Efficient Rechargeable Li-CO2 Battery with a Liquid Electrolyte-Soluble CuCl2 Electrocatalyst.

We demonstrate here a simple liquid electrolyte soluble Cu-compound, viz., cupric chloride (CuCl2) as an alternative electrocatalyst for nonaqueous Li-CO2 batteries. The key point behind the selection of CuCl2 is that the theoretical potential of Li-CO2 batteries (≈2.8 V; Li+|Li) lies within the Cu1+|Cu0 redox couple (2.3-3.3 V; Li+|Li). The presence of CuCl2 in the liquid electrolyte near to the carbon nanotubes (≡ coelectrocatalyst)-loaded porous-CO2 cathode led to efficient electrocatalysis of CO2 and superior Li-CO2 battery performance. The cell overpotential in the presence of CuCl2 is 0.65 V, which is less than half compared to the one without it (≈1.7 V). Extensive investigations precisely elucidate the electrocatalytic mediation of CuCl2 with the redox characteristics of CO2. Additionally, only in the presence of CuCl2, the existence of Li-oxalate (Li2C2O4) is detected, which is a seldomly reported intermediate preceding the formation of Li2CO3.

Probing the Function of a Li-CO2 Battery with a MXene/Graphene Oxide Composite Cathode Electrocatalyst.

We systematically diagnose here the various phases formed at the electrodes in a Li-CO2 battery. The CO2 cathode comprises a mixture of two-dimensional electrocatalysts, MXene and graphene oxide (MXene/GO), configured on Ni foam. The observed overpotential for MXene/GO (2.4 V) is lower than that for GO (2.8 V). MXene/GO also outperforms GO in terms of battery stability and performance. The overall battery reaction (Li2CO3 ↔ Li + CO2) is more efficient in the case of MXene/GO than in the case of GO. This is convincingly demonstrated using ex situ high-resolution synchrotron X-ray diffraction and Raman scattering spectroscopy, which strongly indicates that the MXene/GO composite is more capable than GO in converting Li2CO3 to Li and CO2. When the Li anode is probed, CO2 crossover is evident via the observation of the formation of LiOH/Li2CO3 phases, the proportions of which change during successive cycles.

Transition Metal Phthalocyanines as Redox Mediators in Li-O2 Batteries: A Combined Experimental and Theoretical Study of the Influence of 3d Electrons in Redox Mediation.

Redox mediation is an innovative strategy for ensuring efficient energy harvesting from metal-oxygen systems. This work presents a systematic exploratory analysis of first-row transition-metal phthalocyanines as solution-state redox mediators for lithium-oxygen batteries. Our findings, based on experiment and theory, convincingly demonstrate that d5 (Mn), d7 (Co), and d8 (Ni) configurations function better compared to d6 (Fe) and d9 (Cu) in redox mediation of the discharge step. The d10 configuration (Zn) and non-d analogues (Mg) do not show any redox mediation because of the inability of binding with oxygen. The solution-state discharge product, transition-metal bound Li2O2, undergoes dissociation and oxidation in the charging step of the battery, thus confirming a bifunctional redox mediation. Apart from the reaction pathways predicted based on thermodynamic considerations, density functional theory calculations also reveal interesting effects of electrochemical perturbation on the redox mediation mechanisms and the role of the transition-metal center.

Probing the Polysulfide Confinement in Two Different Sulfur Hosts for a Mg|S Battery Employing Operando Raman and Ex-Situ UV-Visible Spectroscopy.

