Site preferences and ion dynamics in lithium chalcohalide solid solutions with argyrodite structure: II. Multinuclear solid state NMR of the systems Li6PS5−x Se x Cl and Li6PS5−x Se x Br

A comprehensive multinuclear (7Li, 31P, 35Cl, 77Se, 79Br) nuclear magnetic resonance (NMR) study has been conducted to characterize local structural configurations and atomic distributions in the crystallographically disordered solid solutions of composition Li6PS5−x Se x X (0 ≤ x ≤ 1, X = Cl, Br) with the Argyrodite structure. In contrast to the situation with the corresponding iodide homologs, there is no structural ordering between the 4a and 4c sites, with the halide ions occupying both of them with close to statistical probabilities. Nevertheless, throughout the composition range, the 16e Wyckoff sites of the Argyrodite structure are exclusively occupied by the chalcogen atoms, forming PY4 3− (Y = S, Se) tetrahedra, indicating the absence of P-halogen bonds. 31P magic-angle spinning (MAS)-NMR can serve to differentiate between the various possible PS4−n Se n 3− tetrahedral units in a quantitative fashion. Compared to the case of the anion-ordered Li6PS5−x Se x I solid solutions, the preference of P–S over P–Se bonding is significantly stronger, but it is weaker than in the halide free solid solutions Li7PS6−x Se x . Each individual PS4−n Se n 3− tetrahedron is represented by a peak cluster of up to five resonances, representing the five different configurations in which the PY4 3− ions are surrounded by the four closest chalcogenide and halide anions occupying the 4c sites; this distribution is close to statistical and can be used to deduce deviations of sample compositions from ideal stoichiometry. Non-linear 7Li chemical shift trends as a function of x are interpreted to indicate that the Coulombic traps created by sulfur-rich PS4−n Se n 3− ions (n ≤ 2) within the energy landscape of the lithium ions are deeper than those of the other anionic species present (i.e., selenium-richer PY4 3− tetrahedra, isolated chalcogenide or iodide ions), causing the Li+ ions to spend on average more time near them. Temperature dependent static 7Li NMR linewidths indicate higher mobility in the present systems than in the previously studied Li6PS5−x Se x I solid solutions. Unlike the situation in Li6PS5−x Se x I no rate distinction between intra-cage and inter-cage ionic motion is evident. Lithium ionic mobility increases with increasing selenium content. This effect can be attributed to the influences of higher anionic polarizability and a widening of the lithium ion migration pathways caused by lattice expansion. The results offer interesting new insights into the structure/ionic mobility correlations in this new class of compounds.

Nanostructure Engineering via Intramolecular Construction of Carbon Nitride as Efficient Photocatalyst for CO2 Reduction

Light-driven heterogeneous photocatalysis has gained great significance for generating solar fuel; the challenging charge separation process and sluggish surface catalytic reactions significantly restrict the progress of solar energy conversion using a semiconductor photocatalyst. Herein, we propose a novel and feasible strategy to incorporate dihydroxy benzene (DHB) as a conjugated monomer within the framework of urea containing CN (CNU-DHBx) to tune the electronic conductivity and charge separation due to the aromaticity of the benzene ring, which acts as an electron-donating species. Systematic characterizations such as SPV, PL, XPS, DRS, and TRPL demonstrated that the incorporation of the DHB monomer greatly enhanced the photocatalytic CO2 reduction of CN due to the enhanced charge separation and modulation of the ionic mobility. The significantly enhanced photocatalytic activity of CNU–DHB15.0 in comparison with parental CN was 85 µmol/h for CO and 19.92 µmol/h of the H2 source. It can be attributed to the electron–hole pair separation and enhance the optical adsorption due to the presence of DHB. Furthermore, this remarkable modification affected the chemical composition, bandgap, and surface area, encouraging the controlled detachment of light-produced photons and making it the ideal choice for CO2 photoreduction. Our research findings potentially offer a solution for tuning complex charge separation and catalytic reactions in photocatalysis that could practically lead to the generation of artificial photocatalysts for efficient solar energy into chemical energy conversion.

