Comprehensive Electrochemical Impedance Spectroscopy Study of Flow-Electrode Capacitive Deionization Cells.

Flow-electrode capacitive deionization (FCDI) offers infinite ion adsorption for continuous desalination of high-concentration saline water by supplying a flow-electrode to the cell. Although extensive efforts have been made to maximize the desalination rate and efficiency of FCDI cells, the electrochemical properties of these cells are not fully understood. This study investigated the factors affecting the electrochemical properties of FCDI cells containing activated carbon (AC; 1-20 wt %) and various flow rates (6-24 mL/min) for the flow-electrode using electrochemical impedance spectroscopy before and after desalination. Examination of the impedance spectra using the distribution of relaxation time and equivalent circuit fitting analysis revealed three distinctive resistances such as internal, charge transfer, and ion adsorption resistances. The overall impedance decreased significantly after the desalination experiment due to increased ion concentrations in the flow-electrode. The three resistances decreased with increasing concentrations of AC in the flow-electrode due to the extension of electrically connected AC particles that participated in the electrochemical desalination reaction. The ion adsorption resistance decreased significantly due to the flow rate dependence of the impedance spectra. In contrast, the internal and charge transfer resistances were invariant.

Chloroaluminate Anion Intercalation in Graphene and Graphite: From Two-Dimensional Devices to Aluminum-Ion Batteries.

A rechargeable aluminum-ion battery based on chloroaluminate electrolytes has received intense attention due to the high abundance and chemical stability of aluminum. However, the fundamental intercalation processes and dynamics in these battery systems remain unresolved. Here, the energetics and dynamics of chloroaluminate ion intercalation in atomically thin single crystal graphite are investigated by fabricating mesoscopic devices for charge transport and operando optical microscopy. These mesoscopic measurements are compared to the high-performance rechargeable Al-based battery consisting of a few-layer graphene-multiwall carbon nanotube composite cathode. These composites exhibit a 60% capacity enhancement over pyrolytic graphite, while an ∼3-fold improvement in overall ion diffusivity is also obtained exhibiting ∼1% of those in atomically thin single crystals. Our results thus establish the distinction between intrinsic and ensemble electrochemical behavior in Al-based batteries and show that engineering ion transport in these devices can yet lead to vast improvements in battery performance.

5L-Scale Magnesio-Milling Reduction of Nanostructured SiO2 for High Capacity Silicon Anodes in Lithium-Ion Batteries.

Nanostructured silicon (Si) is useful in many applications and has typically been synthesized by bottom-up colloid-based solution processes or top-down gas phase reactions at high temperatures. These methods, however, suffer from toxic precursors, low yields, and impractical processing conditions (i.e., high pressure). The magnesiothermic reduction of silicon oxide (SiO2) has also been introduced as an alternative method. Here, we demonstrate the reduction of SiO2 by a simple milling process using a lab-scale planetary-ball mill and industry-scale attrition-mill. Moreover, an ignition point where the reduction begins was consistently observed for the milling processes, which could be used to accurately monitor and control the reaction. The complete conversion of rice husk SiO2 to high purity Si was demonstrated, taking advantage of the rice husk's uniform nanoporosity and global availability, using a 5L-scale attrition-mill. The resulting porous Si showed excellent performance as a Li-ion battery anode, retaining 82.8% of the initial capacity of 1466 mAh g-1 after 200 cycles.

Three-Dimensional Flower-like MoS2 Nanosheets Grown on Graphite as High-Performance Anode Materials for Fast-Charging Lithium-Ion Batteries.

The demand for fast-charging lithium-ion batteries (LIBs) with long cycle life is growing rapidly due to the increasing use of electric vehicles (EVs) and energy storage systems (ESSs). Meeting this demand requires the development of advanced anode materials with improved rate capabilities and cycling stability. Graphite is a widely used anode material for LIBs due to its stable cycling performance and high reversibility. However, the sluggish kinetics and lithium plating on the graphite anode during high-rate charging conditions hinder the development of fast-charging LIBs. In this work, we report on a facile hydrothermal method to achieve three-dimensional (3D) flower-like MoS2 nanosheets grown on the surface of graphite as anode materials with high capacity and high power for LIBs. The composite of artificial graphite decorated with varying amounts of MoS2 nanosheets, denoted as MoS2@AG composites, deliver excellent rate performance and cycling stability. The 20-MoS2@AG composite exhibits high reversible cycle stability (~463 mAh g-1 at 200 mA g-1 after 100 cycles), excellent rate capability, and a stable cycle life at the high current density of 1200 mA g-1 over 300 cycles. We demonstrate that the MoS2-nanosheets-decorated graphite composites synthesized via a simple method have significant potential for the development of fast-charging LIBs with improved rate capabilities and interfacial kinetics.

