Lithium-ion batteries have had a profound impact on our daily life, but inherent limitations make it difficult for Li-ion chemistries to meet the growing demands for portable electronics, electric vehicles and grid-scale energy storage. Therefore, chemistries beyond Li-ion are currently being investigated and need to be made viable for commercial applications. The use of metallic Li is one of the most favoured choices for next-generation Li batteries, especially Li-S and Li-air systems. After falling into oblivion for several decades because of safety concerns, metallic Li is now ready for a revival, thanks to the development of investigative tools and nanotechnology-based solutions. In this Review, we first summarize the current understanding on Li anodes, then highlight the recent key progress in materials design and advanced characterization techniques, and finally discuss the opportunities and possible directions for future development of Li anodes in applications.

Reviving the lithium metal anode for high-energy batteries

The lithium metal battery is strongly considered to be one of the most promising candidates for high-energy-density energy storage devices in our modern and technology-based society. However, uncontrollable lithium dendrite growth induces poor cycling efficiency and severe safety concerns, dragging lithium metal batteries out of practical applications. This review presents a comprehensive overview of the lithium metal anode and its dendritic lithium growth. First, the working principles and technical challenges of a lithium metal anode are underscored. Specific attention is paid to the mechanistic understandings and quantitative models for solid electrolyte interphase (SEI) formation, lithium dendrite nucleation, and growth. On the basis of previous theoretical understanding and analysis, recently proposed strategies to suppress dendrite growth of lithium metal anode and some other metal anodes are reviewed. A section dedicated to the potential of full-cell lithium metal batteries for practical applicatio...

Toward Safe Lithium Metal Anode in Rechargeable Batteries: A Review.

Rechargeable lithium-sulfur batteries.

Electrolytes and interphases in Li-ion batteries and beyond.

Lithium (Li) metal is an ideal anode material for rechargeable batteries due to its extremely high theoretical specific capacity (3860 mA h g−1), low density (0.59 g cm−3) and the lowest negative electrochemical potential (−3.040 V vs. the standard hydrogen electrode). Unfortunately, uncontrollable dendritic Li growth and limited Coulombic efficiency during Li deposition/stripping inherent in these batteries have prevented their practical applications over the past 40 years. With the emergence of post-Li-ion batteries, safe and efficient operation of Li metal anodes has become an enabling technology which may determine the fate of several promising candidates for the next generation energy storage systems, including rechargeable Li–air batteries, Li–S batteries, and Li metal batteries which utilize intercalation compounds as cathodes. In this paper, various factors that affect the morphology and Coulombic efficiency of Li metal anodes have been analyzed. Technologies utilized to characterize the morphology of Li deposition and the results obtained by modelling of Li dendrite growth have also been reviewed. Finally, recent development and urgent need in this field are discussed.

Lithium metal anodes for rechargeable batteries

Department of Chemical Engineering, University of California, Berkeley, California 94720-1462, USAPast theories of electrode stability assume that the surface tension resists the ampliﬁcation of surface roughness at cathodes andshow that instability at lithium/liquid interfaces cannot be prevented by surface forces alone @Electrochim. Acta, 40, 599 ~1995!#.This work treats interfacial stability in lithium/polymer systems where the electrolyte is solid. Linear elasticity theory is employedto compute the additional effect of bulk mechanical forces on electrode stability. The lithium and polymer are treated as Hookeanelastic materials, characterized by their shear moduli and Poisson’s ratios. Two-dimensional displacement distributions that satisfyforce balances across a periodically deforming interface are derived; these allow computation of the stress and surface-tensionforces. The incorporation of elastic effects into a kinetic model demonstrates regimes of electrolyte mechanical properties whereampliﬁcation of surface roughness can be inhibited. For a polymer material with Poisson’s ratio similar to poly~ethylene oxide!,interfacial roughening is mechanically suppressed when the separator shear modulus is about twice that of lithium.© 2005 The Electrochemical Society. @DOI: 10.1149/1.1850854# All rights reserved.Manuscript submitted January 16, 2004; revised manuscript received July 29, 2004. Available electronically January 11, 2005.

https://iopscience.iop.org/article/10.1149/1.1850854/pdf

The impact of elastic deformation on deposition kinetics at lithium/polymer interfaces

Dendrite growth in a parallel-electrode lithium/polymer cell during galvanostatic charging has been modeled. The growth model is surface-energy controlled, incorporating the effect of dendrite tip curvature into its dendrite growth kinetics. Using data representative of the oxymethylene-linked poly(ethylene oxide)/LiTFSI system, it is shown that dendrites accelerate across cells under all conditions, and that growth is always slowed by lowering the current density. Cell shorting occurs during typical charges at current densities above 75% of the limiting current. Increased interelectrode distance slows failure, but the advantages decrease as distance lengthens. A factor of 1000 increase in surface forces delays cell failure by only 6%. While larger diffusion coefficients usually extend the time to cell failure, this trend is not consistent at high transference numbers. © 2003 The Electrochemical Society. All rights reserved.

https://iopscience.iop.org/article/10.1149/1.1606686/pdf

Dendrite Growth in Lithium/Polymer Systems A Propagation Model for Liquid Electrolytes under Galvanostatic Conditions

Direct in situ measurements of Li transport in Li-ion battery negative electrodes

http://ma.ecsdl.org/content/MA2009-02/8/654.full.pdf

Direct In-Situ Measurements of Li Transport in Li-ion Battery Negative Electrodes

Mullins-Sekerka linear stability analysis and the Barton and Bockris dendrite-propagation model are popular methods used to describe cathodic roughening and dendritic growth. These commonly cited theories employ kinetic relationships that differ in mathematical form, but both contain the effects of surface tension and local concentration deviations induced by surface roughening. Here, a kinetic model is developed which additionally includes mechanical forces such as elasticity, viscous drag, and pressure, showing their effect on exchange current densities and potentials at roughening interfaces. The proposed expression describes the current density in terms of applied overpotential at deformed interfaces with arbitrary three-dimensional interfacial geometry. Both the Mullins-Sekerka and the Barton-Bockris kinetics can be derived as special cases of the general expression, thereby validating the proposed model and elucidating the fundamental assumptions on which the two previous theories rely.

https://iopscience.iop.org/article/10.1149/1.1710893/pdf

Charles W. Monroe

Papers

The impact of elastic deformation on deposition kinetics at lithium/polymer interfaces

Dendrite Growth in Lithium/Polymer Systems A Propagation Model for Liquid Electrolytes under Galvanostatic Conditions

Direct in situ measurements of Li transport in Li-ion battery negative electrodes

Direct In-Situ Measurements of Li Transport in Li-ion Battery Negative Electrodes

The Effect of Interfacial Deformation on Electrodeposition Kinetics