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Title: From Microparticles to Nanowires and Back: Radical Transformations in Plated Li Metal Morphology Revealed via in Situ Scanning Electron Microscopy

Journal Article · · Nano Letters

We report that Li metal is the preferred anode material for all-solid-state Li batteries. However, a stable plating and stripping of Li metal at the anode–solid electrolyte interface remains a significant challenge particularly at practically feasible current densities. This problem usually relates to high and/or inhomogeneous Li-electrode–electrolyte interfacial impedance and formation and growth of high-aspect-ratio dendritic Li deposits at the electrode–electrolyte interface, which eventually shunt the battery. To better understand details of Li metal plating, we use operando electron microscopy and Auger spectroscopy to probe nucleation, growth, and stripping of Li metal during cycling of a model solid-state Li battery as a function of current density and oxygen pressure. We find a linear correlation between the nucleation density of Li clusters and the charging rate in an ultrahigh vacuum, which agrees with a classical nucleation and growth model. Moreover, the trace amount of oxidizing gas (≈10–6 Pa of O2) promotes the Li growth in a form of nanowires due to a fine balance between the ion current density and a growth rate of a thin lithium-oxide shell on the surface of the metallic Li. Interestingly, increasing the partial pressure of O2 to 10–5 Pa resumes Li plating in a form of 3D particles. In conclusion, our results demonstrate the importance of trace amounts of preexisting or ambient oxidizing species on lithiation processes in solid-state batteries.

Research Organization:
Sandia National Lab. (SNL-CA), Livermore, CA (United States); Energy Frontier Research Centers (EFRC) (United States). Nanostructures for Electrical Energy Storage (NEES)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
AC04-94AL85000; EE0007803; SC0001160
OSTI ID:
1485830
Report Number(s):
SAND-2018-11517J; 669387
Journal Information:
Nano Letters, Vol. 18, Issue 3; ISSN 1530-6984
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 38 works
Citation information provided by
Web of Science

References (63)

