Direct Evidence of a Chemical Conversion Mechanism of Atomic-Layer-Deposited TiO2 Anodes During Lithiation Using LiPF6 Salt

Charlton, Matthew R.; Dylla, Anthony G.; Stevenson, Keith J.

doi:10.1021/acs.jpcc.5b08298

Title: Direct Evidence of a Chemical Conversion Mechanism of Atomic-Layer-Deposited TiO₂ Anodes During Lithiation Using LiPF₆ Salt

Journal Article · Mon Nov 30 00:00:00 EST 2015 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.5b08298· OSTI ID:1370043

Charlton, Matthew R. ^[1]; Dylla, Anthony G. ^[1]; Stevenson, Keith J. ^[1]

Univ. of Texas, Austin, TX (United States)

Titanium dioxide has been identified as a prospective anode material for use in lithium ion batteries. The higher lithiation potential of TiO₂ versus other common anodes is more electrochemically compatible with most organic electrolytes, thus leading to reduced solid electrolyte interphase formation and overall more stable battery systems. However, in this study TiO₂ has exhibited poor cycling stability with common electrolytes containing lithium hexafluorophosphate (LiPF₆) salt. Combined electrochemical and spectroscopic analyses have revealed this to be due to the onset of reversible fluorination of the anode and chemical conversion of TiO₂ to TiOF₂ during lithiation. Comparison of electrochemical cycling of atomic-layer-deposited TiO2 anodes using LiPF6 with and without a hydrofluoric acid scavenger, tributylamine, to cycling using a nonfluorinated lithium perchlorate (LiClO₄) salt indicates that the in situ formation of hydrofluoric acid in the electrolyte from decomposition of the PF$$_{6^–}$$ anion alters the lithiation electrochemistry. X-ray photoelectron spectroscopy (XPS) analysis and time-of-flight secondary-ion mass spectrometry (ToF SIMS) depth profiling measurements confirmed the presence of TiF₂ and TiOF surface and bulk phases, respectively, in the electrode upon lithiation.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Understanding Charge Separation and Transfer at Interfaces in Energy Materials (CST)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0001091

OSTI ID:: 1370043

Journal Information:: Journal of Physical Chemistry. C, Vol. 119, Issue 51; Related Information: CST partners with University of Texas at Austin (lead); Sandia National Laboratories; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 10 works

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Title: Direct Evidence of a Chemical Conversion Mechanism of Atomic-Layer-Deposited TiO2 Anodes During Lithiation Using LiPF6 Salt

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Title: Direct Evidence of a Chemical Conversion Mechanism of Atomic-Layer-Deposited TiO₂ Anodes During Lithiation Using LiPF₆ Salt