• A K Shukla

Articles written in Journal of Chemical Sciences

• Fuel cells: Problems and prospects

In recent years, fuel cell technology has advanced significantly. Field trials on certain types of fuel cells have shown promise for electrical use. This article reviews the electrochemistry, problems and prospects of fuel cell systems.

• New lithium-ion conducting perovskite oxides related to (Li, La)TiO3

We describe the synthesis and lithium-ion conductivity of new perovskite-related oxides of the formulas, LiCa1.650.35Ti1.3B1.7O9 (B =Nb,Ta)(I,II), LiSr2Ti2.5W0.5O9 (III) and LiSr1.650.35Ti2.15W0.85O9(IV). OxidesI andII crystallize in orthorhombic (GdFeO3-type) structure, while oxidesIII andIV possess cubic symmetry. All of them exhibit significant lithium-ion conduction at high temperatures, the highest conductivity of ∼ 10−2S/cm at 800°C among the oxides is exhibited by the composition IV. The results are discussed in the light of previous work on lithium-ion conducting perovskite oxides containingd0 cations.

• AC impedance behaviour and state-of-charge dependence of Zr0¨5Ti0¨5V0¨6Cr0¨2Ni1¨2 metal-hydride electrodes

Metal-hydride electrodes made of an AB2 alloy of the composition Zr0¨5Ti0¨5V0¨6Cr0¨2Ni1¨2 are studied for AC impedance behaviour at several of their state-of-charge values. Impedance data at any state-of-chargecomprisetwoRC-time constants and accordingly are analysed by using a nonlinear-least-square-fitting procedure. Resistance of the electrode and frequency maximumf* of the lowfrequency semicircle are found useful for predicting state-of-charge of the metalhydride electrodes.

• Monitoring sealed automotive lead-acid batteries by sparse-impedance spectroscopy

A reliable diagnostics of lead-acid batteries would become mandatory with the induction of an improved power net and the increase of electrically assisted features in future automobiles. Sparse-impedance spectroscopic technique described in this paper estimates the internal resistance of sealed automotive lead-acid batteries in the frequency range 10 Hz-10 kHz, usually produced by the alternators fitted in the automobiles. The state-of-health of the battery could be monitored from its internal resistance.

• A low-cost lead-acid battery with high specific-energy

Lightweight grids for lead-acid battery grids have been prepared from acrylonitrile butadiene styrene (ABS) copolymer followed by coating with lead. Subsequently, the grids have been electrochemically coated with a conductive and corrosion-resistant layer of polyaniline. These grids are about 75% lighter than those employed in conventional lead-acid batteries. Commercial-grade 6V/3.5Ah (C20-rate) lead-acid batteries have been assembled and characterized employing positive and negative plates constituting these grids. The specific energy of such a lead-acid battery is about 50 Wh/kg. The batteries can withstand fast charge-discharge duty cycles.

• Poly (vinyl alcohol) hydrogel membrane as electrolyte for direct borohydride fuel cells

A direct borohydride fuel cell (DBFC) employing a poly (vinyl alcohol) hydrogel membrane electrolyte (PHME) is reported. The DBFC employs an AB5 Misch metal alloy as anode and a goldplated stainless steel mesh as cathode in conjunction with aqueous alkaline solution of sodium borohydride as fuel and aqueous acidified solution of hydrogen peroxide as oxidant. Room temperature performances of the PHME-based DBFC in respect of peak power outputs; ex-situ cross-over of oxidant, fuel, anolyte and catholyte across the membrane electrolytes; utilization efficiencies of fuel and oxidant, as also cell performance durability are compared with a similar DBFC employing a Nafion®-117 membrane electrolyte (NME). Peak power densities of ∼30 and ∼40 mW cm-2 are observed for the DBFCs with PHME and NME, respectively. The crossover of NaBH4 across both the membranes has been found to be very low. The utilization efficiencies of NaBH4 and H2O2 are found to be ∼24 and ∼59%, respectively for the PHME-based DBFC; ∼18 and ∼62%, respectively for the NME-based DBFC. The PHME and NME-based DBFCs exhibit operational cell potentials of ∼ 1.2 and ∼ 1.4 V, respectively at a load current density of 10 mA cm-2 for ∼100 h.

