Pristine and graphitized-MWCNTs as durable cathode-catalyst supports for PEFCs

Long-term deterioration in the performance of PEFCs is attributed largely to reduction in active area of the platinum catalyst at cathode, usually caused by carbon-support corrosion. Multi-walled carbon-nanotubes (MWCNTs) as cathode-catalyst support are found to enhance long-term stability of platinum catalyst (Pt) in relation to non-graphitic carbon. In addition, highly graphitic MWCNTs (G-MWCNTs) are found to be electrochemically more stable than pristine MWCNTs. This is because graphitic-carbon-supported-Pt (Pt/MWCNTs) cathodes exhibit higher resistance to carbon corrosion in-relation to non-graphitic-carbon-supported-Pt (Pt/C) cathodes in PEFCs during accelerated stress-test (AST) as evidenced by chronoamperometry and carbon dioxide studies. The corresponding change in electrochemical surface area (ESA), cell performance, and charge-transfer resistance are monitored through cyclic voltammetry, cell polarization, and impedance measurements, respectively. The extent of crystallinity, namely amorphous or graphitic nature of the three supports, is examined by Raman spectroscopy. X-ray diffraction and transmission electron microscopy studies both prior and after AST suggest lesser deformation in catalyst layer and catalyst particles for Pt/G-MWCNTs and Pt/MWCNTs cathodes in relation to Pt/C cathodes, reflecting that graphitic carbon-support resists carbon corrosion and helps mitigating aggregation of Pt particles. It is also found that with increasing degree of graphitization, the electrochemical stability for MWCNTs increases due to the lesser surface defects.

A 3.8-V earth-abundant sodium battery electrode

Rechargeable lithium batteries have ushered the wireless revolution over last two decades and are now matured to enable green automobiles. However, the growing concern on scarcity and large-scale applications of lithium resources have steered effort to realize sustainable sodium-ion batteries, Na and Fe being abundant and low-cost charge carrier and redox centre, respectively. However, their performance is limited owing to low operating voltage and sluggish kinetics. Here we report a hitherto-unknown material with entirely new composition and structure with the first alluaudite-type sulphate framework, Na2Fe2(SO4)(3), registering the highest-ever Fe3+/ Fe2+ redox potential at 3.8V (versus Na, and hence 4.1V versus Li) along with fast rate kinetics. Rare-metal-free Na-ion rechargeable battery system compatible with the present Li-ion battery is now in realistic scope without sacrificing high energy density and high power, and paves way for discovery of new earth-abundant sustainable cathodes for large-scale batteries.

CuIn1-xAlxSe2 Solar Cells Fabricated on the Flexible Substrates by CoSputtering and Modified Selenization

CuIn1-xAlxSe2 (CIAS) thin films were grown on the flexible stainless steel substrates, by de co-sputtering from the elemental cathodes. CuInAl alloyed precursor films were selenized both by noble gas assisted Se vapor transport and vacuum evaporation of Se. X-ray diffraction, scanning electron microscopy and UV-visible absorption spectroscopy were used to characterize the selenized films The composition (x=Al/Al+In) with 0 <= x <= 0.65 was varied by substituting Al with indium in CuInSe2. Lattice parameters, average crystallite sizes and compact density of the films compared to CuInSe2, decreased and (112) peak shifted to higher Bragg's angle, with Al incorporation. Cells were fabricated with the device structure SS/Mo/CIAS/CdS/iZno-AZO/Al. Best cell showed the efficiency of 6.8%, with x=0.13, Eg=1.17 eV, fill factor 45.04, short circuit current density J 30 mA/cm(2).

t-Na-2(VO)P2O7: A 3.8 V Pyrophosphate Insertion Material for Sodium-Ion Batteries

Pyrophosphate oxyanionic framework compounds offer a great platform to investigate new battery materials. In our continuing effort to explore pyrophosphate cathodes for sodium-ion batteries, we report, for the first time, the synthesis and use of tetragonal Na-2(VO)P2O7 as a potential sodium-ion insertion material. This material can be easily prepared by using a conventional solid-state route at a relatively low temperature of 400 degrees C. Stabilizing as a tetragonal structure with an open framework, the material offers pathways for Na+ diffusion. The as-synthesized material, with no further cathode optimization, yields a reversible capacity (Q) approaching 80 mAh g(-1) (Q(Theoretical) = 93.4 mAh g(-1)) involving a one electron V5+/V4+ redox potential located at 3.8 V (vs. Na/Na+). Furthermore, the material exhibits decent rate kinetics and reversibility. Combining green synthesis and moderate electrochemical properties, t-Na-2(VO)P2O7 is reported as a new addition to the growing family of pyrophosphate cathodes for sodium-ion batteries.

