skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Nanoscale in situ detection of nucleation and growth of Li electrodeposition at various current densities

Journal Article · · Journal of Materials Chemistry. A
DOI:https://doi.org/10.1039/C8TA00343B· OSTI ID:1460946

Li metal batteries can store at least ten times more energy than currently existing Li-ion batteries. However, during routine charging and discharging, Li dendrites grow on the Li metal electrode, which can lead to capacity loss by the consumption of Li salt at the surface of the Li dendrites, and be a safety hazard resulting from the potential for short-circuits. Although past efforts have provided useful information about the morphology and surface area of Li dendrite formation at the microscale, a nanoscale understanding of nucleation and growth of Li nanoparticle electrodeposition is still elusive. In this study, using a new electrochemical cell for transmission mode grazing incidence small angle X-ray scattering, we obtained, for the first time, the primary nucleus size of Li nanoparticles, their size evolution and their fractal structures at various current densities and in real-time. The measured average radius of gyration, Rg, at current densities of 0.1, 0.5, and 2.0 mA cm-2 is 5.4 ± 0.4, 4.5 ± 0.3, and 3.5 ± 0.3 nm, respectively. This variation in size with current density is noteworthy when recognizing that the surface area-to-volume ratio of the Li nanoparticles is 3.7 times higher at 2.0 mA cm-2 than at 0.1 mA cm-2. We also compared a hierarchical fractal structure of Li particles from the nanometer to micrometer scale. Our findings illuminate the role of overpotential in the reactive surface area of Li dendrites at the nanoscale, and provide a novel research platform for suppressing Li dendrite formation in Li metal battery systems.

Research Organization:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1460946
Journal Information:
Journal of Materials Chemistry. A, Vol. 6, Issue 11; ISSN 2050-7488
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 18 works
Citation information provided by
Web of Science

References (42)

In situ NMR observation of the formation of metallic lithium microstructures in lithium batteries journal May 2010
Direct In Situ Observation and Numerical Simulations of Non-Shrinking-Core Behavior in an MCMB Graphite Composite Electrode journal January 2012
Prospects for Dendrite-Free Cycling of Li Metal Batteries journal January 2015
Ionic-Liquid-Nanoparticle Hybrid Electrolytes: Applications in Lithium Metal Batteries journal November 2013
Ultrathin Two-Dimensional Atomic Crystals as Stable Interfacial Layer for Improvement of Lithium Metal Anode journal September 2014
Controlled Lithium Dendrite Growth by a Synergistic Effect of Multilayered Graphene Coating and an Electrolyte Additive journal April 2015
Anode-Free Rechargeable Lithium Metal Batteries journal August 2016
Lithium-coated polymeric matrix as a minimum volume-change and dendrite-free lithium metal anode journal March 2016
Optical observation of Li dendrite growth in ionic liquid journal June 2013
Nanoscale Nucleation and Growth of Electrodeposited Lithium Metal journal January 2017
Designing Safe Electrolyte Systems for a High-Stability Lithium-Sulfur Battery journal January 2018
Electrochemical aspects of the generation of ramified metallic electrodeposits journal December 1990
Lithiophilic Sites in Doped Graphene Guide Uniform Lithium Nucleation for Dendrite-Free Lithium Metal Anodes journal May 2017
Nanoscale Imaging of Fundamental Li Battery Chemistry: Solid-Electrolyte Interphase Formation and Preferential Growth of Lithium Metal Nanoclusters journal February 2015
Effects of current densities on the lithium plating morphology at a lithium phosphorus oxynitride glass electrolyte/copper thin film interface journal July 2013
Magnetosome-like ferrimagnetic iron oxide nanocubes for highly sensitive MRI of single cells and transplanted pancreatic islets journal January 2011
In Situ Observations of Nanoparticle Early Development Kinetics at Mineral−Water Interfaces journal November 2010
Columnar Lithium Metal Anodes journal September 2017
Dendrite-Free Lithium Deposition via Self-Healing Electrostatic Shield Mechanism journal March 2013
Three-dimensional characterization of electrodeposited lithium microstructures using synchrotron X-ray phase contrast imaging journal January 2015
7Li MRI of Li batteries reveals location of microstructural lithium journal February 2012
Design principles for electrolytes and interfaces for stable lithium-metal batteries journal September 2016
The critical role of lithium nitrate in the gas evolution of lithium–sulfur batteries journal January 2016
Heterogeneous Nucleation and Growth of Lithium Electrodeposits on Negative Electrodes journal January 2013
Grazing-incidence transmission small angle X-ray scattering from thin films of block copolymers journal February 2013
Li–O2 and Li–S batteries with high energy storage journal January 2012
A review of lithium deposition in lithium-ion and lithium metal secondary batteries journal May 2014
Lithium metal anodes for rechargeable batteries journal January 2014
Dendritic growth mechanisms in lithium/polymer cells journal September 1999
Transition of lithium growth mechanisms in liquid electrolytes journal January 2016
Observation and Quantification of Nanoscale Processes in Lithium Batteries by Operando Electrochemical (S)TEM journal February 2015
Electroless Formation of Hybrid Lithium Anodes for Fast Interfacial Ion Transport journal September 2017
Branched fractal patterns in non-equilibrium electrochemical deposition from oscillatory nucleation and growth journal November 1997
A highly ordered nanostructured carbon–sulphur cathode for lithium–sulphur batteries journal May 2009
Detection of subsurface structures underneath dendrites formed on cycled lithium metal electrodes journal November 2013
Interconnected hollow carbon nanospheres for stable lithium metal anodes journal July 2014
High rate and stable cycling of lithium metal anode journal February 2015
The interplay between solid electrolyte interface (SEI) and dendritic lithium growth journal October 2017
Lithiophilic Sites in Doped Graphene Guide Uniform Lithium Nucleation for Dendrite-Free Lithium Metal Anodes journal May 2017
Electroless Formation of Hybrid Lithium Anodes for Fast Interfacial Ion Transport journal September 2017
Columnar Lithium Metal Anodes journal September 2017
The critical role of lithium nitrate in the gas evolution of lithium–sulfur batteries text January 2016

Cited By (2)

Favorable lithium deposition behaviors on flexible carbon microtube skeleton enable a high-performance lithium metal anode journal January 2018
An acetylene black modified gel polymer electrolyte for high-performance lithium–sulfur batteries journal January 2019

Figures / Tables (4)


Similar Records

High-performance all-solid-state batteries enabled by salt bonding to perovskite in poly(ethylene oxide)
Journal Article · Thu Aug 29 00:00:00 EDT 2019 · Proceedings of the National Academy of Sciences of the United States of America · OSTI ID:1460946

High Current Cycling in a Superconcentrated Ionic Liquid Electrolyte to Promote Uniform Li Morphology and a Uniform LiF-Rich Solid Electrolyte Interphase
Journal Article · Wed Sep 02 00:00:00 EDT 2020 · ACS Applied Materials and Interfaces · OSTI ID:1460946

Interface Design for High‐Performance All‐Solid‐State Lithium Batteries
Journal Article · Fri Dec 29 00:00:00 EST 2023 · Advanced Energy Materials · OSTI ID:1460946