skip to main content

Attention:

The NSF Public Access Repository (NSF-PAR) system and access will be unavailable from 11:00 PM ET on Thursday, June 13 until 2:00 AM ET on Friday, June 14 due to maintenance. We apologize for the inconvenience.


Title: Electro-Chemo-Mechanical Challenges and Perspective in Lithium Metal Batteries
Abstract The development of next-generation batteries, utilizing electrodes with high capacities and power densities requires a comprehensive understanding and precise control of material interfaces and architectures. Electro-chemo-mechanics plays an integral role in the morphological evolution and stability of such complex interfaces. Volume changes in electrode materials and the chemical interactions of electrode/electrolyte interfaces result in nonuniform stress fields and structurally different interphases, fundamentally affecting the underlying transport and reaction kinetics. The origin of this mechanistic coupling and its implications on degradation is uniquely dependent on the interface characteristics. In this review, the distinct nature of chemo–mechanical coupling and failure mechanisms at solid–liquid interfaces and solid–solid interfaces is analyzed. For lithium metal electrodes, the critical role of surface/microstructural heterogeneities on the solid electrolyte interphase (SEI) stability and dendrite growth in liquid electrolytes, and on the onset of contact loss and filament penetration with solid electrolytes is summarized. With respect to composite electrodes, key differences in the microstructure-coupled electro-chemo-mechanical attributes of intercalation- and conversion-based chemistries are delineated. Moving from liquid to solid electrolytes in such cathodes, we highlight the significant impact of solid–solid point contacts on transport/mechanical response, electrochemical performance, and failure modes such as particle cracking and delamination. Finally, we present our perspective on future research directions and opportunities to address the underlying electro-chemo-mechanical challenges for enabling next-generation lithium metal batteries.  more » « less
Award ID(s):
2041499
NSF-PAR ID:
10436245
Author(s) / Creator(s):
; ; ; ;
Date Published:
Journal Name:
Applied Mechanics Reviews
Volume:
75
Issue:
1
ISSN:
0003-6900
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    As solid‐state batteries (SSBs) with lithium (Li) metal anodes gain increasing traction as promising next‐generation energy storage systems, a fundamental understanding of coupled electro‐chemo‐mechanical interactions is essential to design stable solid‐solid interfaces. Notably, uneven electrodeposition at the Li metal/solid electrolyte (SE) interface arising from intrinsic electrochemical and mechanical heterogeneities remains a significant challenge. In this work, the thermodynamic origins of mechanics‐coupled reaction kinetics at the Li/SE interface are investigated and its implications on electrodeposition stability are unveiled. It is established that the mechanics‐driven energetic contribution to the free energy landscape of the Li deposition/dissolution redox reaction has a critical influence on the interface stability. The study presents the competing effects of mechanical and electrical overpotential on the reaction distribution, and demarcates the regimes under which stress interactions can be tailored to enable stable electrodeposition. It is revealed that different degrees of mechanics contribution to the forward (dissolution) and backward (deposition) reaction rates result in widely varying stability regimes, and the mechanics‐coupled kinetics scenario exhibited by the Li/SE interface is shown to depend strongly on the thermodynamic and mechanical properties of the SE. This work highlights the importance of discerning the underpinning nature of electro‐chemo‐mechanical coupling toward achieving stable solid/solid interfaces in SSBs.