Site preferences and ion dynamics in lithium chalcohalide solid solutions with argyrodite structure: I. A multinuclear solid state NMR study of the system Li6PS5-xSexI and of Li6AsS5I

A comprehensive multinuclear (7Li, 31P, 75As, 77Se, 127I) NMR study has been conducted to characterize local structural configurations and atomic distributions in the crystallographically ordered solid solutions of composition Li6PS5-x Se x I (0 ≤ x ≤ 1) and in Li6AsS5I. Throughout the composition range, structural ordering between the atoms on the Wyckoff sites 4a and 4c is maintained, with the I− ions exclusively occupying the 4a sites. 31P magic-angle spinning nuclear magnetic resonance (MAS NMR) can serve to differentiate between the various possible PS4-n Se n 3− tetrahedral units in a quantitative fashion, indicating a preference of P-S relative to P-Se bonding. Each individual PS4-n Se n 3− tetrahedron is represented by a peak cluster containing up to five resonances, representing the five different configurations in which the PCh4 3− units are surrounded by the four closest chalcogenide anions occupying the 4c sites; the distribution of S2− and Se2− over these sites is close to statistical. Non-linear 7Li chemical shift trends as a function of x are interpreted to indicate that the Coulombic traps created by sulfur-rich PS4-n Se n 3− ions (n ≥ 2) within the energy landscape of the lithium ions are deeper than those of the other anionic species present (i.e. selenium-richer PCh4 3− tetrahedra, isolated chalcogenide or iodide ions), causing the Li+ ions to spend on average more time near them. Temperature dependent static 7Li NMR linewidths measured on Li6PS5I and Li6AsS5I indicate a two-step motional narrowing process characterized by a clear dynamic distinction between a more rapid localized intra-cage process and a slower, long-range inter-cage process. In the solid solutions this differentiation gradually disappears, leading to an overall increase of lithium ionic mobility with increasing selenium content, which can be attributed to the influences of higher anionic polarizability and a widening of the lithium migration pathways caused by lattice expansion. Furthermore, the low-temperature phase transition in Li6PS5I, which tends to immobilize the lithium ions below 170 K, is suppressed in the solid solutions. The results offer interesting new insights into the -structure/ionic mobility correlations in this new class of compounds.

Aging Behavior of Lithium Titanate Battery under High-Rate Discharging Cycle

The high-rate discharging performance of a lithium titanate battery is one of its main properties. In conditions that require ultra-high-rate discharging, a lithium titanate battery can be discharged continuously at a current of 50 C (50 times of its maximum capacity) or higher. In this paper, we take cylindrical steel shell lithium titanate cells as the research object and perform aging cycles at 66 C on these cells. The ultra-high-rate discharging cycles cause a rapid high-power capacity fading while the available capacity at normal current rate is not affected. The capacity at 66 C decreases to 80% of initial value in 10 cycles. This paper also analyzes the aging process of a lithium titanate battery at high-rate discharging with incremental capacity (IC) analysis, and presents the aging behavior of lithium titanate battery qualitatively, which is inconsistent with existing research. We attribute the aging mechanism of ultra-high-rate discharging cycles to the decrease of ionic mobility and increase of polarization resistance. Mechanical damage is observed in the CT scan of an aged cell, which we presume to be the result of rapid strain of cathode material.

Dielectric relaxations and ion transport study of NaCMC:NaNO3 solid polymer electrolyte films

Na+ ion-conducting solid polymer electrolyte (SPE) of sodium salt of carboxymethyl cellulose (NaCMC) doped with sodium nitrate (NaNO3) was developed by solution casting method. FTIR technique confirmed the formation of hydrogen bonding between $$ {NO}_3^{-} $$ NO 3 − anion and functional groups of NaCMC. XRD study revealed the low degree of crystallinity that reduced upon doping. Impedance spectroscopy was adapted in order to analyze the conductivity and dielectric relaxation phenomena of the polymer-salt complex. FTIR deconvolution technique was employed to understand the factor that influences the ionic conductivity in SPE; concentration of mobile ions and ionic mobility both play a vital role. Ion transference number has been found out to be > 0.97 for all samples indicating that the conducting species are primarily ions. The highest ionic conductivity of ̴ 3 × 10−3 Scm−1 with the mechanical strength of 30.12 MPa was achieved for a host containing 30 wt.% NaNO3 at ambient temperature.

Ion Transport in Solid Medium–Evaluation of Ionic Mobility for Design of Ion Transport Pathways in Separator and Gel Electrolyte

Further improvement in the performance of lithium secondary batteries will be an indispensable issue to realize a decarbonized society. Among them, the batteries for electric vehicles still have many issues to be addressed because they are subject to various conditions such as high-power performance, safety, and cost restrictions for widespread use. Those subjects require extensive researches from the improvement of each element material to control the battery system to optimize the total performance. Based on this idea, we have been conducting research focusing on ion movement to elucidate the ion conduction mechanism from the microscopic point of view. It has been recognized that the ionic mobility in the battery, which dominates the power performance of the battery, is affected by the solid environment in which the ions move (separator and electrode materials) and the evaluation of ion movement, including the interaction with the surroundings, is necessary as an essential step for battery design. In this article, I will introduce the evaluation approach of ion dynamics and the evaluation results of mobility and interactive situations of carrier ions in the practical separator membranes and gel electrolytes. Finally, the direction of material design is outlined through this review.