Anion-Induced Interfacial Liquid Layers on LiCoO2 in Salt-in-Water Lithium-Ion Batteries.

The incompatibility of lithium intercalation electrodes with water has impeded the development of aqueous Li-ion batteries. The key challenge is protons which are generated by water dissociation and deform the electrode structures through intercalation. Distinct from previous approaches utilizing large amounts of electrolyte salts or artificial solid-protective films, we developed liquid-phase protective layers on LiCoO2 (LCO) using a moderate concentration of 0.5∼3 mol kg-1 lithium sulfate. Sulfate ion strengthened the hydrogen-bond network and easily formed ion pairs with Li+, showing strong kosmotropic and hard base characteristics. Our quantum mechanics/molecular mechanics (QM/MM) simulations revealed that sulfate ion paired with Li+ helped stabilize the LCO surface and reduced the density of free water in the interface region below the point of zero charge (PZC) potential. In addition, in situ electrochemical surface-enhanced infrared absorption spectroscopy (SEIRAS) proved the appearance of inner-sphere sulfate complexes above the PZC potential, serving as the protective layers of LCO. The role of anions in stabilizing LCO was correlated with kosmotropic strength (sulfate > nitrate > perchlorate > bistriflimide (TFSI-)) and explained better galvanostatic cyclability in LCO cells.

The ligand field in low-crystallinity metal-organic frameworks investigated by soft X-ray core-level absorption spectroscopy.

The ligand field (LF) of transition metal ions is a crucial factor in realizing the mechanism of novel physical and chemical properties. However, the low-crystallinity state, including the amorphous state, precludes the clarification of the electronic structural relationship of transition metal ions using crystallographic techniques, ultraviolet and infrared optical methods, and magnetometry. Here, we demonstrate that soft X-ray 2p → 3d core-level absorption spectroscopy (L2,3-edge XAS) systematically revealed the local 3d electronic states, including in the LF, of nitrogen-coordinated transition-metal ions for low-crystallinity cyanide-bridged metal-organic frameworks (MOFs) M[Ni(CN)4] (MNi; M = Mn, Fe, Co, Ni) and Ni[Pd(CN)4] (NiPd). In NiNi and NiPd, N-coordinated Ni ions with square-planar symmetry exhibit strong orbital hybridization and ligand-to-metal charge transfer effects. In MnNi, FeNi, and CoNi, the correlation between the crystalline electric field splitting in the LF and the transition metal-nitrogen bonding length is revealed using the multiplet LF theory. Regardless of the different local symmetries, our results indicate that L2,3-edge XAS is a powerful tool for gaining element-specific knowledge about the transition-metal ion characterizing the functionality of low-crystallinity MOFs and will be the foundation for an attractive platform, such as adsorption/desorption materials.

Unexpectedly Large Contribution of Oxygen to Charge Compensation Triggered by Structural Disordering: Detailed Experimental and Theoretical Study on a Li3NbO4-NiO Binary System.

Dependence on lithium-ion batteries for automobile applications is rapidly increasing. The emerging use of anionic redox can boost the energy density of batteries, but the fundamental origin of anionic redox is still under debate. Moreover, to realize anionic redox, many reported electrode materials rely on manganese ions through π-type interactions with oxygen. Here, through a systematic experimental and theoretical study on a binary system of Li3NbO4-NiO, we demonstrate for the first time the unexpectedly large contribution of oxygen to charge compensation for electrochemical oxidation in Ni-based materials. In general, for Ni-based materials, e.g., LiNiO2, charge compensation is achieved mainly by Ni oxidation, with a lower contribution from oxygen. In contrast, for Li3NbO4-NiO, oxygen-based charge compensation is triggered by structural disordering and σ-type interactions with nickel ions, which are associated with a unique environment for oxygen, i.e., a linear Ni-O-Ni configuration in the disordered system. Reversible anionic redox with a small hysteretic behavior was achieved for LiNi2/3Nb1/3O2 with a cation-disordered Li/Ni arrangement. Further Li enrichment in the structure destabilizes anionic redox and leads to irreversible oxygen loss due to the disappearance of the linear Ni-O-Ni configuration and the formation of unstable Ni ions with high oxidation states. On the basis of these results, we discuss the possibility of using σ-type interactions for anionic redox to design advanced electrode materials for high-energy lithium-ion batteries.