Structural, magnetic and electrochemical investigation of novel binary Na2-x(Fe1-yMny)P2O7 (0 <= y <= 1) pyrophosphate compounds for rechargeable sodium-ion batteries

Pyrophosphate cathodes have been recently reported as a competent family of insertion compounds for sodium-ion batteries. In the current study, we have investigated the binary Na2 - x(Fe1 - yMny)P2O7 (0 <= y <= 1) pyrophosphate family, synthesized by the classical solid-state method. They form a continuous solid solution maintaining triclinic P-1 (#2) symmetry. The local structural coordination differs mainly by different degrees of Na site occupancy and preferential occupation of the Fe2 site by Mn. The structural and magnetic properties of these mixed-metal pyrophosphate phases have been studied. In each case, complete Fe3+/Fe2+ redox activity has been obtained centered at 3 V vs. Na. The Fe3+/Fe2+ redox process involves multiple steps between 2.5 and 3 V owing to Na-cation ordering during electrochemical cycling, which merge to form a broad single Fe3+/Fe2+ redox peak upon progressive Mn-doping. (C) 2014 Elsevier B.V. All rights reserved.

Sulfate Chemistry for High-Voltage Insertion Materials: Synthetic, Structural and Electrochemical Insights

Rechargeable batteries based on Li and Na ions have been growing leaps and bounds since their inception in the 1970s. They enjoy significant attention from both the fundamental science point of view and practical applications ranging from portable electronics to hybrid vehicles and grid storage. The steady demand for building better batteries calls for discovery, optimisation and implementation of novel positive insertion (cathode) materials. In this quest, chemists have tried to unravel many future cathode materials by taking into consideration their eco-friendly synthesis, material/process economy, high energy density, safety, easy handling and sustainability. Interestingly, sulfate-based cathodes offer a good combination of sustainable syntheses and high energy density owing to their high-voltage operation, stemming from electronegative SO42- units. This review delivers a sneak peak at the recent advances in the discovery and development of sulfate-containing cathode materials by focusing on their synthesis, crystal structure and electrochemical performance. Several family of cathodes are independently discussed. They are 1) fluorosulfates AMSO(4)F], 2) bihydrated fluorosulfates AMSO(4)F2H(2)O], 3) hydroxysulfate AMSO(4)OH], 4) bisulfates A(2)M(SO4)(2)], 5) hydrated bisulfates A(2)M(SO4)(2)nH(2)O], 6) oxysulfates Fe-2(SO4)(2)O] and 7) polysulfates A(2)M(2)(SO4)(3)]. A comparative study of these sulfate-based cathodes has been provided to offer an outlook on the future development of high-voltage polyanionic cathode materials for next-generation batteries.

Ultra-small sulphur nanoparticles configured inside a flexible organic mixed conducting network as a cathode for lithium-sulphur batteries

The major challenges in Li-S batteries are the formation of soluble polysulphides during the reversible conversion of S-8 <-> Li2S, large changes in sulphur particle volume during lithiation and extremely poor charge transport in sulphur. We demonstrate here a novel and simple strategy to overcome these challenges towards practical realization of a stable high performance Li-S battery. For the first time, a strategy is developed which does away with the necessity of pre-fabricated high surface area hollow-structured adsorbates and also multiple nontrivial synthesis steps related to sulphur loading inside such adsorbates. A lithiated polyethylene glycol (PEG) based surfactant tethered on ultra-small sulphur nanoparticles and wrapped up with polyaniline (PAni) (abbreviated as S-MIEC) is demonstrated here as an exceptional cathode for Li-S batteries. The PEG and PAni network around the sulphur nanoparticles serves as an efficient flexible trap for sulphur and polysulphides and also provides distinct pathways for electrons (through PAni) and ions (through PEG) during battery operation. Contrary to the cathodes demonstrated based on various carbon-sulphur composites, the mixed conducting S-MIEC showed an extremely high loading of 75%. The S-MIEC exhibited a stable capacity of nearly 900 mA h g(-1) at the end of 100 cycles at a 1C current rate.

Designing Novel Sulphate-based Ceramic Materials as Insertion Host Compounds for Secondary Batteries

Rechargeable batteries have propelled the wireless revolution and automobiles market over the past 25 years. Developing better batteries with improved energy density demands unveiling of new cathode ceramic materials with suitable diffusion channels and open framework structure. In this pursuit of achieving higher energy density, one approach is to realize enhanced redox voltage of insertion of ceramic compounds. This can be accomplished by incorporating highly electronegative anions in the cathode ceramics. Building on this idea, recently various sulphate- based compounds have been reported as high voltage cathode materials. The current article highlights the use of sulphate (SO4) based cathodes to realize the highest ever Fe3+/Fe2+ redox potentials in Li-ion batteries (LiFeSO4F fluorosulphate: 3.9V vs Li/Li+) and Na-ion batteries (Na2Fe2(SO4)(3) polysulphate: 3.8V vs Na/Na+). These sulphate-based cathode ceramic compounds pave way for newer avenues to design better batteries for future applications.

