物理化学学报 >> 2021, Vol. 37 >> Issue (1): 2007048.doi: 10.3866/PKU.WHXB202007048

所属专题: 金属锂负极

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金属有机骨架材料在金属锂电池界面的应用

孙宇恒1, 高铭达1, 李慧2, 徐丽2, 薛晴2, 王欣然1,*(), 白莹1, 吴川1,3,*()   

  1. 1 环境科学与工程北京市重点实验室,北京理工大学材料学院,北京 100081
    2 先进输电技术国家重点实验室(全球能源互联网研究院有限公司),北京 102209
    3 北京电动汽车协同创新中心,北京 100081
  • 收稿日期:2020-07-20 录用日期:2020-08-23 发布日期:2020-08-31
  • 通讯作者: 王欣然,吴川 E-mail:wangxinran@bit.edu.cn;chuanwu@bit.edu.cn
  • 作者简介:王欣然,北京理工大学材料学院副研究员。从事高比能二次电池及关键材料研究,重点关注金属锂电池技术。发表文章30篇,主持国家自然科学基金项目,参与科技部863、973计划、“中-德”合作、美国AFOSR等项目
    吴川,北京理工大学材料学院教授。长期从事先进能源材料的研究,关注能量储存与转体系及其关键材料,包括锂离子电池、钠离子电池、铝二次电池、锂空电池、锌离子电池及其他二次电池新体系。任Science合作期刊Energy Material Advances副主编第一联系人:

    The authors contributed equally to this work.

  • 基金资助:
    国家自然科学基金(51804290);北京市自然科学基金(L182023);全球能源互联网研究院有限公司科技项目(SGGR0000WLJS1900858);北京理工大学青年学者启动基金(2019CX04092)

Application of Metal-Organic Frameworks to the Interface of Lithium Metal Batteries

Yuheng Sun1, Mingda Gao1, Hui Li2, Li Xu2, Qing Xue2, Xinran Wang1,*(), Ying Bai1, Chuan Wu1,3,*()   

  1. 1 Beijing Key Laboratory of Environmental Science and Engineering, School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081, China
    2 State Key Laboratory of Advanced Power Transmission Technology (Global Energy Interconnection Research Institute Co. Ltd., ) Beijing 102209, China
    3 Collaborative Innovation Center of Electric Vehicles in Beijing, Beijing 100081, China
  • Received:2020-07-20 Accepted:2020-08-23 Published:2020-08-31
  • Contact: Xinran Wang,Chuan Wu E-mail:wangxinran@bit.edu.cn;chuanwu@bit.edu.cn
  • About author:Chuan Wu. Emails: chuanwu@bit.edu.cn (C.W.)
    Xinran Wang. Emails: wangxinran@bit.edu.cn (X.W.)
  • Supported by:
    the National Natural Science Foundation of China(51804290);the Beijing Natural Science Foundation(L182023);the Science and Technology Project of Global Energy Interconnection Research Institute Co. Ltd.(SGGR0000WLJS1900858);the Beijing Institute of Technology Research Fund Program for Young Scholars(2019CX04092)

摘要:

金属锂电池是下一代高能量密度电池体系的代表。然而,高比能金属锂电池的发展受到界面诸多问题的限制,如:金属锂负极枝晶生长、隔膜界面兼容性、正极界面不稳定等,影响了金属锂电池的界面传质传荷过程,并导致金属锂界面环境恶化、电池的容量衰减、安全性能下降等问题。金属有机骨架(MOF)是一种具有稳定多孔结构的有机无机杂化材料,近年来在高比能金属锂电池领域受到广泛关注。其多孔结构与开放的金属位点(OMs)提供了优异的离子电导率,稳定的空间结构提供了较高的机械强度,多样的官能团与金属节点带来丰富的功能性。本文分析了金属锂电池界面的主要挑战,结合金属锂界面的成核模型,总结了MOF及其衍生材料在解决锂金属负极界面、隔膜界面、以及正负极界面稳定性相互作用等方面的研究进展和作用机理,为解决高比能金属锂电池界面失稳问题提供了解决途径,并展望了MOF基材料的设计与发展方向。

关键词: 金属锂负极, 金属有机骨架, 界面防护, 隔膜, 电解液, 金属锂电池

Abstract:

Lithium metal batteries (LMBs) are representative systems for high-energy-density batteries. The design of LMBs with high capacity and high cycle stability is imperative. However, the development of LMBs is hindered by typical interface-related problems such as lithium dendrite growth, incompatible separator interfaces, and unstable cathode interfaces because of the inhomogeneous ionic flux and composition distribution. The intrinsic instability significantly hinders electron/ion transfer at the interface, causing serious issues such as dendrite growth, volume changes, low coulombic efficiency, dead lithium, interface deterioration, capacity degradation, and loss of safety. Metal-organic frameworks (MOFs) are organic-inorganic hybrid materials with a stable highly porous structure, which can allow for highly efficient gas adsorption, separation and purification, catalysis, etc., in addition to facilitating their application in nanomedicine and other fields. In recent years, MOFs have attracted much attention in the field of LMBs as a possible solution to the typical interface problems abovementioned. The porous structure and open metal sites (OMs) of MOFs provide an excellent interface structure for uniform and high ionic conductivity. As additional bonus, the stable structure provides high mechanical strength with different functional groups and metal sites, resulting in significant versatility of functionality for interface stabilization. MOFs are usually synthesized by hydrothermal/solvothermal, microwave-assisted, electrochemical, and spray-drying methods. The excellent properties of MOFs have prompted researchers to pursue their rational design and modification. Much progress has been made in this direction, and exemplary investigations have been performed to solve the abovementioned interfacial problems encountered with LMBs. Consequently, metallic lithium deposition frameworks, artificial solid electrolyte interface films, electrolyte additives, separator materials, cathode materials for lithium-sulfur batteries, and lithium-air batteries have been developed. However, there is a long way to go before the commercialization of batteries based on MOF materials. In practical, more complex electrochemical reactions occur at the lithium-metal interface, and the operating conditions (temperature, over charging/discharging, external stress, etc.) vary widely. Moreover, MOFs as electrode materials have intrinsic drawbacks, including structural collapse, pore blockage, and low inherent conductivity during the cycles. Based on these interfacial challenges, in LMBs, it introduces the structural characterization and optimization of MOFs and the key chemical components that determines the MOFs of structure (central atom, organic ligand, etc.). Subsequently, we summarized the growth mechanism of lithium dendrites and discussed the applications of MOFs and their derivatives to battery cathodes, separators, anodes, and electrolytes.The manuscript contents would be a guide to solve the problem of unstable interfaces in LMBs by the use of MOFs. Furthermore, the prospects and rational design of MOF-based materials are discussed.

Key words: Lithium metal anode, Metal organic framework, Interface protection, Separator, Electrolyte, Lithium metal battery

MSC2000: 

  • O646