Correction to: npj Computational Materials (2016) 2, 16002; doi:10.1038/npjcompumats.2016.2; published online 18 March 2016 Since the online publication of the above article, it has been noted that an acknowledgement section should have been included and the text should read: ‘This work was supported primarily by the U.

Rechargeable ion batteries are efficient energy storage devices widely employed in portable to large-scale applications such as electric vehicles and grids. Electrochemical reactions within batteries are complex phenomena, and they are strongly dependent on the battery materials and systems used. These electrochemical reactions often include detrimental irreversible reactions at various length scales from atomic- to macro-scales, which ultimately determine the overall electrochemical behavior of the system. Understanding such reaction mechanisms is a critical component to improve battery performance. To help this effort, this review article discusses recent advances and remaining challenges in both computational and experimental approaches to better understand dynamic electrochemical reactions in batteries across multiple length scales. Important related findings from this focus issue will also be highlighted. The aim of our focus issue is to contribute to the battery community towards having better understanding of complex reactions occurring in battery devices and of computational and experimental methods to investigate them. Graphical abstract: [Figure not available: see fulltext.]

The development of rechargeable batteries using K ions as charge carriers has recently attracted considerable attention in the search for cost-effective and large-scale energy storage systems. In light of this trend, various materials for positive and negative electrodes are proposed and evaluated for application in K-ion batteries. Here, a comprehensive review of ongoing materials research on nonaqueous K-ion batteries is offered. Information on the status of new materials discovery and insights to help understand the K-storage mechanisms are provided. In addition, strategies to enhance the electrochemical properties of K-ion batteries and computational approaches to better understand their thermodynamic properties are included. Finally, K-ion batteries are compared to competing Li and Na systems and pragmatic opportunities and future research directions are discussed.

Lithium-ion batteries are now reaching the energy density limits set by their electrode materials, requiring new paradigms for Li(+) and electron hosting in solid-state electrodes. Reversible oxygen redox in the solid state in particular has the potential to enable high energy density as it can deliver excess capacity beyond the theoretical transition-metal redox-capacity at a high voltage. Nevertheless, the structural and chemical origin of the process is not understood, preventing the rational design of better cathode materials. Here, we demonstrate how very specific local Li-excess environments around oxygen atoms necessarily lead to labile oxygen electrons that can be more easily extracted and participate in the practical capacity of cathodes. The identification of the local structural components that create oxygen redox sets a new direction for the design of high-energy-density cathode materials.

Recent successes with disordered Li-excess materials and applications of percolation theory have highlighted cation-disordered oxides as high capacity and energy density cathode materials. In this work, we present a new class of high capacity cation-disordered oxides, lithium-excess nickel titanium molybdenum oxides, which deliver capacities up to 250 mA h g-1. These materials were designed from percolation theory which predicts lithium diffusion to become facile in cation-disordered oxides as the lithium-excess level increases (x > 1.09 in LixTM2-xO2). The reversible capacity and rate capability in these compounds are shown to considerably improve with lithium excess. In particular, Li1.2Ni1/3Ti1/3Mo2/15O2 delivers up to 250 mA h g-1 and 750 W h kg-1 (∼3080 W h l-1) at 10 mA g-1. Combining in situ X-ray diffraction, X-ray absorption near edge spectroscopy, electron energy loss spectroscopy, and electrochemistry, we propose that first charging Li1.2Ni1/3Ti1/3Mo2/15O2 to 4.8 V occurs with Ni2+/Ni∼3+ oxidation, oxygen loss, and oxygen oxidation in this sequence, after which Mo6+ and Ti4+ can be reduced upon discharge. Furthermore, we discuss how oxygen loss with lattice densification can affect lithium diffusion in the material by decreasing the Li-excess level. From this understanding, strategies for further improvements are proposed, setting new guidelines for the design of high performance cation-disordered oxides for rechargeable lithium batteries.

Triplite-type LiFeSO4F has attracted considerable attention as a promising cathode for next-generation lithium-ion batteries because of its high redox potential based on earth-abundant Fe2+/3+. However, successful extraction/reinsertion of all the lithium ions in triplite host is challenging even at a low current rate, resulting in a low specific capacity. These experimental findings contrast with previous theoretical works that predicted that the triplite structure would be a fast ionic conductor with low activation barriers for lithium-ion hopping. Origin of this discrepancy is elusive to date. Herein, combined first-principles calculations and high-angle annular dark-field scanning transmission electron microscopy analyses reveal that typical triplite structure is composed of nanodomains consisting of corner-shared FeO4F2 octahedra, whereas their domain boundaries are regions of mixed corner/edge-shared FeO4F2 octahedra. More importantly, these locally disordered domain boundaries significantly reduce the overall lithium diffusivity of the materials. Inspired by these findings, this study redesigns triplite structure with sufficiently small sizes to avoid local bottlenecks arising from the domain boundaries, successfully achieving nearly full lithium extraction/reinsertion with high power and energy density. This work represents the first direct observation of the presence of domain boundaries within a crystalline structure playing a critical role in governing the lithium diffusivity in a battery electrode.