We study here the Mg-polysulfide confinement inside two structurally different model porous materials, viz., toray carbon paper (TC) and multiwalled carbon nanotubes (CNT), using operando Raman and postcycling ex-situ UV-vis spectroscopy. Sulfur encapsulated inside CNT (CNT-S) and TC (TC-S) serves as S-cathodes in a rechargeable room temperature Mg|S battery. Operando Raman spectroscopy indicates the presence of higher-order Mg-polysulfides at the CNT cathode. This is due to the combination of their entrapment inside CNT and also possibly to their localization in the liquid electrolyte in the vicinity of CNT-S. This finding is directly correlated to the ex-situ UV-vis spectroscopy, which shows a lesser degree of Mg-polysulfide dissolution into the electrolyte solution. In comparison, TC-S, where sulfur is encapsulated within the open matrix formed by the nanofiber network of the carbon paper, displays poorer polysulfide confinement. The distinct differences in their abilities to confine the Mg-polysulfides are corroborated by battery performance. In the current density range (0.05-1) C, the battery with CNT-S displays much higher specific capacities, being nearly two times that of TC-S at 1 C.

Structure-Redox Response Correlation in a Few Select Heme Systems Using X-ray Absorption Spectroelectrochemistry.

Heme based biomolecules control some of the most crucial life processes, such as oxygen and electron transport during respiration and energy metabolism, respectively. The active site of the heme, viz., the metal center, plays a key role and attributes functionality to these biomolecules. During the oxygen binding and debinding processes, it is important to note that the oxidation state of iron in hemoglobin (+II in the native form) does not undergo any change. However, the spin states of the metal center change. We present here a comprehensive study of the redox response of such molecules, based on the electronic structure of the active site. The local electronic structure of heme in a few selective molecular systems is studied in operando via synchrotron X-ray absorption spectroscopy (Fe K-edge) and cyclic voltammetry. Our objective is to identify the electronic structural parameters that can effectively be correlated with the redox reversibility. Evolution in these parameters can be followed to trace the overall changes in redox state of the system. Our data indicate that axial coordination and spin state of the iron center are two such parameters that are intimately connected with the redox response.

Thermodynamic Insights into Polymorphism-Driven Lithium-Ion Storage in Monoelemental 2D Materials.

Monoelemental two-dimensional materials (borophene, silicene, etc.) are exciting candidates for electrodes in lithium-ion batteries because of their ultralight molar mass. However, these materials' lithium-ion binding mechanism can be complex as the inherited polymorphism may induce phase changes during the charge-discharge cycles. Here, we combine genetic-algorithm-based bottom-up and stochastic top-down structure searching techniques to conduct thermodynamic scrutiny of the lithiated compounds of 2D allotropes of four elements: B, Al, Si, and P. Our first-principles-based high-throughput computations unveil polymorphism-driven lithium-ion binding process and other nonidealities (e.g., bond cleavage, adsorbent phase change, and electroplating), which lacks mention in earlier works. While monolayer B (2479 mAh/g), Al (993 mAh/g), and Si (954 mAh/g) have been demonstrated here as excellent candidates for Li-ion storage, P falls short of the expectation. Our well-designed computational framework, which always searches for lithiated structures at global minima, provides convincing thermodynamical insights and realistic reversible specific-capacity values. This will expectedly open up future experimental efforts to design monoelemental two-dimensional material-based anodes with specific polymorphic structures.

Mutual Diffusivity of an n-Hexane-2,2-Dimethyl Butane Binary Mixture Confined to Zeolite Y.

A molecular dynamic study of a mixture of n-hexane and 2,2-dimethyl butane (22DMB) confined to zeolite NaY has been carried out to understand the distinct diffusivity and mutual diffusivity. Results have been compared with the bulk mixture. For each of these mixtures, eight different runs were employed to compute distinct and mutual diffusivity. From the velocity auto- and cross-correlation functions between n-hexane and n-hexane, n-hexane and 22DMB, 22DMB and 22DMB, the self- and distinct diffusivity of the mixture has been computed. The thermodynamic factor and mutual diffusivity have been calculated. The ratio of D11 to Ds is seen to be 1.11 and 0.75 for the confined mixture, while they are 1.21 and 0.79 for the bulk mixture at 200 and 300 K, respectively.

Hemoglobin Dynamics in Solution vis-à-vis Under Confinement: An Electrochemical Perspective.