     
    more » « less
  2. null (Ed.)
    Engineering energy dense electrodes (e.g. lithium metal, conversion cathodes, etc.) with solid electrolytes is important for enhancing the practical energy density of solid-state batteries. However, large electrode volumetric strain can cause significant drive fracture, delamination, and accelerate degradation. This review discusses transport and chemo-mechanical challenges associated with energy dense solid state batteries. In particular, this review focuses on summarizing work which provides design strategies for implementation on energy dense anodes with rigid solid electrolytes. This review further assesses the properties which impact the elasticity of inorganic solid electrolytes and inorganic/organic hybrid electrolyte. Finally, this review discusses the advanced characterization approaches for analyzing the coupled electrochemistry/transport/mechanical phenomena that occur at buried solid-solid interfaces 
    more » « less
  3. Electrification of the transportation sector relies on radical re-imagining of energy storage technologies to provide affordable, high energy density, durable and safe systems. Next generation energy storage systems will need to leverage high energy density anodes and high voltage cathodes to achieve the required performance metrics (longer vehicle range, long life, production costs, safety). Solid-state batteries (SSBs) are promising materials technology for achieving these metrics by enabling these electrode systems due to the underlying material properties of the solid electrolyte ( viz. mechanical strength, electrochemical stability, ionic conductivity). Electro-chemo-mechanical degradation in SSBs detrimentally impact the Coulombic efficiencies, capacity retention, durability and safety in SSBs restricting their practical implementation. Solid|solid interfaces in SSBs are hot-spots of dynamics that contribute to the degradation of SSBs. Characterizing and understanding the processes at the solid|solid interfaces in SSBs is crucial towards designing of resilient, durable, high energy density SSBs. This work provides a comprehensive and critical summary of the SSB characterization with a focus on in situ and operando studies. Additionally, perspectives on experimental design, emerging characterization techniques and data analysis methods are provided. This work provides a thorough analysis of current status of SSB characterization as well as highlights important avenues for future work. 
    more » « less
  4. Metal-ion batteries (e.g., lithium and sodium ion batteries) are the promising power sources for portable electronics, electric vehicles, and smart grids. Recent metal-ion batteries with organic liquid electrolytes still suffer from safety issues regarding inflammability and insufficient lifetime.1 As the next generation energy storage devices, all-solid-state batteries (ASSBs) have promising potentials for the improved safety, higher energy density, and longer cycle life than conventional Li-ion batteries.2 The nonflammable solid electrolytes (SEs), where only Li ions are mobile, could prevent battery combustion and explosion since the side reactions that cause safety issues as well as degradation of the battery performance are largely suppressed. However, their practical application is hampered by the high resistance arising at the solid–solid electrode–electrolyte interface (including cathode-electrolyte interface and anode-electrolyte interface).3 Several methods have been introduced to optimize the contact capability as well as the electrochemical/chemical stability between the metal anodes (i.e.: Li and Na) and the SEs, which exhibited decent results in decreasing the charge transfer resistance and broadening the range of the stable energy window (i.e., lowing the chemical potential of metal anode below the highest occupied molecular orbital of the SEs).4 Nevertheless, mitigation for the cathode in ASSB is tardily developed because: (1) the porous structure of the cathode is hard to be infiltrated by SEs;5 (2) SEs would be oxidized and decomposed by the high valence state elements at the surface of the cathode at high state of charge.5 Herein, we demonstrate a universal cathode design strategy to achieve superior contact capability and high electrochemical/chemical stability with SEs. Stereolithography is adopted as a manufacturing technique to realize a hierarchical three-dimensional (HTD) electrode architecture with micro-size channels, which is expected to provide larger contact areas with SEs. Then, the manufactured cathode is sintered at 700 °C in a reducing atmosphere (e.g.: H2) to accomplish the carbonization of the resin, delivering sufficiently high electronic conductivity for the cathode. To avoid the direct exposure of the cathode active materials to the SEs, oxidative chemical vapor deposition technique (oCVD) is leveraged to build conformal and highly conducting poly(3,4-ethylenedioxythiophene) (PEDOT) on the surface of the HTD cathode.6 To demonstrate our design strategy, both NCM811 and Na3V2(PO4)3 is selected as active materials in the HTD cathode, then each cathode is paired with organic (polyacrylonitrile-based) and inorganic (sulfur-based) SEs assembled into two batteries (total four batteries). SEM and TEM reveal the micro-size HTD structure with built-in channels. Featured by the HTD architecture, the intrinsic kinetic and thermodynamic conditions will be enhanced by larger surface contact areas, more active sites, improved infusion and electrolyte ion accessibility, and larger volume expansion capability. Disclosed by X-ray computed tomography, the interface between cathode and SEs in the four modified samples demonstrates higher homogeneity at the interface between the cathode and SEs than that of all other pristine samples. Atomic force microscopy is employed to measure the potential image of the cross-sectional interface by the peak force tapping mode. The average potential of modified samples is lower than that of pristine samples, which confirms a weakened space charge layer by the enhanced contact capability. In addition, through Electron Energy Loss Spectroscopy coupled with Scanning Transmission Electron Microscopy, the preserved interface between HTD cathode and SE is identified; however, the decomposing of the pristine cathode is clearly observed. In addition, Finite element method simulations validate that the diffusion dynamics of lithium ions is favored by HTD structure. Such a demonstrated universal strategy provides a new guideline to engineer cathode electrolyte interface by reconstructing electrode structures that can be applicable to all solid-state batteries in a wide range of chemical conditions. 
    more » « less
  5. Solid inorganic and polymeric electrolytes have the potential to enable rechargeable batteries with higher energy densities, compared to current lithium-ion technology, which uses liquid electrolyte. Inorganic materials such as ceramics and glasses conduct lithium ions well, but they are brittle, which makes incorporation into a battery difficult. Polymers have the flexibility for facile use in a battery, but their transport properties tend to be inferior to inorganics. Thus, there is growing interest in composite electrolytes with inorganic and organic phases in intimate contact. This article begins with a discussion of ion transport in single-phase electrolytes. A dimensionless number (the Newman number) is presented for quantifying the efficacy of electrolytes. An effective medium framework for predicting transport properties of composite electrolytes containing only one conducting phase is then presented. The opportunities and challenges presented by composite electrolytes containing two conducting phases are addressed. Finally, the importance and status of reaction kinetics at the interfaces between solid electrolytes and electrodes are covered, using a lithium-metal electrode as an example. 
    more » « less