g−1, and achieve 85.7% capacity retention after 1000 charge/discharge cycles. Moreover, a high specific capacity of 100 mAh·g−1 could be maintained at 2 A·g−1, exhibiting excellent kinetic performance. The assembled quasi-solid Zn//MnO2 battery, benefiting from the xanthan gum electrolyte and flexible CNT film, possesses intrinsic safety, bending resistance, and high potential in wearable applications.

Key words: Zinc-ion battery, PPy@MnO2, Carbon nanotube, Flexible battery, Long life

MSC2000: 

  • O646