Confining heme protein in silico often leads to beneficial functionalities such as an enhanced electrochemical response from the heme center. This can be harnessed to design effective biosensors for medical diagnostics. Proteins under confinement, surface confinement on the electrode to be precise, have more ordered and monodisperse structure compared to the protein in bulk solution. As the electrochemical response of a protein comes from those protein molecules that are confined within the electrical double layer across the electrode-electrolyte interface, it is expected that restriction of conformational fluctuations of the polymeric protein will help in enhancement of the electrochemical response. This is probably the prima facie reason for electrochemical response enhancement under confinement. We examine the dynamic features of hemoglobin under confinement vis-à-vis that in bulk solution. We use a variety of spectroscopic techniques across a wide time-space window to establish the following facts: (a) hardening of the protein polypeptide backbone, (b) slowing down of protein diffusion, (c) increase in relaxation times in NMR, and (d) slowing down of dielectric relaxation times under confinement. This indicates an overall quenching of protein dynamics when the protein is confined inside silica matrix. Thus, we hypothesize that along with retention of secondary structure, this quenching of dynamics contributes to the enhancement of electrochemical response observed.

Probing the Extent of Polysulfide Confinement Using a CoNi2S4 Additive Inside a Sulfur Cathode of a Na/Li-Sulfur Rechargeable Battery.

The extent of confinement of soluble metal polysulfides inside a sulfur cathode strongly determines the performance of metal-sulfur rechargeable batteries. This challenge has been largely tackled by loading sulfur inside various conducting porous scaffolds. However, this approach has not proven to be fully effective because of poor chemical interaction between the scaffold and polysulfides. Here, we demonstrate an excellent strategy of using a sulfide additive in the sulfur cathode, viz., cobalt nickel sulfide (CoNi2S4), to efficiently trap the soluble polysulfides inside the sulfur cathode. In situ Raman and ex situ UV-vis spectroscopies clearly reveal higher retention of polysulfides inside CoNi2S4/S compared to bare sulfur and carbon-sulfur mixture cathodes. Against sodium, the CoNi2S4/S assembly showed remarkable cyclability both as a function of current density (at room temperature) and temperature (at constant current density). The versatility of CoNi2S4 is further proven by the exemplary cyclability at various current densities at room temperature against lithium.

Planar Heterojunction Solar Cell Employing a Single-Source Precursor Solution-Processed Sb2S3 Thin Film as the Light Absorber.

We discuss here a solution-processed thin film of antimony trisulphide (Sb2S3; band gap ≈ 1.7 eV; electronic configuration: ns2np0) for applications in planar heterojunction (PHJ) solar cells. An alternative solution processing method involving a single-metal organic precursor, viz., metal-butyldithiocarbamic acid complex, is used to grow the thin films of Sb2S3. Because of excess sulphide in the metal complex, the formation of any oxide is nearly retarded. Sb2S3 additionally displays structural anisotropy with a ribbon-like structure along the [001] direction. These ribbon-like structures, if optimally oriented with respect to the electron transport layer (ETL)/glass substrate, can be beneficial for light-harvesting and charge-transport properties. A PHJ solar cell is fabricated comprising Sb2S3 as the light absorber and CdS as an ETL coated on to FTO. With varying film sintering temperature and thickness, the typical ribbon-like structures predominantly with planes hkl: l = 0 stacked horizontally along with respect to CdS/FTO are obtained. The morphology of the films is observed to be a function of the sintering temperature, with higher sintering temperatures yielding compact and smooth films with large-sized grains. Maximum photon to electricity efficiency of 2.38 is obtained for PHJ solar cells comprising 480 nm thick films of Sb2S3 sintered at 350 °C having a grain size of few micrometers (>5 µm). The study convincingly shows that improper grain orientation, which may lead to nonoptimal alignments of the intrinsic structure with regard to the ETL/glass substrate, is not the sole parameter for determining photovoltaics performance. Other solution-processing parameters can still be suitably chosen to generate films with optimum morphology, leading to high photon to electricity efficiency.

Studying Hemoglobin and a Bare Metal-Porphyrin Complex Immobilized on Functionalized Silicon Surfaces Using Synchrotron X-ray Reflectivity.