Oxygen surface exchange kinetics of SrTi(1-x)Fe(x)O(3-δ) mixed conducting oxides.

The oxygen surface exchange kinetics of mixed conducting perovskite oxides SrTi(1-x)Fe(x)O(3-δ) (x = 0, 0.01, 0.05, 0.35, 0.5) has been investigated as a function of temperature and oxygen partial pressure using the pulse-response (18)O-(16)O isotope exchange (PIE) technique. Arrhenius activation energies range from 140 kJ mol(-1) for x = 0 to 86 kJ mol(-1) for x = 0.5. Extrapolating the temperature dependence to the intermediate temperature range, 500-600 °C, indicates that the rate of oxygen exchange, in air, increases with increasing iron mole fraction, but saturates at the highest iron mole fraction for the given series. The observed behavior is concomitant with corresponding increases in both electronic and ionic conductivity with increasing x in SrTi(1-x)Fe(x)O(3-δ). Including literature data of related perovskite-type oxides Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-δ), La(0.6)Sr(0.4)Co(0.2)Fe(0.8)O(3-δ), La(0.6)Sr(0.4)CoO(3-δ), and Sm(0.5)Sr(0.5)CoO(3-δ), a linear relationship is observed in the log-log plot between oxygen exchange rate and oxide ionic conductivity with a slope fairly close to unity, suggesting that it is the magnitude of the oxide ionic conductivity that governs the rate of oxygen exchange in these solids. The distribution of oxygen isotopomers ((16)O(2), (16)O(18)O, (18)O(2)) in the effluent pulse can be interpreted on the basis of a two-step exchange mechanism for the isotopic exchange reaction. Accordingly, the observed power law dependence of the overall surface exchange rate on oxygen partial pressure turns out to be an apparent one, depending on the relative rates of both steps involved in the adopted two-step scheme. Supplementary research is, however, required to elucidate which of the two possible reaction schemes better reflects the actual kinetics of oxygen surface exchange on SrTi(1-x)Fe(x)O(3-δ).

Quantitative analysis of ceria co-doped with samarium and gadolinium using laser-induced breakdown spectroscopy.

Ceria doped with low-valence lanthanide cations has been introduced for use as an electrolyte in solid oxide fuel cells (SOFCs). Improving the performance of SOFCs using doped ceria requires an increase in ion mobility across the solid electrolyte. Recently, ceria doped with multiple low-valence lanthanide ions has been found to show better ion mobility than that of the singly doped one. In this work, the feasibility of laser-induced breakdown spectroscopy (LIBS) for stoichiometric analysis of doubly doped ceria, SmxGd0.1-xCe0.9O2-δ, was investigated. The three lanthanide elements pouring out plenty of emission lines made identifying the well-resolved single emission line of the dopants (Sm and Gd) rarely feasible. However, the spectral feature of the dopants could be extracted from the unresolved spectra successfully by partial least squares-regression (PLS-R). The PLS-R model performance calibrating the LIBS spectra to the concentration of Sm or Gd was dependent on the contribution of the matrix element (Ce) to the latent variable chosen for modeling. The residual feature of Ce in the latent variable could be reduced further by smoothing LIBS spectra using a moving average. The best model showed dependable detection limit (0.83 mol% of Sm) and accuracy (0.24 mol% of Sm) performances. Spectral denoising by moving average and PLS-R modeling based on LIBS spectra can be used as a rapid and reliable methodology for the multiply doped ceria and assist the manufacturing and recycling processes of SOFCs.

Comparative Study of Epoxy-CsH2PO4 Composite Electrolytes and Porous Metal Based Electrocatalysts for Solid Acid Electrochemical Cells.

Electrochemical cells based on acid salts (CsH2PO4) have attracted great interest for intermediate temperature, due to the outstanding proton conductivity of acid salts. In this work, electrodes and electrolyte were optimized following different strategies. An epoxy resin was added to the CsH2PO4 material to enhance the mechanical properties of the electrolyte, achieving good conductivity, enhanced stability, and cyclability. The electrodes configuration was modified, and Ni sponge was selected as active support. The infiltration of different oxide nanoparticles was carried out to tailor the electrodes resistance by promoting the electrocatalyst activity of electrodes. The selection of a cell supported on the electrode and the addition of an epoxy resin enables the reduction of the electrolyte thickness without damaging the mechanical stability of the thinner electrolyte.

Investigation of Lithium Ion Diffusion of Graphite Anode by the Galvanostatic Intermittent Titration Technique.

