Materials that undergo a conversion reaction with lithium (e.g., metal fluorides MF(2): M = Fe, Cu, ...) often accommodate more than one Li atom per transition-metal cation, and are promising candidates for high-capacity cathodes for lithium ion batteries. However, little is known about the mechanisms involved in the conversion process, the origins of the large polarization during electrochemical cycling, and why some materials are reversible (e.g., FeF(2)) while others are not (e.g., CuF(2)). In this study, we investigated the conversion reaction of binary metal fluorides, FeF(2) and CuF(2), using a series of local and bulk probes to better understand the mechanisms underlying their contrasting electrochemical behavior. X-ray pair-distribution-function and magnetization measurements were used to determine changes in short-range ordering, particle size and microstructure, while high-resolution transmission electron microscopy (TEM) and electron energy-loss spectroscopy (EELS) were used to measure the atomic-level structure of individual particles and map the phase distribution in the initial and fully lithiated electrodes. Both FeF(2) and CuF(2) react with lithium via a direct conversion process with no intercalation step, but there are differences in the conversion process and final phase distribution. During the reaction of Li(+) with FeF(2), small metallic iron nanoparticles (<5 nm in diameter) nucleate in close proximity to the converted LiF phase, as a result of the low diffusivity of iron. The iron nanoparticles are interconnected and form a bicontinuous network, which provides a pathway for local electron transport through the insulating LiF phase. In addition, the massive interface formed between nanoscale solid phases provides a pathway for ionic transport during the conversion process. These results offer the first experimental evidence explaining the origins of the high lithium reversibility in FeF(2). In contrast to FeF(2), no continuous Cu network was observed in the lithiated CuF(2); rather, the converted Cu segregates to large particles (5-12 nm in diameter) during the first discharge, which may be partially responsible for the lack of reversibility in the CuF(2) electrode.

Expectations for the next generation of lithium batteries include greater energy and power densities along with a substantial increase in both calendar and cycle life. Developing new materials to meet these goals requires a better understanding of how electrodes function by tracking physical and chemical changes of active components in a working electrode. Here we develop a new, simple in-situ electrochemical cell for the transmission electron microscope and use it to track lithium transport and conversion in FeF 2 nanoparticles by nanoscale imaging, diffraction and spectroscopy. In this system, lithium conversion is initiated at the surface, sweeping rapidly across the FeF 2 particles, followed by a gradual phase transformation in the bulk, resulting in 1-3 nm iron crystallites mixed with amorphous LiF. The real-time imaging reveals a surprisingly fast conversion process in individual particles (complete in a few minutes), with a morphological evolution resembling spinodal decomposition. This work provides new insights into the inter-and intra-particle lithium transport and kinetics of lithium conversion reactions, and may help to pave the way to develop highenergy conversion electrodes for lithium-ion batteries.

No abstract

Behaviors of functional interfaces are crucial factors in the performance and safety of energy storage and conversion devices. Indeed, solid electrode-solid electrolyte interfacial impedance is now considered the main limiting factor in all-solid-state batteries rather than low ionic conductivity of the solid electrolyte. Here, we present a new approach to conducting in situ scanning transmission electron microscopy (STEM) coupled with electron energy loss spectroscopy (EELS) in order to uncover the unique interfacial phenomena related to lithium ion transport and its corresponding charge transfer. Our approach allowed quantitative spectroscopic characterization of a galvanostatically biased electrochemical system under in situ conditions. Using a LiCoO2/LiPON/Si thin film battery, an unexpected structurally disordered interfacial layer between LiCoO2 cathode and LiPON electrolyte was discovered to be inherent to this interface without cycling. During in situ charging, spectroscopic characterization revealed that this interfacial layer evolved to form highly oxidized Co ions species along with lithium oxide and lithium peroxide species. These findings suggest that the mechanism of interfacial impedance at the LiCoO2/LiPON interface is caused by chemical changes rather than space charge effects. Insights gained from this technique will shed light on important challenges of interfaces in all-solid-state energy storage and conversion systems and facilitate improved engineering of devices operated far from equilibrium.

