In situ transmission electron microscopy of lead dendrites and lead ions in aqueous solution.

An ideal technique for observing nanoscale assembly would provide atomic-resolution images of both the products and the reactants in real time. Using a transmission electron microscope we image in situ the electrochemical deposition of lead from an aqueous solution of lead(II) nitrate. Both the lead deposits and the local Pb(2+) concentration can be visualized. Depending on the rate of potential change and the potential history, lead deposits on the cathode in a structurally compact layer or in dendrites. In both cases the deposits can be removed and the process repeated. Asperities that persist through many plating and stripping cycles consistently nucleate larger dendrites. Quantitative digital image analysis reveals excellent correlation between changes in the Pb(2+) concentration, the rate of lead deposition, and the current passed by the electrochemical cell. Real-time electron microscopy of dendritic growth dynamics and the associated local ionic concentrations can provide new insight into the functional electrochemistry of batteries and related energy storage technologies.

[1]  V. Radmilović,et al.  Morphology of lead dendrites electrodeposited by square-wave pulsating overpotential , 1997 .

[2]  Niels de Jonge,et al.  Electron microscopy of specimens in liquid. , 2011, Nature nanotechnology.

[3]  Mikazu Yui,et al.  Ionic Diffusion Coefficients of Cs+ Pb2+, Sm3+ Ni2+, SeO42- and TcO4- in Free Water Determined from Conductivity Measurements , 1996 .

[4]  H. Perrot,et al.  Growth of electrolytic copper dendrites. I: Current transients and optical observation , 2007 .

[5]  James E. Evans,et al.  Controlled growth of nanoparticles from solution with in situ liquid transmission electron microscopy. , 2011, Nano letters.

[6]  J. Spence.  High-Resolution Electron Microscopy , 2003 .

[7]  F. Ross,et al.  Dynamic microscopy of nanoscale cluster growth at the solid–liquid interface , 2003, Nature materials.

[8]  M. Mecklenburg,et al.  Charged nanoparticle dynamics in water induced by scanning transmission electron microscopy. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[9]  Jean-Marie Tarascon,et al.  Li-O2 and Li-S batteries with high energy storage. , 2011, Nature materials.

[10]  Pankaj Arora,et al.  Battery separators. , 2004, Chemical reviews.

[11]  S. Aloni,et al.  Imaging Nanobubbles in Water with Scanning Transmission Electron Microscopy , 2011 .

[12]  Axel Voigt,et al.  Three-dimensional phase-field crystal modeling of fcc and bcc dendritic crystal growth , 2011 .

[13]  H. White,et al.  Electrochemistry at Pt band electrodes of width approaching molecular dimensions. Breakdown of transport equations at very small electrodes , 1987 .

[14]  E. Chassaing,et al.  Shape evolution of metals electrodeposited from binary electrolytes , 2003 .

[15]  J. Tarascon,et al.  In Situ Observation and Long-Term Reactivity of Si/C/CMC Composites Electrodes for Li-Ion Batteries , 2011 .

[16]  Peter C Searson,et al.  Quantifying electrochemical nucleation and growth of nanoscale clusters using real-time kinetic data. , 2006, Nano letters.

[17]  Jeffrey W Bullard.  Approximate rate constants for nonideal diffusion and their application in a stochastic model. , 2007, The journal of physical chemistry. A.

[18]  Reza S. Yassar,et al.  Real-time observation of lithium fibers growth inside a nanoscale lithium-ion battery , 2011 .

[19]  H. Minoura,et al.  Formation of Highly Crystallized β‐PbO Thin Films by Cathodic Electrodeposition of Pb and Its Rapid Oxidation in Air , 2005 .

[20]  Jean-Marie Tarascon,et al.  Live Scanning Electron Microscope Observations of Dendritic Growth in Lithium/Polymer Cells , 2002 .

[21]  J. Rasaiah,et al.  Solvent Structure, Dynamics, and Ion Mobility in Aqueous Solutions at 25 °C , 1998 .

[22]  A. Alivisatos,et al.  Observation of Single Colloidal Platinum Nanocrystal Growth Trajectories , 2009, Science.

[23]  J. Langer.  Instabilities and pattern formation in crystal growth , 1980 .

[24]  John P. Sullivan,et al.  Lithium Fiber Growth on the Anode in a Nanowire Lithium Ion Battery During Charging , 2011 .

[25]  J. Dufrêche,et al.  Analytical theories of transport in concentrated electrolyte solutions from the MSA. , 2005, The journal of physical chemistry. B.

[26]  G. Wranglén.  Dendrites and growth layers in the electrocrystallization of metals , 1960 .

[27]  L. Abrantes,et al.  Lead electrodeposition from very alkaline media , 2005 .

[28]  Kenneth G. Libbrecht,et al.  The physics of snow crystals , 2005 .