To advance current Li rechargeable batteries further, tremendous emphasis has been made on the development of anode materials with higher capacities than the widely commercialized graphite. Some of these anode materials exhibit capacities above the theoretical value predicted based on conventional mechanisms of Li storage, namely insertion, alloying, and conversion. In addition, in contrast to conventional observations of loss upon cycling, the capacity has been found to increase during repeated cycling in a significant number of cases. As the internal environment in the battery is very complicated and continuously changing, these abnormal charge storage behaviors are caused by diverse reactions. In this review, we will introduce our current understanding of reported reactions accounting for the extra capacity. It includes formation/decomposition of electrolyte-derived surface layer, the possibility of additional charge storage at sharp interfaces between electronic and ionic sinks, redox reactions of Li-containing species, unconventional activity of structural defects, and metallic-cluster like Li storage. We will also discuss how the changes in the anode can induce capacity increase upon cycling. With this knowledge, new insights into possible strategies to effectively and sustainably utilize these abnormal charge storage mechanisms to produce vertical leaps in performance of anode materials will be laid out.

batteries (LMBs) with high energy density and greatly improved stability over the last 4 decades. [3][4][5] The conventional LIBs, consisting of the graphite anode and Li 0.5 CoO 2 cathode, have a low theoretical energy density of 387 Wh kg −1 , whereas the Li metal anode in LMBs coupled with sulfur cathode (Li-S) and air cathode have a striking increment in theoretical energy density of 2567 Wh kg −1 and 3505 Wh kg −1 , respectively. The two novel battery systems based on Li metal anode are receiving an intense attention at present as next-generation high energy storage devices. [6][7][8] The essential aspect in developing new energy storage materials and systems, including the continued improvement of current LIBs, is based on complete understanding of how the battery works. This is accompanied by the development of advanced analytical techniques for characterizing the electrochemical behavior of electrode materials. [9][10][11][12][13] The battery operates within electrolyte in a closed cell, but an ex situ characterization experiment is

A three dimensional vanadium pentoxide/reduced graphene oxide/carbon nanotube (3D V2O5/RGO/CNT) composite is synthesized by microwave-assisted hydrothermal method. The combination of 2D RGO and 1D CNT establishes continuous 3D conductive network, and most notably, the 1D CNT is designed to form hierarchically porous structure by penetrating into V2O5 microsphere assembly constituted of numerous V2O5 nanoparticles. The highly porous V2O5 microsphere enhances electrolyte contact and shortens Li+ diffusion path as a consequence of its developed surface area and mesoporosity. The successive phase transformations of 3D V2O5/RGO/CNT from α-phase to ε-, δ-, γ-, and ω-phase and its structural reversibility upon Li+ intercalation/de-intercalation are investigated by in situ XRD analysis, and the electronic and local structure reversibility around vanadium atom in 3D V2O5/RGO/CNT is observed by in situ XANES analysis. The 3D V2O5/RGO/CNT achieves a high capacity of 220 mAh g−1 at 1 C after 80 cycles and an excellent rate capability of 100 mAh g−1 even at a considerably high rate of 20 C. The porous 3D V2O5/RGO/CNT structure not only provides facile Li+ diffusion into bulk but contributes to surface Li+ storage as well, which enables the design of 3D V2O5/RGO/CNT composite to become a promising cathode architecture for high performance LIBs.

The conventional view of conversion reaction is based on the reversibility, returning to an initial material structure through reverse reaction at each cycle in cycle life, which impedes the complete understanding on a working mechanism upon a progression of cycles in conversion-reaction-based battery electrodes. Herein, a series of tin-doped ferrites (Fe3–x Sn x O4, x = 0–0.36) are prepared and applied to a lithium-ion battery anode. By achieving the ideal reoxidation into SnO2, the Fe2.76Sn0.24O4 composite anchored on reduced graphene oxide shows a high reversible capacity of 1428 mAh g–1 at 200 mA g–1 after 100 cycles, which is the best performance of Sn-based anode materials so far. Significantly, a newly formed γ-FeOOH phase after 100 cycles is identified from topological features through synchrotron X-ray absorption spectroscopy with electronic and atomic structural information, suggesting the phase transformation from magnetite to lepidocrocite upon cycling. Contrary to the conventional view, our work suggests a variable working mechanism in an iron-based composite with the dynamic phases from iron oxide to iron oxyhydroxide in the battery cycle life, based on the reactivity of metal nanoparticles formed during reaction toward the solid electrolyte interface layer.

This review focuses on a comprehensive summary of and future perspectives on stable lithium metal batteries.