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Graphite (Gr)‐based lithium‐ion batteries with admirable electrochemical performance below −20 °C are desired but are hindered by sluggish interfacial charge transport and desolvation process. Li salt dissociation via Li+‐solvent interaction enables mobile Li+ liberation and contributes to bulk ion transport, while is contradictory to fast interfacial desolvation. Designing kinetically‐stable solid electrolyte interphase (SEI) without compromising strong Li+‐solvent interaction is expected to compatibly improve interfacial charge transport and desolvation kinetics. However, the relationship between physicochemical features and temperature‐dependent kinetics properties of SEI remains vague. Herein, we propose four key thermodynamics parameters of SEI potentially influencing low‐temperature electrochemistry, including electron work function, Li+ transfer barrier, surface energy, and desolvation energy. Based on the above parameters, we further define a novel descriptor, separation factor of SEI (SSEI), to quantitatively depict charge (Li+/e−) transport and solvent deprivation processes at Gr/electrolyte interface. A Li3PO4‐based, inorganics‐enriched SEI derived by Li difluorophosphate (LiDFP) additive exhibits the highest SSEI (4.89×103) to enable efficient Li+ conduction, e− blocking and rapid desolvation, and as a result, much suppressed Li‐metal precipitation, electrolyte decomposition and Gr sheets exfoliation, thus improving low‐temperature battery performances. Overall, our work originally provides visualized guides to improve low‐temperature reaction kinetics/thermodynamics by constructing desirable SEI chemistry. [ABSTRACT FROM AUTHOR]

In situ analysis of Li plating/stripping processes and evolution of solid electrolyte interphase (SEI) are critical for optimizing all‐solid‐state Li metal batteries (ASSLMB). However, the buried solid‐solid interfaces present a challenge for detection which preclude the employment of multiple analysis techniques. Herein, by employing complementary in situ characterizations, morphological/chemical evolution, Li plating/stripping dynamics and SEI dynamics were directly detected. As a mixed ionic‐electronic conducting interface, Li|Li10GeP2S12 (LGPS) performed distinct interfacial morphological/chemical evolution and dynamics from ionic‐conducting/electronic‐isolating interface like Li|Li3PS4 (LPS), which were revealed by combination of in situ atomic force microscopy and in situ X‐ray photoelectron spectroscopy. Though Li plating speed in LGPS was higher than LPS, speed of SSE decomposition was similar and ~85 % interfacial SSE turned into SEI during plating and remained unchanged in stripping. To leverage strengths of different SSEs, an LPS‐LGPS‐LPS sandwich electrolyte was developed, demonstrating enhanced ionic conductivity and improved interfacial stability with less SSE decomposition (25 %). Using in situ Kelvin probe force microscopy, Li‐ion behavior at interface between different SSEs was effectively visualized, uncovering distribution of Li ions at LGPS|LPS interface under different potentials. [ABSTRACT FROM AUTHOR]

Rechargeable sodium-ion batteries (SIBs) have emerged as an advanced electrochemical energy storage technology with potential to alleviate the dependence on lithium resources. Similar to Li-ion batteries, the cathode materials play a decisive role in the cost and energy output of SIBs. Among various cathode materials, Na layered transition-metal (TM) oxides have become an appealing choice owing to their facile synthesis, high Na storage capacity/voltage that are suitable for use in high-energy SIBs, and high adaptivity to the large-scale manufacture of Li layered oxide analogues. However, going from the lab to the market, the practical use of Na layered oxide cathodes is limited by the ambiguous understanding of the fundamental structure-performance correlation of cathode materials and lack of customized material design strategies to meet the diverse demands in practical storage applications. In this review, we attempt to clarify the fundamental misunderstandings by elaborating the correlations between the electron configuration of the critical capacity-contributing elements (e.g., TM cations and oxygen anion) in oxides and their influence on the Na (de)intercalation (electro)chemistry and storage properties of the cathode. Subsequently, we discuss the issues that hinder the practical use of layered oxide cathodes, their origins and the corresponding strategies to address their issues and accelerate the target-oriented research and development of cathode materials. Finally, we discuss several new Na layered cathode materials that show prospects for next-generation SIBs, including layered oxides with anion redox and high entropy and highlight the use of layered oxides as cathodes for solid-state SIBs with higher energy and safety. In summary, we aim to offer insights into the rational design of high-performance Na layered oxide cathode materials towards the practical realization of sustainable electrochemical energy storage at a low cost. [ABSTRACT FROM AUTHOR]