CuIn1-xAlxSe2 Thin Films Grown by Co-Sputtering and Modified Selenization: Application in Flexible Solar Cells

Thin films of CuIn1-xAlxSe2 (CIAS) were grown on the flexible 10 micrometer thin stainless steel substrates, by dc co-sputtering from the elemental cathodes, followed by annealing with modified selenization. CuInAl alloyed precursor films were selenized both by noble gas assisted Se vapor transport in a tubular furnace and vacuum evaporation of Se in an evaporation chamber. CIAS thin films were optimized for better adhesion. X-ray diffraction, scanning electron microscopy, and UV-visible absorption spectroscopy were used to characterize the selenized films. The composition of CIAS films was varied by substituting In with Al in CuInSe2 (CIS) from 0 <= x <= 0.65 (x = Al/Al+In). Lattice parameters, average crystallite sizes, and compact density of the films, decreased when compared to CIS and (112) peak shifted to higher Bragg's angle, upon Al incorporation. The dislocation density and strain were found to increase with Al doping. Solar cells with SS/Mo/CIAS/CdS/iZnO: AZnO/Al configuration were fabricated and were tested for current-voltage characteristics for various `x' values, under Air Mass 1.5 Global one sun illumination. The best CIAS solar cell showed the efficiency of 6.8%, with x = 0.13, Eg = 1.17 eV, fill factor 45.04, and short circuit current density J(sc) 30 mA/cm(2).

CuIn1-xAlxSe2 Thin Films Grown by Co-Sputtering and Modified Selenization: Application in Flexible Solar Cells

Thin films of CuIn1-xAlxSe2 (CIAS) were grown on the flexible 10 micrometer thin stainless steel substrates, by dc co-sputtering from the elemental cathodes, followed by annealing with modified selenization. CuInAl alloyed precursor films were selenized both by noble gas assisted Se vapor transport in a tubular furnace and vacuum evaporation of Se in an evaporation chamber. CIAS thin films were optimized for better adhesion. X-ray diffraction, scanning electron microscopy, and UV-visible absorption spectroscopy were used to characterize the selenized films. The composition of CIAS films was varied by substituting In with Al in CuInSe2 (CIS) from 0 <= x <= 0.65 (x = Al/Al+In). Lattice parameters, average crystallite sizes, and compact density of the films, decreased when compared to CIS and (112) peak shifted to higher Bragg's angle, upon Al incorporation. The dislocation density and strain were found to increase with Al doping. Solar cells with SS/Mo/CIAS/CdS/iZnO: AZnO/Al configuration were fabricated and were tested for current-voltage characteristics for various `x' values, under Air Mass 1.5 Global one sun illumination. The best CIAS solar cell showed the efficiency of 6.8%, with x = 0.13, Eg = 1.17 eV, fill factor 45.04, and short circuit current density J(sc) 30 mA/cm(2).

Ionothermal Synthesis of High-Voltage Alluaudite Na2+2xFe2-x(SO4)(3) Sodium Insertion Compound: Structural, Electronic, and Magnetic Insights

Exploring future cathode materials for sodium-ion batteries, alluaudite class of Na2Fe2II(SO4)(3) has been recently unveiled as a 3.8 V positive insertion candidate (Barpanda et al. Nat. Commun. 2014, 5, 4358). It forms an Fe-based polyanionic compound delivering the highest Fe-redox potential along with excellent rate kinetics and reversibility. However, like all known SO4-based insertion materials, its synthesis is cumbersome that warrants careful processing avoiding any aqueous exposure. Here, an alternate low temperature ionothermal synthesis has been described to produce the alluaudite Na2+2xFe2-xII(SO4)(3). It marks the first demonstration of solvothermal synthesis of alluaudite Na2+2xM2-xII(SO4)(3) (M = 3d metals) family of cathodes. Unlike classical solid-state route, this solvothermal route favors sustainable synthesis of homogeneous nanostructured alluaudite products at only 300 degrees C, the lowest temperature value until date. The current work reports the synthetic aspects of pristine and modified ionothermal synthesis of Na2+2xFe2-xII(SO4)(3) having tunable size (300 nm similar to 5 mu m) and morphology. It shows antiferromagnetic ordering below 12 K. A reversible capacity in excess of 80 mAh/g was obtained with good rate kinetics and cycling stability over 50 cycles. Using a synergistic approach combining experimental and ab initio DFT analysis, the structural, magnetic, electronic, and electrochemical properties and the structural limitation to extract full capacity have been described.

