Voltage fade is a major problem in battery applications for high-energy lithium- and manganese-rich (LMR) layered materials. As a result of the complexity of the LMR structure, the voltage fade mechanism is not well understood. Here we conduct both in situ and ex situ studies on a typical LMR material (Li1.2Ni0.15Co0.1Mn0.55O2) during charge–discharge cycling, using multi-length-scale X-ray spectroscopic and three-dimensional electron microscopic imaging techniques. Through probing from the surface to the bulk, and from individual to whole ensembles of particles, we show that the average valence state of each type of transition metal cation is continuously reduced, which is attributed to oxygen release from the LMR material. Such reductions activate the lower-voltage Mn3+/Mn4+ and Co2+/Co3+ redox couples in addition to the original redox couples including Ni2+/Ni3+, Ni3+/Ni4+ and O2−/O−, directly leading to the voltage fade. We also show that the oxygen release causes microstructural defects such as the formation of large pores within particles, which also contributes to the voltage fade. Surface coating and modification methods are suggested to be effective in suppressing the voltage fade through reducing the oxygen release.Voltage decay is a major problem in applications of high-energy Li- and Mn-rich layer-structured battery materials. Here, the authors report the evolution of redox couples as the origin of the voltage decay and discuss strategies to suppress the problem.

(Invited) Evolution of Redox Couples in Li- and Mn-Rich Cathode Materials and Mitigation of Voltage Fade by Reducing Oxygen Release

For sodium (Na)‐rechargeable batteries to compete, and go beyond the currently prevailing Li‐ion technologies, mastering the chemistry and accompanying phenomena is of supreme importance. Among the crucial components of the battery system, the electrolyte, which bridges the highly polarized positive and negative electrode materials, is arguably the most critical and indispensable of all. The electrolyte dictates the interfacial chemistry of the battery and the overall performance, having an influence over the practical capacity, rate capability (power), chemical/thermal stress (safety), and lifetime. In‐depth knowledge of electrolyte properties provides invaluable information to improve the design, assembly, and operation of the battery. Thus, the full‐scale appraisal of both tailored electrolytes and the concomitant interphases generated at the electrodes need to be prioritized. The deployment of large‐format Na‐based rechargeable batteries also necessitates systematic evaluation and detailed appraisal of the safety‐related hazards of Na‐based batteries. Hence, this review presents a comprehensive account of the progress, status, and prospect of various Na+‐ion electrolytes, including solvents, salts and additives, their interphases and potential hazards.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/aenm.202000093

Electrolytes and Interphases in Sodium-Based Rechargeable Batteries: Recent Advances and Perspectives

Energy storage materials are finding increasing applications in our daily lives, for devices such as mobile phones and electric vehicles. Current commercial batteries use flammable liquid electrolytes, which are unsafe, toxic, and environmentally unfriendly with low chemical stability. Recently, solid electrolytes have been extensively studied as alternative electrolytes to address these shortcomings. Herein, we report the early history, synthesis and characterization, mechanical properties, and Li+ ion transport mechanisms of inorganic sulfide and oxide electrolytes. Furthermore, we highlight the importance of the fabrication technology and experimental conditions, such as the effects of pressure and operating parameters, on the electrochemical performance of all-solid-state Li batteries. In particular, we emphasize promising electrolyte systems based on sulfides and argyrodites, such as LiPS5Cl and β-Li3PS4, oxide electrolytes, bare and doped Li7La3Zr2O12 garnet, NASICON-type structures, and perovskite electrolyte materials. Moreover, we discuss the present and future challenges that all-solid-state batteries face for large-scale industrial applications.

Sulfide and Oxide Inorganic Solid Electrolytes for All-Solid-State Li Batteries: A Review

The development of ultrastable carbon materials for potassium storage poses key limitations caused by the huge volume variation and sluggish kinetics. Nitrogen-enriched porous carbons have recently emerged as promising candidates for this application; however, rational control over nitrogen doping is needed to further suppress the long-term capacity fading. Here we propose a strategy based on pyrolysis-etching of a pyridine-coordinated polymer for deliberate manipulation of edge-nitrogen doping and specific spatial distribution in amorphous high-surface-area carbons; the obtained material shows an edge-nitrogen content of up to 9.34 at %, richer N distribution inside the material, and high surface area of 616 m2  g-1 under a cost-effective low-temperature carbonization. The optimized carbon delivers unprecedented K-storage stability over 6000 cycles with negligible capacity decay (252 mA h g-1 after 4 months at 1 A g-1 ), rarely reported for potassium storage.

https://onlinelibrary.wiley.com/doi/epdf/10.1002/anie.202005118

Ultrastable Surface-Dominated Pseudocapacitive Potassium Storage Enabled by Edge-Enriched N-Doped Porous Carbon Nanosheets.

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Metal chalcogenides for potassium storage

Nitrogen-doped carbon derived from pre-oxidized pitch for surface dominated potassium-ion storage

Facilely tunable core-shell Si@SiOx nanostructures prepared in aqueous solution for lithium ion battery anode

Potassium Prussian blue-coated Li-rich cathode with enhanced lithium ion storage property

Composite solid electrolyte of Na3PS4-PEO for all-solid-state SnS2/Na batteries with excellent interfacial compatibility between electrolyte and Na metal

Jun Cheng

Papers

Nitrogen-doped carbon derived from pre-oxidized pitch for surface dominated potassium-ion storage

Facilely tunable core-shell Si@SiOx nanostructures prepared in aqueous solution for lithium ion battery anode

Potassium Prussian blue-coated Li-rich cathode with enhanced lithium ion storage property

Composite solid electrolyte of Na3PS4-PEO for all-solid-state SnS2/Na batteries with excellent interfacial compatibility between electrolyte and Na metal

Cold-pressing PEO/LAGP composite electrolyte for integrated all-solid-state lithium metal battery