Over the last decade, Na-ion batteries have been extensively studied as low-cost alternatives to Li-ion batteries for large-scale grid storage applications; however, the development of high-energy positive electrodes remains a major challenge. Materials with a polyanionic framework, such as Na superionic conductor (NASICON)-structured cathodes with formula NaxM2(PO4)3, have attracted considerable attention because of their stable 3D crystal structure and high operating potential. Herein, a novel NASICON-type compound, Na4MnCr(PO4)3, is reported as a promising cathode material for Na-ion batteries that deliver a high specific capacity of 130 mAh g−1 during discharge utilizing high-voltage Mn2+/3+ (3.5 V), Mn3+/4+ (4.0 V), and Cr3+/4+ (4.35 V) transition metal redox. In addition, Na4MnCr(PO4)3 exhibits a high rate capability (97 mAh g−1 at 5 C) and excellent all-temperature performance. In situ X-ray diffraction and synchrotron X-ray diffraction analyses reveal reversible structural evolution for both charge and discharge.

The electrochemical properties of NaNi0.5Co0.5O2 and NaNi0.5Fe0.5O2 and their structural transitions as a function of Na extraction associated with redox reactions are investigated in this work. Synthesized in the O3-type layered structure, both materials show reasonable electrochemical activities at room temperature, delivering approximately 0.5 Na per formula unit at C/10 discharge. More Na can be reversibly cycled in NaNi0.5Co0.5O2 at elevated temperature and/or in an extended voltage window, while NaNi0.5Fe0.5O2 shows significant capacity fading at a high voltage cutoff which is likely due to Fe4+ migration. In situ X-ray diffraction shows that the structural changes in the two materials upon desodiation are very different. NaNi0.5Co0.5O2 goes through many different two-phase reactions including three different O3-type and three different P3-type structures during cycling, producing a voltage profile with multiple plateau-like features. In contrast, NaNi0.5Fe0.5O2 has a smooth voltage profile and shows the typical O3-P3 phase transition without lattice distortion seen in other materials. This different structural evolution upon desodiation and re-sodiation can be explained by the electronic structure of the mixed transition metals and how it perturbs the ordering between Na ions differently.

Fast-charging batteries typically use electrodes capable of accommodating lithium continuously by means of solid-solution transformation because they have few kinetic barriers apart from ionic diffusion. One exception is lithium titanate (Li₄Ti₅O₁₂), an anode exhibiting extraordinary rate capability apparently inconsistent with its two-phase reaction and slow Li diffusion in both phases. Through real-time tracking of Li⁺ migration using operando electron energy-loss spectroscopy, we reveal that facile transport in Li_{4+ x} Ti₅O₁₂ is enabled by kinetic pathways comprising distorted Li polyhedra in metastable intermediates along two-phase boundaries. Our work demonstrates that high-rate capability may be enabled by accessing the energy landscape above the ground state, which may have fundamentally different kinetic mechanisms from the ground-state macroscopic phases. This insight should present new opportunities in searching for high-rate electrode materials.

The effects of cation (Ti4+) and anion (O2−) substitution on the electrochemical properties of KVPO4F cathodes are investigated in this work. Both forms of substitution lead to smoothing of the associated voltage profile as well as reduced charging time at high voltage (>4.8 V vs. K/K+). These changes effectively suppress electrolyte decomposition, thereby enhancing the capacity retention in the ion-substituted KV(1 −x)TixPO4+yF1−y materials. Ionic substitution also enables the intercalation of excess K ions at a reasonably high voltage (∼1.8 V vs. K/K+) relative to that required in pure KVPO4F (<1.0 V vs. K/K+). Finally, this study reveals that detours in the synthesis reaction pathways can be created by using a pre-reacted precursor, VPO4, rather than the conventional precursors V2O3 and NH4H2PO4 to form stoichiometric (or non-substituted) KVPO4F. These results highlight several design criteria that can be used to optimize KVPO4F and related compositions to prepare K-ion batteries with high capacity, good cyclability, and fast rate capability.