Graphite is used as a state-of-the-art anode in commercial lithium-ion batteries (LIBs) due to its highly reversible lithium-ion storage capability and low electrode potential. However, graphite anodes exhibit sluggish diffusion kinetics for lithium-ion intercalation/deintercalation, thus limiting the rate capability of commercial LIBs. In order to determine the lithium-ion diffusion coefficient of commercial graphite anodes, we employed a galvanostatic intermittent titration technique (GITT) to quantify the quasi-equilibrium open circuit potential and diffusion coefficient as a function of lithium-ion concentration and potential for a commercial graphite electrode. Three plateaus are observed in the quasi-equilibrium open circuit potential curves, which are indicative of a mixed phase upon lithium-ion intercalation/deintercalation. The obtained diffusion coefficients tend to increase with increasing lithium concentration and exhibit an insignificant difference between charge and discharge conditions. This study reveals that the diffusion coefficient of graphite obtained with the GITT (1 × 10-11 cm2/s to 4 × 10-10 cm2/s) is in reasonable agreement with literature values obtained from electrochemical impedance spectroscopy. The GITT is comparatively simple and direct and therefore enables systematic measurements of ion intercalation/deintercalation diffusion coefficients for secondary ion battery materials.

Enhanced Desalination Performance of Capacitive Deionization Using Nanoporous Carbon Derived from ZIF-67 Metal Organic Frameworks and CNTs.

Capacitive deionization (CDI) based on ion electrosorption has recently emerged as a promising desalination technology due to its low energy consumption and environmental friendliness compared to conventional purification technologies. Carbon-based materials, including activated carbon (AC), carbon aerogel, carbon cloth, and carbon fiber, have been mostly used in CDI electrodes due their high surface area, electrochemical stability, and abundance. However, the low electrical conductivity and non-regular pore shape and size distribution of carbon-based electrodes limits the maximization of the salt removal performance of a CDI desalination system using such electrodes. Metal-organic frameworks (MOFs) are novel porous materials with periodic three-dimensional structures consisting of metal center and organic ligands. MOFs have received substantial attention due to their high surface area, adjustable pore size, periodical unsaturated pores of metal center, and high thermal and chemical stabilities. In this study, we have synthesized ZIF-67 using CNTs as a substrate to fully utilize the unique advantages of both MOF and nanocarbon materials. Such synthesis of ZIF-67 carbon nanostructures was confirmed by TEM, SEM, and XRD. The results showed that the 3D-connected ZIF-67 nanostructures bridging by CNTs were successfully prepared. We applied this nanostructured ZIF-67@CNT to CDI electrodes for desalination. We found that the salt removal performance was significantly enhanced by 88% for 30% ZIF-67@CNTs-included electrodes as compared with pristine AC electrodes. This increase in salt removal behavior was analyzed by electrochemical analysis such as cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements, and the results indicate reduced electrical impedance and enhanced electrode capacitance in the presence of ZIF-67@CNTs.

Synchrotron study of the garnet-type oxide Li(6)CaSm(2)Ta(2)O(12).

Hexalithium calcium disamarium(III) ditantalum(V) dodeca-oxide, Li(6)CaSm(2)Ta(2)O(12), crystallizes in a cubic garnet-type structure. In the crystal structure, disordered Li atoms occupy two crystallographic sites. One Li has a tetra-hedral coordination environment in the oxide lattice, whereas the other Li atom occupies a significantly distorted octa-hedral site, with site occupancies for the two Li atoms of 0.26 (7) and 0.44 (2), respectively. Ca and Sm atoms are statistically distributed over the same crystallographic position with a occupancy of 2/3 for Sm and of 1/3 for Ca, and are eightfold coordinated by O atoms. The TaO(6) octa-hedron is joined to six others via corner-sharing LiO(4) tetra-hedra. One Li and the O atoms lie on general positions, while the other atoms are situated on special positions. The Sm/Ca position has 222, Ta has , and the tetra-hedrally coordinated Li atom has site symmetry.

Flow-electrode capacitive deionization with highly enhanced salt removal performance utilizing high-aspect ratio functionalized carbon nanotubes.

Flow-electrode-based capacitive deionization (FCDI) has attracted much attention owing to its continuous and scalable desalination process without the need for a discharging step, which is required in conventional fixed-electrode capacitive deionization. However, flow electrode slurry is poorly conductive, which restricts desalination performance, but higher carbon mass loading in the slurry could improve salt removal capacity due to enhanced connectivity. However, increased viscosity restricts higher loading of active materials. Herein, we report a significant increase in salt removal performance by introducing functionalized carbon nanotubes (FCNTs) into activated carbon (AC)-based flow electrodes, which led to the generation of conducting bridges between AC particles. The salt removal rate in the presence of 0.25 wt% FCNT with 5 wt% AC improved four-fold from that obtained with only 5 wt% AC, which is the highest value reported in the literature so far (from 1.45 to 5.72 mmol/m2s, at a saline water concentration of 35.0 g/L and applied potential of 1.2 V). Further, FCNTs with a high aspect ratio (∼50,000) can more effectively enhance salt removal than low-aspect ratio FCNTs (∼1300). Electrochemical analysis further confirms that the addition of FCNTs can efficiently form a connecting percolation network, thus enhancing the conductivity of the flow electrode slurry for the practical application of highly efficient desalination systems.

