Non-Equilibrium Sodiation Pathway of CuSbS2.

Binary metal sulfides have been explored as sodium storage materials owing to their high theoretical capacity and high stable cyclability. Nevertheless, their relative high charge voltage and relatively low practical capacity make them less attractive as an anode material. To resolve the problem, addition of alloying elements is considerable. Copper antimony sulfide is investigated as a representative case. In this study, we do not only perform electrochemical characterization on CuSbS2, but also investigate its nonequilibrium sodiation pathway employing in-/ex situ transmission electron microscopy, in situ X-ray diffraction, and density functional theory calculations. Our finding provides valuable insights on sodium storage into ternary metal sulfide including an alloying element.

In-Depth TEM Investigation on Structural Inhomogeneity within a Primary Lix Ni0.835 Co0.15 Al0.015 O2 Particle: Origin of Capacity Decay during High-Rate Discharge.

The structural stability of cathode materials during electrochemical reactions, in particular, under high-rate discharge, is pertinent to the design and development of new electrode materials. This study investigates the structural inhomogeneity that develops within a single LiNi0.835 Co0.15 Al0.015 O2 (NCA83) particle during a fast discharging process under different cutoff voltages. Some of the NCA83 particles discharged from a high cutoff voltage (4.8 V) developed surface areas in which the layered structure was recovered, although the interiors retained the degraded spinel structure. These micro- and nano-scale structural inversions from high cutoff voltage seem highly correlated with structural evolutions in the initial charged state, and may ultimately degrade the cycling stability. This study advances understanding of the structural inhomogeneity within primary particles during various electrochemical processes and may facilitate the development of new Ni-rich cathode materials.

Carbon with Expanded and Well-Developed Graphene Planes Derived Directly from Condensed Lignin as a High-Performance Anode for Sodium-Ion Batteries.

In this study, we demonstrate that lignin, which constitutes 30-40 wt % of the terrestrial lignocellulosic biomass and is produced from second generation biofuel plants as a cheap byproduct, is an excellent precursor material for sodium-ion battery (NIB) anodes. Because it is rich in aromatic monomers that are highly cross-linked by ether and condensed bonds, the lignin material carbonized at 1300 °C (C-1300) in this study has small graphitic domains with well-developed graphene layers, a large interlayer spacing (0.403 nm), and a high micropore surface area (207.5 m2 g-1). When tested as an anode in an NIB, C-1300 exhibited an initial Coulombic efficiency of 68% and a high reversible capacity of 297 mA h g-1 at 50 mA g-1 after 50 cycles. The high capacity of 199 mA h g-1 at less than 0.1 V with a flat voltage profile and an extremely low charge-discharge voltage hysteresis (<0.03 V) make C-1300 a promising energy-dense electrode material. In addition, C-1300 exhibited an excellent high-rate performance of 116 mA h g-1 at 2.5 A g-1 and showed stable cycling retention (0.2% capacity decay per cycle after 500 cycles). By comparing the properties of the lignin-derived carbon with oak sawdust-derived and sugar-derived carbons and a low-temperature carbonized sample (900 °C), the reasons for the excellent performance of C-1300 were determined to result from facilitated Na+-ion transport to the graphitic layer and the microporous regions that penetrate through the less defective and enlarged interlayer spacings.

Structural Evolution of LixNiyMnzCo1-y-zO2 Cathode Materials during High-Rate Charge and Discharge.

Ni-rich lithium transition metal oxides have received significant attention due to their high capacities and rate capabilities determined via theoretical calculations. Although the structural properties of these materials are strongly correlated with the electrochemical performance, their structural stability during the high-rate electrochemical reactions has not been fully evaluated yet. In this work, transmission electron microscopy is used to investigate the crystallographic and electronic structural modifications of Ni-based cathode materials at a high charge/discharge rate of 10 C. It is found that the high-rate electrochemical reactions induce structural inhomogeneity near the surface of Ni-rich cathode materials, which limits Li transport and reduces their capacities. This study establishes a correlation between the high-rate electrochemical performance of the Ni-based materials and their structural evolution, which can provide profound insights for designing novel cathode materials having both high energy and power densities.

Investigation of Thermal Stability of P2-NaxCoO2 Cathode Materials for Sodium Ion Batteries Using Real-Time Electron Microscopy.

Here, we take advantage of in situ transmission electron microscopy (TEM) to investigate the thermal stability of P2-type NaxCoO2 cathode materials for sodium ion batteries, which are promising candidates for next-generation lithium ion batteries. A double-tilt TEM heating holder was used to directly characterize the changes in the morphology and the crystallographic and electronic structures of the materials with increase in temperature. The electron diffraction patterns and the electron energy loss spectra demonstrated the presence of cobalt oxides (Co3O4, CoO) and even metallic cobalt (Co) at higher temperatures as a result of reduction of Co ions and loss of oxygen. The bright-field TEM images revealed that the surface of NaxCoO2 becomes porous at high temperatures. Higher cutoff voltages result in degrading thermal stability of NaxCoO2. The observations herein provide a valuable insight that thermal stability is one of the important factors to be considered in addition to the electrochemical properties when developing new electrode materials for novel battery systems.

Lithium intercalation mechanism into FeF3·0.5H2O as a highly stable composite cathode material.

