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The cathode material in a lithium (Li) battery determines the system cost, energy density, and thermal stability. In anode-free batteries, the cathode also serves as the source of Li for electrodeposition, thus impacting the reversibility of plating and stripping. Here, we show that the reason LiNi0.8Mn0.1Co0.1O2 (NMC811) cathodes deliver lower Coulombic efficiencies than LiFePO4 (LFP) is the formation of tortuous Li deposits, acidic species in the electrolyte, and accumulation of “dead” Li0. Batteries containing an LFP cathode generate dense Li deposits that can be reversibly stripped, but Li is lost to the solid electrolyte interphase (SEI) and corrosion according to operando 7Li NMR, which seemingly “revives” dead Li0. X-ray photoelectron spectroscopy (XPS) and in situ 19F/1H NMR indicate that these differences arise because upper cutoff voltage alters electrolyte decomposition, where low-voltage LFP cells prevent anodic decomposition, ultimately mitigating the formation of protic species that proliferate upon charging NMC811. 

The performance of Li metal batteries is tightly coupled to the composition and properties of the solid electrolyte interphase (SEI). Even though the role of the SEI in battery function is well understood (e.g., it must be electronically insulating and ionically conductive, it must enable uniform Li+ flux to the electrode to prevent filament growth, it must accommodate the large volume changes of Li electrodeposition), the challenges associated with probing this delicate composite layer have hindered the development of Li metal batteries for practical applications. In this review, we detail how nuclear magnetic resonance (NMR) spectroscopy can help bridge this gap in characterization due to its unique ability to describe local structure (e.g., changes in crystallite size and amorphous species in the SEI) in conjunction with ion dynamics while connecting these properties to electrochemical behavior. By leveraging NMR, we can gain molecular-level insight to aid in the design of Li surfaces and enable reactive anodes for next-generation, high-energy-density batteries. 

The role of the cathode–electrolyte interphase (CEI) on battery performance has been historically overlooked due to the anodic stability of carbonate-based electrolytes used in Li-ion batteries. Yet, over the past few decades, degradation in device lifetime has been attributed to cathode surface reactivity, ion transport at the cathode/electrolyte interface, and structural transformations that occur at the cathode surface. In this review, we highlight recent progress in analytical techniques that have facilitated these insights and elucidated not only the CEI composition but also the spatial distribution of electrolyte decomposition products in the CEI as well as cathode-driven reactions that occur during battery operation. With a deeper understanding of the CEI and the processes that lead to its formation, these advanced characterization tools can unlock routes to mitigate impedance rise, particle cracking, transition metal dissolution, and electrolyte consumption, ultimately enabling longer lasting, safer batteries. 

Abstract The dynamic behavior of the interface between the lithium metal electrode and a solid-state electrolyte plays a critical role in all-solid-state battery performance. The evolution of this interface throughout cycling involves multiscale mechanical and chemical heterogeneity at the micro- and nano-scale. These features are dependent on operating conditions such as current density and stack pressure. Here we report the coupling of operando acoustic transmission measurements with nuclear magnetic resonance spectroscopy and magnetic resonance imaging to correlate changes in interfacial mechanics (such as contact loss and crack formation) with the growth of lithium microstructures during cell cycling. Together, the techniques reveal the chemo-mechanical behavior that governs lithium metal and Li 7 La 3 Zr 2 O 12 interfacial dynamics at various stack pressure regimes and with voltage polarization.