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Electrochemical Interphases for High-Energy Storage Using Reactive Metal Anodes

Stable electrochemical interphases play a critical role in regulating transport of mass and charge in all electrochemical energy storage (EES) systems. In state-of-the-art rechargeable lithium ion batteries, they are rarely formed by design but instead spontaneously emerge from electrochemical degradation of electrolyte and electrode components. High-energy secondary batteries that utilize reactive metal anodes (e.g., Li, Na, Si, Sn, Al) to store large amounts of charge by alloying and/or electrodeposition reactions introduce fundamental challenges that require rational design in order to stabilize the interphases. Chemical instability of the electrodes in contact with electrolytes, morphological instability of the metal–electrolyte interface upon plating and stripping, and hydrodynamic-instability-induced electroconvection of the electrolyte at high currents are all known to cause metal electrode–electrolyte interfaces to continuously evolve in morphology, uniformity, and composition. Additionally, metal anodes undergo large changes in volume during lithiation and delithiation, which means that even in the rare cases where spontaneously formed solid electrode–electrolyte interphases (SEIs) are in thermodynamic equilibrium with the electrode, the SEI is under dynamic strain, which inevitably leads to cracking and/or rupture during extended battery cycling. There is an urgent need for interphases that are able to overcome each of these sources of instability with minimal losses of electrolyte and electrode components. Complementary chemical synthesis strategies are likewise urgently needed to create self-limited and mechanically durable SEIs that are able to flex and shrink to accommodate volume change. These needs are acute for practically relevant cells that cannot utilize large excesses of anode and electrolyte as employed in proof-of-concept-type experiments reported in the scientific literature. This disconnect between practical needs and research practices makes it difficult to translate promising literature results, underscoring the importance of research designed to reveal principles for good interphase design.

This Account considers the fundamental processes involved in interphase formation, stability, and failure and on that basis identifies design principles, synthesis procedures, and characterization methods for enabling stable metal anode–electrolyte interfaces for EES. We first review results from experimental, continuum theoretical, and computational analyses of interfacial transport to identify fundamental connections between the composition of the SEI at metal–electrolyte interfaces and stability. Design principles and tools for creating stable artificial solid–electrolyte interphases (ASEIs) based on polymers, ionic liquids, ceramics, nanoparticles, salts, and their combinations are subsequently discussed. Interphases composed of a second electrochemically active material that stores charge by different processes from the underlying metal electrode emerge as particularly attractive routes toward so-called hybrid electrodes that enable facile scale-up of ASEI designs for commercially relevant EES.

http://pubs.acs.org/doi/10.1021/acs.accounts.7b00484

发布日期:2017/12/18 发布者:网站管理员 点击数:136