The growing demand for lithium-ion batteries (LIBs) requires investigation of high-performance electrode materials with the advantages of being environmentally friendly and cost-effective. In this study, a nanocomposite of open-pyrochlore-structured FeF3·0.5H2O and reduced graphene oxide (RGO) is synthesized for use as a high-performance cathode in LIBs, where RGO provides high electrical conductivity to the composite material. The morphology of the composite shows that FeF3·0.5H2O spheres are embedded into RGO layers and high-resolution TEM image shows that those spheres are composed of primary nanoparticles with a size of ~5 nm. The cycling performance indicates that the composite electrode delivers an initial high discharge capacity of 223 mAh g-1 at 0.05 C, a rate capability up to a high C-rate of 10 C (47 mAh g-1) and stable cycle performance at 0.05 C (145 mAh g-1 after 100 cycles) and 0.2 C (93 mAh g-1 after 100 cycles) while maintaining high electrochemical reversibility. Furthermore, the responsible electrochemical reaction is investigated using in-situ XRD and synchrotron-based X-ray absorption spectroscopy (XAS), and the XRD results show that FeF3·0.5H2O transitions to an amorphous-like phase through a lithiation process. However, a reversible oxidation change of Fe3+ ↔ Fe2+ is identified by the XAS results.

Carbon-, binder-, and precious metal-free cathodes for non-aqueous lithium-oxygen batteries: nanoflake-decorated nanoneedle oxide arrays.

Rechargeable lithium-oxygen (Li-O2) batteries have higher theoretical energy densities than today's lithium-ion batteries and are consequently considered to be an attractive energy storage technology to enable long-range electric vehicles. The main constituents comprising a cathode of a lithium-oxygen (Li-O2) battery, such as carbon and binders, suffer from irreversible decomposition, leading to significant performance degradation. Here, carbon- and binder-free cathodes based on nonprecious metal oxides are designed and fabricated for Li-O2 batteries. A novel structure of the oxide-only cathode having a high porosity and a large surface area is proposed that consists of numerous one-dimensional nanoneedle arrays decorated with thin nanoflakes. These oxide-only cathodes with the tailored architecture show high specific capacities and remarkably reduced charge potentials (in comparison with a carbon-only cathode) as well as excellent cyclability (250 cycles).

Investigating local degradation and thermal stability of charged nickel-based cathode materials through real-time electron microscopy.

In this work, we take advantage of in situ transmission electron microscopy (TEM) to investigate thermally induced decomposition of the surface of Li(x)Ni(0.8)Co(0.15)Al(0.05)O2 (NCA) cathode materials that have been subjected to different states of charge (SOC). While uncharged NCA is stable up to 400 °C, significant changes occur in charged NCA with increasing temperature. These include the development of surface porosity and changes in the oxygen K-edge electron energy loss spectra, with pre-edge peaks shifting to higher energy losses. These changes are closely related to O2 gas released from the structure, as well as to phase changes of NCA from the layered structure to the disordered spinel structure, and finally to the rock-salt structure. Although the temperatures where these changes initiate depend strongly on the state of charge, there also exist significant variations among particles with the same state of charge. Notably, when NCA is charged to x = 0.33 (the charge state that is the practical upper limit voltage in most applications), the surfaces of some particles undergo morphological and oxygen K-edge changes even at temperatures below 100 °C, a temperature that electronic devices containing lithium ion batteries (LIB) can possibly see during normal operation. Those particles that experience these changes are likely to be extremely unstable and may trigger thermal runaway at much lower temperatures than would be usually expected. These results demonstrate that in situ heating experiments are a unique tool not only to study the general thermal behavior of cathode materials but also to explore particle-to-particle variations, which are sometimes of critical importance in understanding the performance of the overall system.

Mechanochemical synthesis of Li2MnO3 shell/LiMO2 (M = Ni, Co, Mn) core-structured nanocomposites for lithium-ion batteries.

Core/shell-like nanostructured xLi2MnO3·(1-x)LiMO2 (M = Ni, Co, Mn) composite cathode materials are successfully synthesized through a simple solid-state reaction using a mechanochemical ball-milling process. The LiMO2 core is designed to have a high-content of Ni, which increases the specific capacity. The detrimental surface effects arising from the high Ni-content are countered by the Li2MnO3 shell, which stabilizes the nanoparticles. The electrochemical performances and thermal stabilities of the synthesized nanocomposites are compared with those of bare LiMO2. In particular, the results of time-resolved X-ray diffraction (TR-XRD) analyses of xLi2MnO3·(1-x)LiMO2 nanocomposites as well as their differential scanning calorimetry (DSC) profiles demonstrate that the Li2MnO3 shell is effective in stabilizing the LiMO2 core at high temperatures, making the nanocomposites highly suitable from a safety viewpoint.

Carbon-free cobalt oxide cathodes with tunable nanoarchitectures for rechargeable lithium-oxygen batteries.

Carbon-free cobalt oxide cathodes for lithium-oxygen batteries are fabricated via an electrodeposition-conversion process. The Co3O4-only cathodes show a remarkably reduced voltage gap (by ca. 550 mV compared to the carbon-only cathode) as well as excellent long-term cyclability.