Aluminum Impurity from Current Collectors Reactivates Degraded NCM Cathode Materials toward Superior Electrochemical Performance.

The huge amount of degraded NCM (LiNi0.5Co0.2Mn0.3O2) cathode materials from spent lithium-ion batteries is arising as a serious environmental issue as well as a severe waste of metal resources, and therefore, direct recycling of them toward usable electrode materials again is environmentally and economically more attractive in contrast to present metallurgical treatments. In this work, we design a robust two-step method for direct recycling of degraded NCM materials, which uses the aluminum impurity from the attached current collector to supplement the transition metal vacancies for simultaneous elemental compensation and structural restoration. This single-element compensation strategy leads to the regeneration of high-quality NCM material with depressed cation disordering and stabilized layered structure. Moreover, the regenerated NCM material with controllable Al doping delivered an outstanding electrochemical performance; specifically, the capacity (158.6 mAh g-1), rate capability (91.6 mAh g-1 at 5 C), and cycling stability (89.6% capacity retention after 200 cycles) of the regenerated NCM material are even comparable with those of fresh materials. The as-established regeneration protocol has its chance in simplifying the industrial recycling process of degraded NCM materials.

Multistep nucleation visualized during solid-state crystallization.

Mechanisms of nucleation have been debated for more than a century, despite successes of classical nucleation theory. The nucleation process has been recently argued as involving a nonclassical mechanism (the "two-step" mechanism) in which an intermediate step occurs before the formation of a nascent ordered phase. However, a thorough understanding of this mechanism, in terms of both microscopic kinetics and thermodynamics, remains experimentally challenging. Here, in situ observations using transmission electron microscopy on a solid-state nucleation case indicate that early-stage crystallization can follow the non-classical pathway, yet proceed via a more complex manner in which multiple metastable states precede the emergence of a stable nucleus. The intermediate steps were sequentially isolated as spinodal decomposition of amorphous precursor, mass transport and structural oscillations between crystalline and amorphous states. Our experimental and theoretical analyses support the idea that the energetic favorability is the driving force for the observed sequence of events. Due to the broad applicability of solid-state crystallization, the findings of this study offer new insights into modern nucleation theory and a potential avenue for materials design.

Intensified Energy Storage in High-Voltage Nanohybrid Supercapacitors via the Efficient Coupling between TiNb2O7/Holey-rGO Nanoarchitectures and Ionic Liquid-Based Electrolytes.

Obtaining a comprehensive understanding of the energy storage mechanisms, interface compatibility, electrode-electrolyte coupling, and synergistic effects in carefully programmed nanoarchitectural electrodes and complicated electrolyte systems will provide a shortcut for designing better supercapacitors. Here, we report the intrinsic relationships between the electrochemical performances and microstructures or composition of complex nanoarchitectures and formulated electrolytes. We observed that isolated TiNb2O7 nanoparticles provided both a Faradaic intercalation contribution and a surface pseudocapacitance. The holey graphenes partitioned by nanoparticles not only fostered the fast transport of both electrons and ions but also provided additional electrical double-layer capacitance. The charge contributions from the diffusion-controlled intercalation process and capacitive behaviors, double-layer charging, and pseudocapacitance, were quantitatively distinguished in different electrolytes including a formulated ionic-liquid mixture, various nanocomposite ionogel electrolytes, and an organic LiPF6 electrolyte. A steered molecular dynamics simulation method was used to unveil the underlying principles governing the high-rate capability of holey nanoarchitectures. High energy density and high rate capability in solid-state supercapacitors were achieved using the Faradaic contributions from the lithium-ion insertion process and its surface charge-transfer process in combination with the non-Faradaic contribution from the double-layer effects. The work suggests that practical high-voltage supercapacitors with programmed performances and high safety can be realized via the efficient coupling between emerging nanoarchitectural electrodes and formulated high-voltage electrolytes.

Roadmap on Ionic Liquid Electrolytes for Energy Storage Devices.

Ionic liquids are considered to be promising electrolyte solvents or additives for rechargeable batteries (i. e., lithium-ion batteries, sodium-ion batteries, lithium-sulfur batteries, aluminum-ion batteries, etc.) and supercapacitors. This is related with the superior physical and electrochemical properties of ionic liquids, which can influence the performance of rechargeable batteries. Therefore, it is necessary to write a roadmap on ionic liquids for rechargeable batteries. In this roadmap, some progress, critical techniques, opportunities and challenges of ionic liquid electrolytes for various batteries and supercapacitors are pointed out. Especially, properties and roles of ionic liquids should be considered in energy storage. Ionic liquids can be used as electrolyte salts, electrolyte additives, and solvents. For optimizing ionic liquid-based electrolytes for energy storage, their applications in various energy storage devices should be considered by combing native chemical/physical properties and their roles. We expect that this roadmap will give a useful guidance in directing future research in ionic liquid electrolytes for rechargeable batteries and supercapacitors.

Recognition of Ionic Liquids as High-Voltage Electrolytes for Supercapacitors.

The electrochemical stability of electrolytes is essential to the working potential of supercapacitors. Ionic liquids (ILs) are being considered as safe alternatives to current organic electrolytes and attracting extensive interests owing to their inflammability, widened potential windows, and superior ionic conductivity. Novel supercapacitors with IL electrolytes exhibit attractive energy density and can be utilized in various energy storage systems. Most previous studies focused on electrochemical performances, while rare attentions were devoted to energy storage process details or mechanisms. This review comprehensively summarizes the latest progress on formulated IL electrolytes for different types of supercapacitors, with an emphasis on the intrinsic understanding of the related energy storage mechanisms. Subsequently, comparisons of various IL-based liquid-state electrolytes as well as the state-of-the-art advancements in optimizing ILs electrolytes are introduced. The authors attempt to reveal the inherent correlation between the usage of IL electrolytes and the properties of supercapacitors via referenced works. Some emerging applications of ionogel electrolytes based on conventional polymers and poly(IL)s for flexible supercapacitors are also presented, including the existing problems. In addition, challenges and future perspectives of research in this field are highlighted.