We evaluate here, using synchrotron X-ray reflectivity, hemoglobin adsorption characteristics on silicon substrates with varying chemical functionalities. Hemoglobin at isoelectronic point and at negative charge is immobilized on functionalized hydrophilic (hydroxyl, carboxylic, amine) and hydrophobic (alkylated) silicon surfaces for the study. As a control, the bare cofactor hemin (containing only the metal and porphyrin with no amino acid residues) is also studied under similar conditions. Ordered layers (grown using the Langmuir-Blodgett technique) are observed to be less affected by the surface chemistry compared to the multilayers formed by physical absorption. Surface chemistry and charge of the proteins are critical in controlling the protein adsorption characteristics on silicon, such as thickness (correlated to molecule size) and roughness. In this study, this is very well realized by varying both the hydrophobicity and hydrophilicity of the substrate. The fundamental studies discussed here provide us with a set of important guidelines as to how electrode surface functionalization can control molecular conformation/orientation, especially protein adsorption on the substrate. This in turn is expected to have a significant impact on the protein electrochemical function and response of biomolecular devices.

Time-Temperature Scaling and Dielectric Modeling of Conductivity Spectra of Single-Ion Conducting Liquid Dendrimer Electrolytes.

We discuss here the time-temperature scaling and dielectric modeling of the variation of single-ion conductivity with frequency of first generation (G1) liquid dendrimer electrolyte, viz., Poly(propyl ether imine) (PETIM):Li-salt. The PETIM:Li-salt electrolyte exhibits a cation/anion transference number close to unity in the liquid state. On switching from an ester (G1-COOR) to cyano (G1-CN) peripheral group, keeping constant the linker (ether) and branching groups (amine), an interesting transformation from cationic ( t+ ∼1) to anionic conductor ( t- ∼1) takes place. The switch in the nature of the predominant charge carrier is directly related to the change in the magnitude of anion diffusion ( D-), which increases by 1 order of magnitude from D- = 1.1 × 10-12 m2 s-1 (at 30 °C) in G1-COOR to D- = 1.3 × 10-11 m2 s-1 (at 30 °C) in G1-CN. This intriguing ion transport mechanism is probed comprehensively using ac-impedance spectroscopy. The frequency dependent ionic conductivity of G1-CN/G1-COOR, comprised of distinct frequency regimes, is analyzed using the time-temperature superposition scaling principle (TTSP) based on Summerfield and Baranovski scaling methods. To gain insight into the electrical polarization (EP) phenomenon, the relevant frequency regime is converted from conductivity to dielectric versus frequency. The dielectric versus frequency data is modeled using Macdonald and Coelho. The combined approach of TTSP and dielectric modeling provide explicitly the extent of the influence of ion-dendrimer, ion-ion interactions, and also the mobile charge carrier density on the effective ion transport in the homogeneous single-ion conducting dendrimer electrolytes. The combined analysis suggests that ion transport in PETIM-COOR is only due to enhanced ion mobility, whereas in PETIM-CN it is due to both mobile charge carrier concentration and ion mobility. To the best of our knowledge, the scaling and modeling approaches employed here constitute a rare example for validation of such concepts in the context of dendrimer electrolytes.

Using porphyrin-amino acid pairs to model the electrochemistry of heme proteins: experimental and theoretical investigations.

Quasi reversibility in electrochemical cycling between different oxidation states of iron is an often seen characteristic of iron containing heme proteins that bind dioxygen. Surprisingly, the system becomes fully reversible in the bare iron-porphyrin complex: hemin. This leads to the speculation that the polypeptide bulk (globin) around the iron-porphyrin active site in these heme proteins is probably responsible for the electrochemical quasi reversibility. To understand the effect of such polypeptide bulk on iron-porphyrin, we study the interaction of specific amino acids with the hemin center in solution. We choose three representative amino acids-histidine (a well-known iron coordinator in bio-inorganic systems), tryptophan (a well-known fluoroprobe for proteins), and cysteine (a redox-active organic molecule). The interactions of these amino acids with hemin are studied using electrochemistry, spectroscopy, and density functional theory. The results indicate that among these three, the interaction of histidine with the iron center is strongest. Further, histidine maintains the electrochemical reversibility of iron. On the other hand, tryptophan and cysteine interact weakly with the iron center but disturb the electrochemical reversibility by contributing their own redox active processes to the system. Put together, this study attempts to understand the molecular interactions that can control electrochemical reversibility in heme proteins. The results obtained here from the three representative amino acids can be scaled up to build a heme-amino acid interaction database that may predict the electrochemical properties of any protein with a defined polypeptide sequence.

