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 C Hersam, Jeffrey W. Elam

Research output: Contribution to journalArticle

3 Citations (Scopus)

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
Pages (from-to)26972-26981
Number of pages10
JournalACS Applied Materials and Interfaces
Volume10
Issue number32
DOIs
Publication statusPublished - Aug 15 2018

Fingerprint

Atomic layer deposition
Lithium
Anodes
Coatings
Temperature
Metals
lithium fluoride
Graphite
Secondary batteries
Solid electrolytes
Protective coatings
Silicon
Nanoindentation
Plating
Electrolytes
Strength of materials
Elastic moduli

Keywords

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

ASJC Scopus subject areas

  • Materials Science(all)

Cite this

Novel ALD Chemistry Enabled Low-Temperature Synthesis of Lithium Fluoride Coatings for Durable Lithium Anodes. / Chen, Lin; Chen, Kan Sheng; Chen, Xinjie; Ramirez, Giovanni; Huang, Zhennan; Geise, Natalie R.; Steinrück, Hans Georg; Fisher, Brandon L.; Shahbazian-Yassar, Reza; Toney, Michael F.; Hersam, Mark C; Elam, Jeffrey W.

In: ACS Applied Materials and Interfaces, Vol. 10, No. 32, 15.08.2018, p. 26972-26981.

Research output: Contribution to journalArticle

Chen, L, Chen, KS, Chen, X, Ramirez, G, Huang, Z, Geise, NR, Steinrück, HG, Fisher, BL, Shahbazian-Yassar, R, Toney, MF, Hersam, MC & Elam, JW 2018, 'Novel ALD Chemistry Enabled Low-Temperature Synthesis of Lithium Fluoride Coatings for Durable Lithium Anodes', ACS Applied Materials and Interfaces, vol. 10, no. 32, pp. 26972-26981. https://doi.org/10.1021/acsami.8b04573
Chen, Lin ; Chen, Kan Sheng ; Chen, Xinjie ; Ramirez, Giovanni ; Huang, Zhennan ; Geise, Natalie R. ; Steinrück, Hans Georg ; Fisher, Brandon L. ; Shahbazian-Yassar, Reza ; Toney, Michael F. ; Hersam, Mark C ; Elam, Jeffrey W. / Novel ALD Chemistry Enabled Low-Temperature Synthesis of Lithium Fluoride Coatings for Durable Lithium Anodes. In: ACS Applied Materials and Interfaces. 2018 ; Vol. 10, No. 32. pp. 26972-26981.
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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 {\AA}/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.",
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