Metal fluorides and oxides can store multiple lithium ions through conversion chemistry to enable high-energy-density lithium-ion batteries. However, their practical applications have been hindered by an unusually large voltage hysteresis between charge and discharge voltage profiles and the consequent low-energy efficiency (<80%). The physical origins of such hysteresis are rarely studied and poorly understood. Here we employ in situ X-ray absorption spectroscopy, transmission electron microscopy, density functional theory calculations, and galvanostatic intermittent titration technique to first correlate the voltage profile of iron fluoride (FeF3), a representative conversion electrode material, with evolution and spatial distribution of intermediate phases in the electrode. The results reveal that, contrary to conventional belief, the phase evolution in the electrode is symmetrical during discharge and charge. However, the spatial evolution of the electrochemically active phases, which is controlled by reaction kinetics, is different. We further propose that the voltage hysteresis in the FeF3 electrode is kinetic in nature. It is the result of ohmic voltage drop, reaction overpotential, and different spatial distributions of electrochemically active phases (i.e., compositional inhomogeneity). Therefore, the large hysteresis can be expected to be mitigated by rational design and optimization of material microstructure and electrode architecture to improve the energy efficiency of lithium-ion batteries based on conversion chemistry.

The cooperative Jahn-Teller effect (CJTE) refers to the correlation of distortions arising from individual Jahn-Teller centres in complex compounds. The effect usually induces strong coupling between the static or dynamic charge, orbital and magnetic ordering, which has been related to many important phenomena such as colossal magnetoresistance and superconductivity. Here we report a Na5/8MnO2 superstructure with a pronounced static CJTE that is coupled to an unusual Na vacancy ordering. We visualize this coupled distortion and Na ordering down to the atomic scale. The Mn planes are periodically distorted by a charge modulation on the Mn stripes, which in turn drives an unusually large displacement of some Na ions through long-ranged Na-O-Mn(3+)-O-Na interactions into a highly distorted octahedral site. At lower temperatures, magnetic order appears, in which Mn atomic stripes with different magnetic couplings are interwoven with each other. Our work demonstrates the strong interaction between alkali ordering, displacement, and electronic and magnetic structure, and underlines the important role that structural details play in determining electronic behaviour.

CONSPECTUS: Lithium ion batteries (LIBs) not only power most of today's hybrid electric vehicles (HEV) and electric vehicles (EV) but also are considered as a promising system for grid-level storage. Large-scale applications for LIBs require substantial improvement in energy density, cost, and lifetime. Layered lithium transition metal (TM) oxides, in particular, Li(Ni x Mn y Co z )O 2 (NMC, x + y + z = 1) are the most promising candidates as cathode materials with the potential to increase energy densities and lifetime, reduce costs, and improve safety. In order to further boost Li storage capacity, a great deal of attention has been directed toward developing Ni-rich layered TM oxides. However, structural disorder as a result of Ni/Li exchange in octahedral sites becomes a critical issue when Ni content increases to high values, as it leads to a detrimental effect on Li diffusivity, cycling stability, first-cycle efficiency, and overall electrode performance. Increasing effort has been dedicated to improving the electrochemical performance of layered TM oxides via reduction of cationic mixing. Therefore, it is important to summarize this research field and provide in-depth insight into the impact of Ni/Li disordering on electrochemical characteristics in layered TM oxides and its origin to accelerate the future development of layered TM oxides with high performance. In this Account, we start by introducing the Ni/Li disordering in LiNiO 2 , the experimental characterization of Ni/Li disordering, and analyzing the impact of Ni/Li disordering on electrochemical characteristics of layered TM oxides. The antisite Ni in the Li layer can limit the rate performance by impeding the Li ion transport. It will also degrade the cycling stability by inducing anisotropic stress in the bulk structure. Nevertheless, the antisite Ni ions do not always bring drawbacks to the electrochemical performance; some studies including our works found that it can improve the thermal stability and the cycling structure stability of Ni-rich NMC materials. We next discuss the driving forces and the kinetic advantages accounting for the Ni/Li exchange and conclude that the steric effect of cation size and the magnetic interactions between TM cations are the two main driving forces to promote the Ni/Li exchange during synthesis and the electrochemical cycling, and the low energy barrier of Ni 2+ migration from the 3a site in the TM layer to the 3b site in the Li layer further provides a kinetic advantage. Based on this understanding, we then review the progress made to control the Ni/Li disordering through three main ways: (i) suppressing the driving force from the steric effect by ion exchange; (ii) tuning the magnetic interaction by cationic substitution; (iii) kinetically controlling Ni migration. Finally, our brief outlook on the future development of layered TM oxides with controlled Ni/Li disordering is provided. It is believed that this Account will provide significant understanding and inspirations toward developing high-performance la...

No abstract