Unique Features of Metformin: A Combined Experimental, Theoretical, and Simulation Study of Its Structure, Dynamics, and Interaction Energetics with DNA Grooves.

There are certain small molecules that exhibit extraordinarily diverse biological activities. Metformin is one of them. It is widely used as an antidiabetic drug for type-two diabetes. Recent lines of evidence of its role in antitumor activities and increasing the survival rates of cancer patients (namely, colorectal, breast, pancreas, and prostate cancer) are emerging. However, theoretical studies of the structure and dynamics of metformin have not yet been fully explored. In this work, we investigate the characteristic structural and dynamical features of three monoprotonated forms of metformin hydrochloride with the help of experiments, quantum chemical calculations, and atomistic molecular dynamics simulations. We validate our force field by comparing simulation results to those of the experimental findings. Energetics of proton transfer between two planar monoprotonated forms reveals a low energy barrier, which leads us to speculate a possible coexistence of them. Nevertheless, among the protonation states, we find that the nonplanar tautomeric form is the most stable. Our calculated values of the self-diffusion coefficient agree quantitatively with NMR results. Metformin forms strong hydrogen bonds with surrounding water molecules, and its solvation dynamics shows unique features. Because of an extended positive charge distribution, metformin possesses features of being a permanent cationic partner toward several targets. We study its interaction and binding ability with DNA using UV spectroscopy, circular dichroism, fluorimetry, and metadynamics simulation. We find a nonintercalative mode of interaction. Metformin feasibly forms a minor/major groove-bound state within a few tens of nanoseconds, preferably with AT-rich domains. A significant decrease in the free energy of binding is observed when it binds to a minor groove of DNA.

Alloying in an Intercalation Host: Metal Titanium Niobates as Anodes for Rechargeable Alkali-Ion Batteries.

We discuss here a unique flexible non-carbonaceous layered host, namely, metal titanium niobates (M-Ti-niobate, M: Al3+ , Pb2+ , Sb3+ , Ba2+ , Mg2+ ), which can synergistically store both lithium ions and sodium ions via a simultaneous intercalation and alloying mechanisms. M-Ti-niobate is formed by ion exchange of the K+ ions, which are specifically located inside galleries between the layers formed by edge and corner sharing TiO6 and NbO6 octahedral units in the sol-gel synthesized potassium titanium niobate (KTiNbO5 ). Drastic volume changes (approximately 300-400 %) typically associated with an alloying mechanism of storage are completely tackled chemically by the unique chemical composition and structure of the M-Ti-niobates. The free space between the adjustable Ti/Nb octahedral layers easily accommodates the volume changes. Due to the presence of an optimum amount of multivalent alloying metal ions (50-75 % of total K+ ) in the M-Ti-niobate, an efficient alloying reaction takes place directly with ions and completely eliminates any form of mechanical degradation of the electroactive particles. The M-Ti-niobate can be cycled over a wide voltage range (as low as 0.01 V) and displays remarkably stable Li+ and Na+ ion cyclability (>2 Li+ /Na+ per formula unit) for widely varying current densities over few hundreds to thousands of successive cycles. The simultaneous intercalation and alloying storage mechanisms is also studied within the density functional theory (DFT) framework. DFT expectedly shows a very small variation in the volume of Al-titanium niobate following lithium alloying. Moreover, the theoretical investigations also conclusively support the occurrence of the alloying process of Li ions with the Al ions along with the intercalation process during discharge. The M-Ti-niobates studied here demonstrate a paradigm shift in chemical design of electrodes and will pave the way for the development of a multitude of improved electrodes for different battery chemistries.