Coordination Geometry Changes in Amorphous Cyanide-Bridged Metal-Organic Frameworks upon Water Adsorption.

Amorphous coordination polymers and metal-organic frameworks (MOFs) have attracted much attention owing to their various functionalities. Here, we demonstrate the tunable water adsorption behavior of a series of amorphous cyanide-bridged MOFs with different metals (M[Ni(CN)4]: MNi; M = Mn, Fe, and Co). All three compounds adsorb up to six water molecules at a certain vapor pressure (Pads) and undergo conversion to crystalline Hofmann-type MOFs, M(H2O)2[Ni(CN)4]·4H2O (MNi-H2O; M = Mn, Fe, and Co). The Pads of MnNi, FeNi, and CoNi for water adsorption is P/P0 = 0.4, 0.6, and 0.9, respectively. Although the amorphous nature of these materials prevented structural elucidation using X-ray crystallography techniques, the local-scale structure around the N-coordinated M2+ centers was analyzed using L2,3-, K-edge X-ray absorption fine structure, and magnetic measurements. Upon hydration, the coordination geometry of these metal centers changed from tetrahedral to octahedral, resulting in significant reorganization of the MOF local structure. On the other hand, Ni[Ni(CN)4] (NiNi) containing square-planar Ni2+ centers did not undergo significant structural transformation and therefore abruptly adsorbed H2O in the low-pressure region. We could thus define how changes in the bond lengths and coordination geometry are related to the adsorption properties of amorphous MOF systems.

Development of Simultaneous Measurement System for X-ray Absorption Spectra at Two Absorption Edges.

Dispersive X-ray absorption fine structure (DXAFS) spectroscopy is a versatile measurement technique for analyzing chemical reactions in real time. We have developed a novel time-resolved DXAFS instrument based on two polychromators and a wide-range position-sensitive detector that permits direct observation of the synergistic effects of two elements. This system enables simultaneous acquisition of the X-ray absorption spectra for two different elements without any mechanical movement of the X-ray optics. The developed system was successfully applied to monitor both the synthesis of a Ni-Cu bimetallic catalyst, which revealed that the reduction of Ni occurred at a higher temperature than that of Cu, and the charge-discharge processes of a LixNi0.5Mn1.5O4-based lithium-ion battery, which demonstrated that the redox reactions of Ni and Mn occurred sequentially at specific electrode potentials.

Development of dispersive XAFS system for analysis of time-resolved spatial distribution of electrode reaction.

Apparatus for a technique based on the dispersive optics of X-ray absorption fine structure (XAFS) has been developed at beamline BL-5 of the Synchrotron Radiation Center of Ritsumeikan University. The vertical axis of the cross section of the synchrotron light is used to disperse the X-ray energy using a cylindrical polychromator and the horizontal axis is used for the spatially resolved analysis with a pixel array detector. The vertically dispersive XAFS (VDXAFS) instrument was designed to analyze the dynamic changeover of the inhomogeneous electrode reaction of secondary batteries. The line-shaped X-ray beam is transmitted through the electrode sample, and then the dispersed transmitted X-rays are detected by a two-dimensional detector. An array of XAFS spectra in the linear footprint of the transmitted X-ray on the sample is obtained with the time resolution of the repetition frequency of the detector. Sequential measurements of the space-resolved XAFS data are possible with the VDXAFS instrument. The time and spatial resolutions of the VDXAFS instrument depend on the flux density of the available X-ray beam and the size of the light source, and they were estimated as 1 s and 100 µm, respectively. The electrode reaction of the LiFePO4 lithium ion battery was analyzed during the constant current charging process and during the charging process after potential jumping.