• Hydrogel membrane electrolyte for electrochemical capacitors

Polymer electrolytes are known to possess excellent physicochemical properties that are very useful for electrochemical energy systems. The mobility in polymer electrolytes is understood to be mainly due to the segmental motion of polymer chains and the ion transport is generally restricted to the amorphous phase of the polymer. Gel polymer electrolytes (GPE) that are formed using plastizicers and polymers along with ionic salts are known to exhibit liquid-like ionic conductivity while maintaining the dimensional stability of a solid matrix. In the present study, the preparation and characterization of poly(vinyl alcohol)-based hydrogel membranes (PHMEs) as electrolytes for electrochemical capacitors have been reported. Varying HClO4 dopant concentration leads to different characteristics of the capacitors. The EC comprising PHME doped with 2 M HClO4 and black pearl carbon (BPC) electrodes has been found to exhibit a maximum specific capacitance value of 97 F g-1, a phase angle value of 78°, and a maximum charge-discharge coulombic efficiency of 88%.

• A solid-polymer-electrolyte direct methanol fuel cell (DMFC) with Pt-Ru nanoparticles supported onto poly(3,4-ethylenedioxythiophene) and polystyrene sulphonic acid polymer composite as anode

Nano-sized Pt-Ru supported onto a mixed-conducting polymer composite comprising poly(3,4-ethylenedioxythiophene)-polystyrene sulphonic acid (PEDOT-PSSA) is employed as anode in a solid-polymer-electrolyte direct methanol fuel cell (SPE-DMFC) and its performance compared with the SPE-DMFC employing conventional Vulcan XC-72R carbon supported Pt-Ru anode. Physical characterization of the catalyst is conducted by Fourier-transform infra-red (FTIR) spectroscopy, X-ray diffraction (XRD), Scanning electron microscopy (SEM) and Energy dispersive X-ray analysis (EDAX) in conjunction with cyclic voltammetry and chronoamperometry. The study suggests that PEDOT-PSSA to be a promising alternative catalyst-support-material for SPE-DMFCs.

• A self-supported 40W direct methanol fuel cell system

A self-supported 40W Direct Methanol Fuel Cell (DMFC) system has been developed and performance tested. The auxiliaries in the DMFC system comprise a methanol sensor, a liquid-level indicator, and fuel and air pumps that consume a total power of about 5W. The system has a 15-cell DMFC stack with active electrode-area of 45 cm2. The self-supported DMFC system addresses issues related to water recovery from the cathode exhaust, and maintains a constant methanol-feed concentration with thermal management in the system. Pure methanol and water from cathode exhaust are pumped to the methanol-mixing tank where the liquid level is monitored and controlled with the help of a liquid-level indicator. During the operation, methanol concentration in the feed solution at the stack outlet is monitored using a methanol sensor, and pure methanol is added to restore the desired methanol concentration in the feed tank by adding the product water from the cathode exhaust. The feed-rate requirements of fuel and oxidant are designed for the stack capacity of 40W. The self-supported DMFC system is ideally suited for various defense and civil applications and, in particular, for charging the storage batteries.

• Photocatalytic properties of KBiO3 and LiBiO3 with tunnel structures

In the present study, KBiO3 is synthesized by a standard oxidation technique while LiBiO3 is prepared by hydrothermal method. The synthesized catalysts are characterized by X-ray diffraction (XRD), Scanning ElectronMicroscopy (SEM), BET surface area analysis and Diffuse Reflectance Spectroscopy (DRS). The XRD patterns suggest that KBiO3 crystallizes in the cubic structure while LiBiO3 crystallizes in orthorhombic structure and both of these adopt the tunnel structure. The SEM images reveal micron size polyhedral shaped KBiO3 particles and rod-like or prismatic shape particles for LiBiO3. The band gap is calculated from the diffuse reflectance spectrum and is found to be 2.1 eV and 1.8 eV for KBiO3 and LiBiO3, respectively. The band gap and the crystal structure data suggest that these materials can be used as photocatalysts. The photocatalytic activity of KBiO3 and LiBiO3 are evaluated for the degradation of anionic and cationic dyes, respectively, under UV and solar radiations.