Determination of Redox Sensitivity in Structurally Similar Biological Redox Sensors.

Redox stimuli govern a variety of biological processes. The relative sensitivity of redox sensors plays an important role in providing a calibrated response to environmental stimuli and cellular homeostasis. This cellular machinery plays a crucial role in the human pathogen Mycobacterium tuberculosis as it encounters diverse microenvironments in the host. The redox sensory mechanism in M. tuberculosis is governed by two component and one-component systems, alongside a class of transcription factors called the extra cytoplasmic function (ECF) σ factors. ECF σ factors that govern the cellular response to redox stimuli are negatively regulated by forming a complex with proteins called zinc associated anti-σ factors (ZAS). ZAS proteins release their cognate σ factor in response to oxidative stress. The relative sensitivity of the ZAS sensors to redox processes dictate the concentration of free ECF σ factors in the cell. However, factors governing the redox threshold of these sensors remain unclear. We describe here, the molecular characterization of three σ factor/ZAS pairs-σL/RslA, σE/RseA, and σH/RshA-using a combination of biophysical and electrochemical techniques. This study reveals, conclusively, the differences in redox sensitivity in these proteins despite apparent structural similarity and rationalizes the hierarchy in the activation of the cognate ECF σ factors. Put together, the study provides a basis for examining sequence and conformational features that modulate redox sensitivity within the confines of a conserved structural scaffold. The findings provide the guiding principles for the design of intracellular redox sensors with tailored sensitivity and predictable redox thresholds, providing a much needed biochemical tool for understanding host-pathogen interaction.

Probing the Critical Role of Sn Content in SnSb@C Nanofiber Anode on Li Storage Mechanism and Battery Performance.

The minimization of the detrimental effects as a result of the drastic volume changes (few hundred times) occurring during repeated alloying-dealloying of lithium with group IV elements, e.g., tin (Sn), is a major challenge. An important design strategy is to have Sn as a component in a binary compound. SnSb is an important example where the antimony (Sb) itself is redox active at a potential higher than that of Sn. The ability of Sb to alloy with Li reduces the Li uptake amount of Sn in SnSb compared to that in bare Sn. Thus, the volume changes of Sn in SnSb will expectedly be much lower compared to that in bare Sn, leading to greater mechanical stability and cyclability. As revealed recently, the complete reformation of SnSb (for a molar ratio of Sn/Sb = 1:1) during charging is not achieved due to the loss of some fraction of Sn. Thus, the molar concentration of Sn and Sb in SnSb is also absolutely important for the optimization of battery performance. We discuss here SnSb with varying compositions of Sn encapsulated inside an electrospun carbon nanofiber (abbreviated as CF). The carbon-nanofiber matrix not only provides electron transport pathways for the redox process but also provides ample space to accommodate the drastic volume changes occurring during successive charge and discharge cycles. The systematic changes in the chemical composition of SnSb minimize the instabilities in SnSb structure as well as replenish any loss in Sn during repeated cycling. The composition plays a very crucial role, as magnitude of specific capacities and cyclability of SnSb are observed to depend on the variable percentage of Sn. SnSb-75-25-CF, which contains excess Sn, exhibits the highest specific capacity of 550 mAh g-1 after 100 cycles in comparison with pure SnSb (1:1) anode material at a current density of 0.2 A g-1 and shows excellent rate capability over widely varying current densities (0.2-5 A g-1).

Ion Transport Mechanism of a Gel Electrolyte Comprising a Salt in Binary Plastic Crystalline Mixtures Confined inside a Polymer Network.

