Toward quantitative electrochemical measurements on the nanoscale by scanning probe microscopy: Environmental and current spreading effects

Thomas M. Arruda, Amit Kumar, Stephen Jesse, Gabriel M. Veith, Alexander Tselev, Arthur P. Baddorf, Nina Balke, Sergei V. Kalinin

Research output: Contribution to journalArticlepeer-review

21 Scopus citations

Abstract

The application of electric bias across tip-surface junctions in scanning probe microscopy can readily induce surface and bulk electrochemical processes that can be further detected though changes in surface topography, Faradaic or conductive currents, or electromechanical strain responses. However, the basic factors controlling tip-induced electrochemical processes, including the relationship between applied tip bias and the thermodynamics of local processes, remains largely unexplored. Using the model Li-ion reduction reaction on the surface in Li-ion conducting glass ceramic, we explore the factors controlling Li-metal formation and find surprisingly strong effects of atmosphere and back electrode composition on the process. We find that reaction processes are highly dependent on the nature of the counter electrode and environmental conditions. Using a nondepleting Li counter electrode, Li particles could grow significantly larger and faster than a depleting counter electrode. Significant Li ion depletion leads to the inability for further Li reduction. Time studies suggest that Li diffusion replenishes the vacant sites after ∼12 h. These studies suggest the feasibility of SPM-based quantitative electrochemical studies under proper environmental controls, extending the concepts of ultramicroelectrodes to the single-digit nanometer scale.

Original languageEnglish
Pages (from-to)8175-8182
Number of pages8
JournalACS Nano
Volume7
Issue number9
DOIs
StatePublished - Sep 24 2013

Keywords

  • Li ion battery
  • counter electrode effects
  • nanoscale electrochemistry
  • scanning probe microscopy
  • solid state electrolyte

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