• Endurance of Nafion-composite membranes in PEFCs operating at elevated temperature under low relative-humidity

PEFCs employing Nafion-silica (Nafion-SiO2) and Nafion-mesoporous zirconium phosphate (Nafion-MZP) composite membranes are subjected to accelerated-durability test at 100°C and 15% relative humidity (RH) at open-circuit voltage (OCV) for 50 h and performance compared with the PEFC employing pristine Nafion-1135 membrane. PEFCs with composite membranes sustain the operating voltage better with fluoride-ion-emission rate at least an order of magnitude lower than PEFC with pristine Nafion-1135 membrane. Reduced gas-crossover, fast fuel-cell-reaction kinetics and superior performance of the PEFCs with Nafion-SiO2 and Nafion-MZP composite membranes in relation to the PEFC with pristine Nafion-1135 membrane support the long-term operational usage of the former in PEFCs. An 8-cell PEFC stack employing Nafion-SiO2 composite membrane is also assembled and successfully operated at 60°C without external humidification.

• Substrate integrated Lead-Carbon hybrid ultracapacitor with flooded, absorbent glass mat and silica-gel electrolyte configurations

Lead-Carbon hybrid ultracapacitors (Pb-C HUCs) with flooded, absorbent-glass-mat (AGM) and silica-gel sulphuric acid electrolyte configurations are developed and performance tested. Pb-C HUCs comprise substrate-integrated PbO2 (SI-PbO2) as positive electrodes and high surface-area carbon with graphite-sheet substrate as negative electrodes. The electrode and silica-gel electrolyte materials are characterized by XRD, XPS, SEM, TEM, Rheometry, BET surface area, and FTIR spectroscopy in conjunction with electrochemistry. Electrochemical performance of SI-PbO2 and carbon electrodes is studied using cyclic voltammetry with constant-current charge and discharge techniques by assembling symmetric electrical-double-layer capacitors and hybrid Pb-C HUCs with a dynamic Pb(porous)/PbSO4 reference electrode. The specific capacitance values for 2 V Pb-C HUCs are found to be 166 F/g, 102 F/g and 152 F/g with a faradaic efficiency of 98%, 92% and 88% for flooded, AGM and gel configurations, respectively.

• Influence of binder solvent on carbon-layer structure in electrical-double-layer capacitors

Porous activated-carbons with a large surface-area have been the most common materials for electrical-double-layer capacitors (EDLCs). These carbons having a wide pore distribution ranges from micropores to macropores in conjunction with a random pore connection that facilitates the high specific-capacitance values. Pore distribution plays a central role in controlling the capacitance value of EDLCs, since electrolyte distribution inside the active material mainly depends on the pore distribution. This has a direct influence on the distribution of resistance and capacitance values within the electrode. As a result, preparation of electrodes remains a vital issue in realising high-performance EDLCs. Generally, carbon materials along with some binders are dispersed into a solvent and coated onto the current collectors. This study examines the role of binder solvents used for the carbon-ink preparation on the microstructure of the electrodes and the consequent performance of the EDLCs. It is observed that the physical properties of the binder solvent namely its dielectric constant, viscosity and boiling point have important role in determining the pore-size distribution as well as the microstructure of electrodes which influence their specific capacitance values.

• Studies on 12 V substrate-integrated lead-carbon hybrid ultracapacitors

A cost-effective 12 V substrate-integrated lead-carbon hybrid ultracapacitor is developed and performance tested. These hybrid ultracapacitors employ flexible-graphite sheets as negative plate currentcollectors that are coated amperometrically with a thin layer of conducting polymer, namely poly-aniline to provide good adhesivity to activated-carbon layer. The positive plate of the hybrid ultracapacitors comprise conventional lead-sheet that is converted electrochemically into a substrate-integrated lead-dioxide electrode. 12 V substrate-integrated lead-carbon hybrid ultracapacitors both in absorbent-glass-mat and polymeric silicagel electrolyte configurations are fabricated and characterized. It is possible to realize 12 V configurations with capacitance values of ∼200 F and ∼300 F, energy densities of ∼1.9 Wh kg$^{−1}$ and ∼2.5 Wh kg$^{−1}$ and power densities of ∼2 kW kg$^{−1}$ and ∼0.8 kW kg$^{−1}$, respectively, having faradaic-efficiency values of ∼90 % with cycle-life in excess of 100,000 cycles. The effective cost of the mentioned hybrid ultracapacitors is estimated to be about ∼4 US$/Wh as compared to ∼20 US$/Wh for commercially available ultracapacitors.

• # Journal of Chemical Sciences

Volume 132, 2020
All articles
Continuous Article Publishing mode

• # Editorial Note on Continuous Article Publication

Posted on July 25, 2019