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Title: Formation and Inhibition of Metallic Lithium Microstructures in Lithium Batteries Driven by Chemical Crossover

Abstract

The formation of metallic lithium microstructures in the form of dendrites or mosses at the surface of anode electrodes (e.g., lithium metal, graphite, and silicon) leads to rapid capacity fade and poses grave safety risks in rechargeable lithium batteries. In this work, we present here a direct, relative quantitative analysis of lithium deposition on graphite anodes in pouch cells under normal operating conditions, paired with a model cathode material, the layered nickel-rich oxide LiNi0.61Co0.12Mn0.27O2, over the course of 3000 charge-discharge cycles. Secondary-ion mass spectrometry chemically dissects the solid-electrolyte interphase (SEI) on extensively cycled graphite with virtually atomic depth resolution and reveals substantial growth of Li-metal deposits. With the absence of apparent kinetic (e.g., fast charging) or stoichiometric restraints (e.g., overcharge) during cycling, we show lithium deposition on graphite is triggered by certain transition-metal ions (manganese in particular) dissolved from the cathode in a disrupted SEI. This insidious effect is found to initiate at a very early stage of cell operation (<200 cycles) and can be effectively inhibited by substituting a small amount of aluminum (~1 mol %) in the cathode, resulting in much reduced transition-metal dissolution and drastically improved cyclability. In conclusion, our results may also be applicable to studyingmore » the unstable electrodeposition of lithium on other substrates, including Li metal.« less

Authors:
 [1];  [2]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of Texas, Austin, TX (United States). Materials Science and Engineering Program and Texas Materials Institute
  2. Hanyang University, Seoul (Korea, Republic of). Department of Energy Engineering
Publication Date:
Research Org.:
Univ. of Texas, Austin, TX (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1430486
Grant/Contract Number:  
EE0007762
Resource Type:
Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 11; Journal Issue: 6; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE; carbon anodes; lithium deposition; lithium-ion batteries; nickel-rich layered oxides; secondary-ion mass spectrometry; transition-metal dissolution

Citation Formats

Li, Wangda, Kim, Un-Hyuck, Dolocan, Andrei, Sun, Yang-Kook, and Manthiram, Arumugam. Formation and Inhibition of Metallic Lithium Microstructures in Lithium Batteries Driven by Chemical Crossover. United States: N. p., 2017. Web. https://doi.org/10.1021/acsnano.7b01494.
Li, Wangda, Kim, Un-Hyuck, Dolocan, Andrei, Sun, Yang-Kook, & Manthiram, Arumugam. Formation and Inhibition of Metallic Lithium Microstructures in Lithium Batteries Driven by Chemical Crossover. United States. https://doi.org/10.1021/acsnano.7b01494
Li, Wangda, Kim, Un-Hyuck, Dolocan, Andrei, Sun, Yang-Kook, and Manthiram, Arumugam. Sun . "Formation and Inhibition of Metallic Lithium Microstructures in Lithium Batteries Driven by Chemical Crossover". United States. https://doi.org/10.1021/acsnano.7b01494. https://www.osti.gov/servlets/purl/1430486.
@article{osti_1430486,
title = {Formation and Inhibition of Metallic Lithium Microstructures in Lithium Batteries Driven by Chemical Crossover},
author = {Li, Wangda and Kim, Un-Hyuck and Dolocan, Andrei and Sun, Yang-Kook and Manthiram, Arumugam},
abstractNote = {The formation of metallic lithium microstructures in the form of dendrites or mosses at the surface of anode electrodes (e.g., lithium metal, graphite, and silicon) leads to rapid capacity fade and poses grave safety risks in rechargeable lithium batteries. In this work, we present here a direct, relative quantitative analysis of lithium deposition on graphite anodes in pouch cells under normal operating conditions, paired with a model cathode material, the layered nickel-rich oxide LiNi0.61Co0.12Mn0.27O2, over the course of 3000 charge-discharge cycles. Secondary-ion mass spectrometry chemically dissects the solid-electrolyte interphase (SEI) on extensively cycled graphite with virtually atomic depth resolution and reveals substantial growth of Li-metal deposits. With the absence of apparent kinetic (e.g., fast charging) or stoichiometric restraints (e.g., overcharge) during cycling, we show lithium deposition on graphite is triggered by certain transition-metal ions (manganese in particular) dissolved from the cathode in a disrupted SEI. This insidious effect is found to initiate at a very early stage of cell operation (<200 cycles) and can be effectively inhibited by substituting a small amount of aluminum (~1 mol %) in the cathode, resulting in much reduced transition-metal dissolution and drastically improved cyclability. In conclusion, our results may also be applicable to studying the unstable electrodeposition of lithium on other substrates, including Li metal.},
doi = {10.1021/acsnano.7b01494},
journal = {ACS Nano},
number = 6,
volume = 11,
place = {United States},
year = {2017},
month = {5}
}

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Works referencing / citing this record:

A Material Perspective of Rechargeable Metallic Lithium Anodes
journal, February 2018


Mn versus Al in Layered Oxide Cathodes in Lithium-Ion Batteries: A Comprehensive Evaluation on Long-Term Cyclability
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  • Advanced Energy Materials, Vol. 8, Issue 15
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Hybrid Lithium-Sulfur Batteries with an Advanced Gel Cathode and Stabilized Lithium-Metal Anode
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  • Xu, Henghui; Wang, Shaofei; Manthiram, Arumugam
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Extending the Service Life of High-Ni Layered Oxides by Tuning the Electrode-Electrolyte Interphase
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Cross Talk between Transition Metal Cathode and Li Metal Anode: Unraveling Its Influence on the Deposition/Dissolution Behavior and Morphology of Lithium
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  • Betz, Johannes; Brinkmann, Jan‐Paul; Nölle, Roman
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Ethylene Carbonate‐Free Electrolytes for High‐Nickel Layered Oxide Cathodes in Lithium‐Ion Batteries
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  • Li, Wangda; Dolocan, Andrei; Li, Jianyu
  • Advanced Energy Materials, Vol. 9, Issue 29
  • DOI: 10.1002/aenm.201901152

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journal, January 2020


Reviving lithium cobalt oxide-based lithium secondary batteries-toward a higher energy density
journal, January 2018

  • Wang, Longlong; Chen, Bingbing; Ma, Jun
  • Chemical Society Reviews, Vol. 47, Issue 17
  • DOI: 10.1039/c8cs00322j

A highly stabilized nickel-rich cathode material by nanoscale epitaxy control for high-energy lithium-ion batteries
journal, January 2018

  • Kim, Junhyeok; Ma, Hyunsoo; Cha, Hyungyeon
  • Energy & Environmental Science, Vol. 11, Issue 6
  • DOI: 10.1039/c8ee00155c

Ultrathin Al foils to fabricate dendrite-free Li–Al anodes
journal, January 2019

  • Wu, Lan; He, Guang; Ding, Yi
  • Journal of Materials Chemistry A, Vol. 7, Issue 44
  • DOI: 10.1039/c9ta09464d