Novel ALD Chemistry Enabled Low-Temperature Synthesis of Lithium Fluoride Coatings for Durable Lithium Anodes

Lin Chen, Kan Sheng Chen, Xinjie Chen, Giovanni Ramirez, Zhennan Huang, Natalie R. Geise, Hans Georg Steinrück, Brandon L. Fisher, Reza Shahbazian-Yassar, Michael F. Toney, Mark Hersam, Jeffrey W. Elam*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

124 Scopus citations

Abstract

Lithium metal anodes can largely enhance the energy density of rechargeable batteries because of the high theoretical capacity and the high negative potential. However, the problem of lithium dendrite formation and low Coulombic efficiency (CE) during electrochemical cycling must be solved before lithium anodes can be widely deployed. Herein, a new atomic layer deposition (ALD) chemistry to realize the low-temperature synthesis of homogeneous and stoichiometric lithium fluoride (LiF) is reported, which then for the first time, as far as we know, is deposited directly onto lithium metal. The LiF preparation is performed at 150 °C yielding 0.8 Å/cycle. The LiF films are found to be crystalline, highly conformal, and stoichiometric with purity levels >99%. Nanoindentation measurements demonstrate the LiF achieving a shear modulus of 58 GPa, 7 times higher than the sufficient value to resist lithium dendrites. When used as the protective coating on lithium, it enables a stable Coulombic efficiency as high as 99.5% for over 170 cycles, about 4 times longer than that of bare lithium anodes. The remarkable battery performance is attributed to the nanosized LiF that serves two critical functions simultaneously: (1) the high dielectric value creates a uniform current distribution for excellent lithium stripping/plating and ultrahigh mechanical strength to suppress lithium dendrites; (2) the great stability and electrolyte isolation by the pure LiF on lithium prevents parasitic reactions for a much improved CE. This new ALD chemistry for conformal LiF not only offers a promising avenue to implement lithium metal anodes for high-capacity batteries but also paves the way for future studies to investigate failure and evolution mechanisms of solid electrolyte interphase (SEI) using our LiF on anodes such as graphite, silicon, and lithium.

Original languageEnglish (US)
Pages (from-to)26972-26981
Number of pages10
JournalACS Applied Materials and Interfaces
Volume10
Issue number32
DOIs
StatePublished - Aug 15 2018

Funding

This work was supported as part of the Joint Center for Energy Storage Research (JCESR), an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences (BES). The use of the Center for Nanoscale Materials was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract no. DE-AC02-06CH11357. The GIWAXS measurements were performed at the Stanford Synchrotron Radiation Lightsource SLAC National Accelerator Laboratory, which is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515. The AFM measurements were supported by the Center for Electrochemical Energy Science, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science Basic Energy Sciences (DE-AC02-06CH11357). R.S.-Y. and Z.H. acknowledge the financial support from NSF-DMR Award no. 1620901. N.R.G. acknowledges support by the Department of Defense (DoD) through the National Defense Science & Engineering Graduate Fellowship (NDSEG) Program. This work was supported as part of the Joint Center for Energy Storage Research (JCESR), an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences (BES). The use of the Center for Nanoscale Materials was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract no. DE-AC02-06CH11357. The GIWAXS measurements were performed at the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, which is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515. The AFM measurements were supported by the Center for Electrochemical Energy Science, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Basic Energy Sciences (DE-AC02-06CH11357). R.S.-Y. and Z.H. acknowledge the financial support from NSF-DMR Award no. 1620901. N.R.G. acknowledges support by the Department of Defense (DoD) through the National Defense Science & Engineering Graduate Fellowship (NDSEG) Program.

Keywords

  • atomic layer deposition
  • high shear modulus
  • lithium fluoride
  • lithium metal anode
  • new chemistry

ASJC Scopus subject areas

  • General Materials Science

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