Fabrication of carbon nanotube lateral field emitters

We report on the fabrication and field emission of carbon nanotube lateral field emitters. Due to its high aspect ratio and mechanical strength, we use vertically aligned multi-wall carbon nanotubes prepared by plasma-enhanced chemical vapour deposition as cathodes, which makes the fabrication of cantilever type lateral field emitters possible. The emission characteristics show that the field emission initiates at 11-17 V. The device has high geometrical enhancement factors (9.3 × 106 cm-1) compared to standard Spindt tips, which may be due to increased field concentration at the nanotube tip and the close proximity of the anode (<1 μm). The relative ease of fabrication compared to vertical field emitters and enhanced field emission characteristics observed makes the carbon nanotube lateral field emitter a good candidate for future integrated nano-electronic devices.

Study of multi-walled carbon nanotube structures fabricated by PMMA suspended dispersion

We report on the electrical characteristics of plasma enhanced chemical vapour deposition (PECVD)-grown, multi-walled carbon nanotube (MWCNT) devices made by a new fabrication method, PMMA suspended dispersion. This method makes it possible to suspend nanotubes between metal electrodes and to remove unwanted nanotubes from the substrate. The measurements show that the MWCNTs are metallic and able to maintain a current density ∼2×106 A/cm2 for more than 15 days with a maximum current density of ∼1.8×107 A/cm2. This high current density and reliability will make PECVD-grown MWCNTs applicable to field emission cathodes. © 2002 Elsevier Science B.V. All rights reserved.

Self-aligned, gated arrays of individual nanotube and nanowire emitters

We demonstrate the production of integrated-gate nanocathodes which have a single carbon nanotube or silicon nanowire/whisker per gate aperture. The fabrication is based on a technologically scalable, self-alignment process in which a single lithographic step is used to define the gate, insulator, and emitter. The nanotube-based gated nanocathode array has a low turn-on voltage of 25 V and a peak current of 5 μA at 46 V, with a gate current of 10 nA (i.e., 99% transparency). These low operating voltage cathodes are potentially useful as electron sources for field emission displays or miniaturizing electron-based instrumentation.

Wastewater Electrolysis Cell for Environmental Pollutants Degradation and Molecular Hydrogen Generation

This study proposes a wastewater electrolysis cell (WEC) for on-site treatment of human waste coupled with decentralized molecular H₂ production. The core of the WEC includes mixed metal oxides anodes functionalized with bismuth doped TiO₂ (BiO_x/TiO₂). The BiO_x/TiO₂ anode shows reliable electro-catalytic activity to oxidize Cl- to reactive chlorine species (RCS), which degrades environmental pollutants including chemical oxygen demand (COD), protein, NH4⁺, urea, and total coliforms. The WEC experiments for treatment of various kinds of synthetic and real wastewater demonstrate sufficient water quality of effluent for reuse for toilet flushing and environmental purposes. Cathodic reduction of water and proton on stainless steel cathodes produced molecular H2 with moderate levels of current and energy efficiency. This thesis presents a comprehensive environmental analysis together with kinetic models to provide an in-depth understanding of reaction pathways mediated by the RCS and the effects of key operating parameters. The latter part of this thesis is dedicated to bilayer hetero-junction anodes which show enhanced generation efficiency of RCS and long-term stability.

Chapter 2 describes the reaction pathway and kinetics of urea degradation mediated by electrochemically generated RCS. The urea oxidation involves chloramines and chlorinated urea as reaction intermediates, for which the mass/charge balance analysis reveals that N₂ and CO₂ are the primary products. Chapter 3 investigates direct-current and photovoltaic powered WEC for domestic wastewater treatment, while Chapter 4 demonstrates the feasibility of the WEC to treat model septic tank effluents. The results in Chapter 2 and 3 corroborate the active roles of chlorine radicals (Cl•/Cl₂^-•) based on iR-compensated anodic potential (thermodynamic basis) and enhanced pseudo-first-order rate constants (kinetic basis). The effects of operating parameters (anodic potential and [Cl^-] in Chapter 3; influent dilution and anaerobic pretreatment in Chapter 4) on the rate and current/energy efficiency of pollutants degradation and H₂ production are thoroughly discussed based on robust kinetic models. Chapter 5 reports the generation of RCS on Ir_0.7Ta_0.3O_y/Bi_xTi_1-xO_z hetero-junction anodes with enhanced rate, current efficiency, and long-term stability compared to the Ir_0.7Ta_0.3O_y anode. The effects of surficial Bi concentration are interrogated, focusing on relative distributions between surface-bound hydroxyl radical and higher oxide.