Ultrafast charge transfer coupled with lattice phonons in two-dimensional covalent organic frameworks.

Covalent organic frameworks (COFs) have emerged as a promising light-harvesting module for artificial photosynthesis and photovoltaics. For efficient generation of free charge carriers, the donor-acceptor (D-A) conjugation has been adopted for two-dimensional (2D) COFs recently. In the 2D D-A COFs, photoexcitation would generate a polaron pair, which is a precursor to free charge carriers and has lower binding energy than an exciton. Although the character of the primary excitation species is a key factor in determining optoelectronic properties of a material, excited-state dynamics leading to the creation of a polaron pair have not been investigated yet. Here, we investigate the dynamics of photogenerated charge carriers in 2D D-A COFs by combining femtosecond optical spectroscopy and non-adiabatic molecular dynamics simulation. From this investigation, we elucidate that the polaron pair is formed through ultrafast intra-layer hole transfer coupled with coherent vibrations of the 2D lattice, suggesting a mechanism of phonon-assisted charge transfer.

Electrochemical Synthesis of Ammonia from Water and Nitrogen: A Lithium-Mediated Approach Using Lithium-Ion Conducting Glass Ceramics.

Lithium-mediated reduction of dinitrogen is a promising method to evade electron-stealing hydrogen evolution, a critical challenge which limits faradaic efficiency (FE) and thus hinders the success of traditional protic-solvent-based ammonia electro-synthesis. A viable implementation of the lithium-mediated pathway using lithium-ion conducting glass ceramics involves i) lithium deposition, ii) nitridation, and iii) ammonia formation. Ammonia was successfully synthesized from molecular nitrogen and water, yielding a maximum FE of 52.3 %. With an ammonia synthesis rate comparable to previously reported approaches, the fairly high FE demonstrates the possibility of using this nitrogen fixation strategy as a substitute for firmly established, yet exceedingly complicated and expensive technology, and in so doing represents a next-generation energy storage system.

Substantial Oxygen Flux in Dual-Phase Membrane of Ceria and Pure Electronic Conductor by Tailoring the Surface.

The oxygen permeation flux of dual-phase membranes, Ce0.9Gd0.1O2-δ-La0.7Sr0.3MnO3±Î´ (GDC/LSM), has been systematically studied as a function of their LSM content, thickness, and coating material. The electronic percolation threshold of this GDC/LSM membrane occurs at about 20 vol % LSM. The coated LSM20 (80 vol % GDC, 20 vol % LSM) dual-phase membrane exhibits a maximum oxygen flux of 2.2 mL·cm(-2)·min(-1) at 850 °C, indicating that to enhance the oxygen permeation flux, the LSM content should be adjusted to the minimum value at which electronic percolation is maintained. The oxygen ion conductivity of the dual-phase membrane is reliably calculated from oxygen flux data by considering the effects of surface oxygen exchange. Thermal cycling tests confirm the mechanical stability of the membrane. Furthermore, a dual-phase membrane prepared here with a cobalt-free coating remains chemically stable in a CO2 atmosphere at a lower temperature (800 °C) than has previously been achieved.

A new layered perovskite, KSrNb2O6F, by powder neutron diffraction.

The structure of a new layered oxyfluoride, viz. potassium strontium diniobium hexaoxide fluoride, KSrNb(2)O(6)F, was refined from powder neutron diffraction data in the orthorhombic space group Immm. The oxyfluoride compound is an n = 2 member of the Dion-Jacobson-type family of general formula A[A'(n-1)B(n)X(3n+1)], which consists of double layered perovskite slabs, [SrNb(2)O(6)F](-), between which K(+) ions are located. Within the perovskite slabs, the NbO(5)F octahedra are significantly distorted and tilted about the a axis. A bond-valence-sum calculation gives evidence for O/F ordering in KSrNb(2)O(6)F, with the F(-) ions located in the central sites of the corner-sharing NbO(5)F octahedra along the b axis. All atoms lie on special positions, namely Nb on m, Sr on mmm, K on m2m, F on mm2, and O on sites of symmetry m and m2m.