Negating interfacial impedance in garnet-based solid-state Li metal batteries journal December 2016
Transparent cubic garnet-type solid electrolyte of Al2O3-doped Li7La3Zr2O12 journal October 2015
Issues and challenges facing rechargeable lithium batteries journal November 2001
Temperature effects on cycling stability of Li plating/stripping on Ta-doped Li7La3Zr2O12 journal March 2017
Origin of lithium whisker formation and growth under stress journal October 2019
Self-diffusion coefficient of lithium in lithium oxide journal December 1979
Some fundamental aspects of levelling and brightening in metal electrodeposition journal July 1991
In-Situ Electron Microscope Observations of Electrochemical Li Deposition/Dissolution with a LiPON Electrolyte journal January 2014
Room temperature elastic moduli and Vickers hardness of hot-pressed LLZO cubic garnet journal July 2012
Lithium Dendrite Formation on a Lithium Metal Anode from Liquid, Polymer and Solid Electrolytes journal January 2016
Interface Limited Lithium Transport in Solid-State Batteries journal December 2013
The chemical and electrochemical stability of beta-alumina journal February 1986
Electromechanical Probing of Li/Li2CO3 Core/Shell Particles in a TEM journal January 2013
Mechanisms of dendritic growth investigated by in situ light microscopy during electrodeposition and dissolution of lithium journal September 2014
Oxide-Assisted Growth of Semiconducting Nanowires journal April 2003
Nanocomposite NiTi shape memory alloy with high strength and fatigue resistance journal January 2021
Fabrication, Testing, and Simulation of All-Solid-State Three-Dimensional Li-Ion Batteries journal November 2016
Modeling the Nucleation and Growth of Li at Metal Current Collector/LiPON Interfaces journal January 2015
Beam-assisted large elongation of in situ formed Li2O nanowires journal July 2012
Making Li-metal electrodes rechargeable by controlling the dendrite growth direction journal June 2017
Transition from Superlithiophobicity to Superlithiophilicity of Garnet Solid-State Electrolyte journal September 2016
Secondary electron emission in the scanning electron microscope journal November 1983
Elastic, plastic, and creep mechanical properties of lithium metal journal October 2018
Growth and Properties of "Whiskers": Further research is needed to show why crystal filaments are many times as strong as large crystals journal September 1958
Interactions between Lithium Growths and Nanoporous Ceramic Separators journal November 2018
The Impact of Elastic Deformation on Deposition Kinetics at Lithium/Polymer Interfaces journal January 2005
Opportunities and challenges for a sustainable energy future journal August 2012
Real Space Mapping of Li-Ion Transport in Amorphous Si Anodes with Nanometer Resolution journal September 2010
Self-diffusion in solid lithium journal October 2010
Oxidation-assisted ductility of aluminium nanowires journal June 2014
General Relationship for the Thermal Oxidation of Silicon journal December 1965
Liquid cell transmission electron microscopy observation of lithium metal growth and dissolution: Root growth, dead lithium and lithium flotsams journal February 2017
Dendrite-free Li deposition using trace-amounts of water as an electrolyte additive journal July 2015
Enhanced strength and temperature dependence of mechanical properties of Li at small scales and its implications for Li metal anodes journal December 2016
Layered reduced graphene oxide with nanoscale interlayer gaps as a stable host for lithium metal anodes journal March 2016
In situ SEM study of a lithium deposition and dissolution mechanism in a bulk-type solid-state cell with a Li2S–P2S5 solid electrolyte journal January 2013
Colloquium : Cluster growth on surfaces: Densities, size distributions, and morphologies journal July 2013
Toward garnet electrolyte–based Li metal batteries: An ultrathin, highly effective, artificial solid-state electrolyte/metallic Li interface journal April 2017
Ion‐ and electron‐assisted gas‐surface chemistry—An important effect in plasma etching journal May 1979
Stress-driven lithium dendrite growth mechanism and dendrite mitigation by electroplating on soft substrates journal March 2018
An XPS study of the adsorption of oxygen and water vapor on clean lithium films journal May 1984
Resolution of the Modulus versus Adhesion Dilemma in Solid Polymer Electrolytes for Rechargeable Lithium Metal Batteries journal January 2012
Suppression of dendritic lithium growth in lithium metal-based batteries journal January 2018
Reviving Lithium-Metal Anodes for Next-Generation High-Energy Batteries journal June 2017
A solid future for battery development journal September 2016
A new examination of secondary electron yield data journal January 2005
Nanoscale Nucleation and Growth of Electrodeposited Lithium Metal journal January 2017
Reviving the lithium metal anode for high-energy batteries journal March 2017
Surface/Interface Effects on High-Performance Thin-Film All-Solid-State Li-Ion Batteries journal October 2015
Atomic Insight into the Lithium Storage and Diffusion Mechanism of SiO 2 /Al 2 O 3 Electrodes of Lithium Ion Batteries: ReaxFF Reactive Force Field Modeling journal March 2016
Building better batteries journal February 2008
Revealing Nanoscale Passivation and Corrosion Mechanisms of Reactive Battery Materials in Gas Environments journal July 2017
A preliminary investigation of fracture toughness of Li7La3Zr2O12 and its comparison to other solid Li-ionconductors journal April 2013
The Effect of Tension on the Electrical Resistance of Certain Abnormal Metals journal January 1922
Mechanical Deformation of a Lithium-Metal Anode Due to a Very Stiff Separator journal January 2014
Insights into capacity loss mechanisms of all-solid-state Li-ion batteries with Al anodes journal January 2014
Self-heating–induced healing of lithium dendrites journal March 2018
In Situ Scanning Electron Microscopy Characterization of the Mechanism for Li Dendrite Growth journal January 2016
Air-Stable Lithium Spheres Produced by Electrochemical Plating journal August 2018
Direct observation of lithium dendrites inside garnet-type lithium-ion solid electrolyte journal August 2015
Thin-film lithium and lithium-ion batteries journal November 2000
Elastic Modulus of Isotopically-Concentrated Lithium journal January 1960
In-Situ Cross-Sectional SEM Observations of Li Plating and Stripping on Oxide-Based-Solid-State Electrolytes journal September 2016

Cited By (5)

Engineering stable interfaces for three-dimensional lithium metal anodes journal July 2018
Review of Recent Development of In Situ/Operando Characterization Techniques for Lithium Battery Research journal May 2019
Mechanical and Electronic Stabilization of Solid Electrolyte Interphase with Sulfite Additive for Lithium Metal Batteries journal January 2019
In Situ Scanning Electron Microscope Observations of Li Plating/Stripping Reactions with Pt Current Collectors on LiPON Electrolyte journal January 2018
Lithium whisker growth and stress generation in an in situ atomic force microscope–environmental transmission electron microscope set-up journal January 2020