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Title: Wrinkled Graphene Cages as Hosts for High-Capacity Li Metal Anodes Shown by Cryogenic Electron Microscopy

Abstract

Lithium (Li) metal has long been considered the “holy grail” of battery anode chemistry but is plagued by low efficiency and poor safety due to its high chemical reactivity and large volume fluctuation, respectively. Here we introduce a new host of wrinkled graphene cage (WGC) for Li metal. Different from recently reported amorphous carbon spheres, WGC show highly improved mechanical stability, better Li ion conductivity, and excellent solid electrolyte interphase (SEI) for continuous robust Li metal protection. At low areal capacities, Li metal is preferentially deposited inside the graphene cage. Cryogenic electron microscopy characterization shows that a uniform and stable SEI forms on the WGC surface that can shield the Li metal from direct exposure to electrolyte. With increased areal capacities, Li metal is plated densely and homogeneously into the outer pore spaces between graphene cages with no dendrite growth or volume change. As a result, a high Coulombic efficiency (CE) of ~98.0% was achieved under 0.5 mA/cm2 and 1–10 mAh/cm2 in commercial carbonate electrolytes, and a CE of 99.1% was realized with high-concentration electrolytes under 0.5 mA/cm2 and 3 mAh/cm2. Full cells using WGC electrodes with prestored Li paired with Li iron phosphate showed greatly improved cycle lifetime. Withmore » 10 mAh/cm2 Li metal deposition, the WGC/Li composite anode was able to provide a high specific capacity of ~2785 mAh/g. Furthermore, with its roll-to-roll compatible fabrication procedure, WGC serves as a highly promising material for the practical realization of Li metal anodes in next-generation high energy density secondary batteries.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [1];  [1];  [1]; ORCiD logo [1];  [1]; ORCiD logo [1];  [1];  [1]; ORCiD logo [1];  [1];  [1];  [1]; ORCiD logo [1];  [1]; ORCiD logo [2]
  1. Stanford Univ., Stanford, CA (United States)
  2. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1507152
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Nano Letters
Additional Journal Information:
Journal Volume: 19; Journal Issue: 2; Journal ID: ISSN 1530-6984
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Coulombic efficiency; cryo-EM; Li metal anode; wrinkled graphene cage

Citation Formats

Wang, Hansen, Li, Yuzhang, Li, Yanbin, Liu, Yayuan, Lin, Dingchang, Zhu, Cheng, Chen, Guangxu, Yang, Ankun, Yan, Kai, Chen, Hao, Zhu, Yangying, Li, Jun, Xie, Jin, Xu, Jinwei, Zhang, Zewen, Vilá, Rafael, Pei, Allen, Wang, Kecheng, and Cui, Yi. Wrinkled Graphene Cages as Hosts for High-Capacity Li Metal Anodes Shown by Cryogenic Electron Microscopy. United States: N. p., 2019. Web. doi:10.1021/acs.nanolett.8b04906.
Wang, Hansen, Li, Yuzhang, Li, Yanbin, Liu, Yayuan, Lin, Dingchang, Zhu, Cheng, Chen, Guangxu, Yang, Ankun, Yan, Kai, Chen, Hao, Zhu, Yangying, Li, Jun, Xie, Jin, Xu, Jinwei, Zhang, Zewen, Vilá, Rafael, Pei, Allen, Wang, Kecheng, & Cui, Yi. Wrinkled Graphene Cages as Hosts for High-Capacity Li Metal Anodes Shown by Cryogenic Electron Microscopy. United States. https://doi.org/10.1021/acs.nanolett.8b04906
Wang, Hansen, Li, Yuzhang, Li, Yanbin, Liu, Yayuan, Lin, Dingchang, Zhu, Cheng, Chen, Guangxu, Yang, Ankun, Yan, Kai, Chen, Hao, Zhu, Yangying, Li, Jun, Xie, Jin, Xu, Jinwei, Zhang, Zewen, Vilá, Rafael, Pei, Allen, Wang, Kecheng, and Cui, Yi. Thu . "Wrinkled Graphene Cages as Hosts for High-Capacity Li Metal Anodes Shown by Cryogenic Electron Microscopy". United States. https://doi.org/10.1021/acs.nanolett.8b04906. https://www.osti.gov/servlets/purl/1507152.
@article{osti_1507152,
title = {Wrinkled Graphene Cages as Hosts for High-Capacity Li Metal Anodes Shown by Cryogenic Electron Microscopy},
author = {Wang, Hansen and Li, Yuzhang and Li, Yanbin and Liu, Yayuan and Lin, Dingchang and Zhu, Cheng and Chen, Guangxu and Yang, Ankun and Yan, Kai and Chen, Hao and Zhu, Yangying and Li, Jun and Xie, Jin and Xu, Jinwei and Zhang, Zewen and Vilá, Rafael and Pei, Allen and Wang, Kecheng and Cui, Yi},
abstractNote = {Lithium (Li) metal has long been considered the “holy grail” of battery anode chemistry but is plagued by low efficiency and poor safety due to its high chemical reactivity and large volume fluctuation, respectively. Here we introduce a new host of wrinkled graphene cage (WGC) for Li metal. Different from recently reported amorphous carbon spheres, WGC show highly improved mechanical stability, better Li ion conductivity, and excellent solid electrolyte interphase (SEI) for continuous robust Li metal protection. At low areal capacities, Li metal is preferentially deposited inside the graphene cage. Cryogenic electron microscopy characterization shows that a uniform and stable SEI forms on the WGC surface that can shield the Li metal from direct exposure to electrolyte. With increased areal capacities, Li metal is plated densely and homogeneously into the outer pore spaces between graphene cages with no dendrite growth or volume change. As a result, a high Coulombic efficiency (CE) of ~98.0% was achieved under 0.5 mA/cm2 and 1–10 mAh/cm2 in commercial carbonate electrolytes, and a CE of 99.1% was realized with high-concentration electrolytes under 0.5 mA/cm2 and 3 mAh/cm2. Full cells using WGC electrodes with prestored Li paired with Li iron phosphate showed greatly improved cycle lifetime. With 10 mAh/cm2 Li metal deposition, the WGC/Li composite anode was able to provide a high specific capacity of ~2785 mAh/g. Furthermore, with its roll-to-roll compatible fabrication procedure, WGC serves as a highly promising material for the practical realization of Li metal anodes in next-generation high energy density secondary batteries.},
doi = {10.1021/acs.nanolett.8b04906},
journal = {Nano Letters},
number = 2,
volume = 19,
place = {United States},
year = {2019},
month = {1}
}

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