Journal of Energy Chemistry

Journal of Energy Chemistry ›› 2022, Vol. 69 ›› Issue (6): 270-281.DOI: 10.1016/j.jechem.2021.12.046

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MnO2 nanosheet modified N, P co-doping carbon nanofibers on carbon cloth as lithiophilic host to construct high-performance anodes for Li metal batteries

Xiaoqiang Liua,1, Qian Zhanga,1, Yiru Maa, Zhenzhen Chia, Huixiang Yina, Jie Liud, Junfei Huange, Ziyang Guoa,c,*, Lei Wanga,b,*   

  1. aKey Laboratory of Eco-chemical Engineering, Taishan Scholar Advantage and Characteristic Discipline Team of Eco-Chemical Process and Technology, College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, Shandong, China;
    bCollege of Environment and Safety Engineering, Qingdao University of Science and Technology, Qingdao 266042, Shandong, China;
    cKey Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Nankai University, Tianjin 300071, China;
    dKey Laboratory of Eco-chemical Engineering, Taishan Scholar Advantage and Characteristic Discipline Team of Eco-Chemical Process and Technology, College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042, Shandong, China;
    eShimadzu (China) Co., Ltd., Shenzhen Branch, Shenzhen 518000, Guangdong, China
  • Received:2021-09-13 Revised:2021-12-25 Accepted:2021-12-28 Online:2022-06-15 Published:2022-10-25
  • Contact: * E-mail addresses: zyguo@qust.edu.cn (Z. Guo), inorchemwl@126.com (L. Wang).
  • About author:1 These authors contributed equally to this work.

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Abstract: Lithium (Li) metal batteries have attracted much attention owing to its ultra-high energy density. However, as important part of Li metal batteries, Li anodes still face many challenges, mainly including uncontrolled dendritic Li formation, dramatical volume variation and serious pulverization. Herein, man-ganese dioxide (MnO2) nanosheet modified nitrogen (N), phosphorus (P) co-doping carbon nanofibers (NPC) on carbon cloth (CC) (MnO2@NPC-CC) is successfully fabricated through electrodeposition approach and further treated with Li by the molten-infusion method to prepare Li based Mn@NPC-CC (Li-Mn@NPC-CC) electrode. The synergy of MnO2 and NPC obviously increases the reaction rate between MnO2@NPC-CC and Li and guides even Li distribution over infusion process. Additionally, theoretical cal-culation, simulation and experimental results further indicate that N, P, Mn multi-doping effectively improves the superior lithiophilicity of Li-Mn@NPC-CC, which induces uniform Li deposition/dissolution to suppress dendrite growth over cycles. Moreover, conductive and porous NPC matrix not only effec-tively improves the stability of Li-Mn@NPC-CC, but also provides abundant spaces to accelerate the trans-fer of ion/electron and buffer electrode dimension variation during cycling. Hence, Li-Mn@NPC-CC-based symmetric cells exhibit extra-long cycling life (over 2200 h) with small hysteresis of 20 mV. When the Li-Mn@NPC-CC anode couples with air, Li iron phosphate (LiFePO4), or hard carbon (C) cathode, the assem-bled full cells exhibit outstanding performance with low hysteresis and stable cycling properties. Especially, the corresponding pouch-typed Li-air cells also exhibit good performance at different bending angles and even power a series of electronic devices.

Key words: N,P co-doped carbon nanofibers on carbon cloth, MnO2 nanosheet coating, Molten-infusion method, Li metal anodes, Li metal batteries