We discuss here the ion transport mechanism of a gel electrolyte comprising lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) solvated by two plastic crystalline solvents, one a solid (succinonitrile, abbreviated as SN) and another (a room temperature ionic liquid) (1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide, (abbreviated as IL) confined inside a linear network of poly(methyl methacrylate) (PMMA). The concentration of the IL component (x) determines the physical properties of the unconfined electrolyte (i.e., SN1-xILx-LiTFSI) and when confined inside the polymer network (GPE-x). The extent of disorder in the SN1-xILx-LiTFSI and the GPE-x electrolytes is enhanced compared to both the bare SN-LiTFSI and IL-LiTFSI electrolytes. The enhanced disordering in the plastic phase alters both the local ion environment and viscosity. These changes strongly influence the ion mobility and nature of predominant charge carriers and thus the ion conduction mechanism in SN1-xILx-LiTFSI and GPE-x. The proposed SN1-xILx-LiTFSI and the GPE-x electrolytes show predominantly anion conduction (tTFSI ≈ 0.5); however, lithium transference number (tLi ≈ 0.2) is nearly an order higher than the IL-LiTFSI (tLi ≈ 0.02-0.06). The ionic conductivity of SN1-xILx-LiTFSI is much higher (especially for x ≈ 0.1) compared to both SN-LiTFSI and IL-LiTFSI. The ionic conductivity of the GPE-x, though lower than the unconfined SN1-xILx-LiTFSI electrolytes, is still very promising, displaying values of ∼10-3 Ω-1 cm-1. The GPE-x displayed compliable mechanical properties, stable Li-electrode/electrolyte interface, low rate of Al corrosion, and stable cyclability over several tens of charge-discharge cycles when assembled in a separator-free Li-graphite cell. The promising electrochemical performance further justifies the simple strategy of employing mixed physical state plasticizers to tune the physical properties of polymer electrolytes requisite for application in rechargeable batteries.

Tungsten Trioxide (WO3) Nanoparticles as a New Anode Material for Sodium-Ion Batteries.

Tungsten trioxide (WO3) is investigated for the first time as an anode material for sodium-ion batteries. Pristine WO3 displays a discharge potential plateau at 1 V and exhibits a 1st discharge cycle sodium storage capacity of 640 mAh g-1. Electronic wiring of WO3 with graphene oxide (GO, 1% by weight) led to a significant increase in the storage capacity and cyclability of WO3. As a result, the discharge capacity of 1% GO-WO3 is enhanced to 927 mAh g-1 in the 1st discharge cycle. The electrochemical intercalation of Na in to WO3 and (1%) GO-WO3 as obtained from galvanostatic charge/discharge cycling is also supported by cyclic voltammetry.

Probing the pseudo-1-D ion diffusion in lithium titanium niobate anode for Li-ion battery.

Comprehensive understanding of the charge transport mechanism in the intrinsic structure of an electrode material is essential in accounting for its electrochemical performance. We present here systematic experimental and theoretical investigations of Li(+)-ion diffusion in a novel layered material, viz. lithium titanium niobate. Lithium titanium niobate (exact composition Li0.55K0.45TiNbO5·1.06H2O) is obtained from sol-gel synthesized potassium titanium niobate (KTiNbO5) by an ion-exchange method. The Li(+)-ions are inserted and de-inserted preferentially into the galleries between the octahedral layers formed by edge and corner sharing TiO6 and NbO6 octahedral units and the effective chemical diffusion coefficient, is estimated to be 3.8 × 10(-11) cm(2) s(-1) using the galvanostatic intermittent titration technique (GITT). Calculations based on density functional theory (DFT) strongly confirm the anisotropic Li(+)-ion diffusion in the interlayer galleries and that Li(+)-ions predominantly diffuse along the crystallographic b-direction. The preferential Li(+)-ion diffusion along the b-direction is assisted by line-defects, which are observed to be higher in concentration along the b-direction compared to the a- and c-directions, as revealed by high resolution electron microscopy. The Li-Ti niobate can be cycled to low voltages (≈0.2 V) and show stable and satisfactory battery performance over 100 cycles. Due to the possibility of cycling to low voltages, cyclic voltammetry and X-ray photoelectron spectroscopy convincingly reveal the reversibility of Ti(3+) ↔ Ti(2+) along with Ti(4+) ↔ Ti(3+) and Nb(5+) ↔ Nb(4+).