A Polyaniline-Deposited Nonplatinum Metal as a Potentiometric Sensor—An Inexpensive Alternate to Conventional Platinum for Some Potentiometric Redox Reactions

For the purpose of employing an inexpensive alternative to conventional platinum for use by upper-division as well as graduate students, polyaniline (PANI)-deposited stainless steel (SS) and mild steel (MS) electrodes are described as indicator electrodes for potentiometry and potentiometric titrations of some redox reactions. PANI is deposited on the nonplatinum metal by electrochemical polymerization of aniline using cyclic voltammetric technique. Alternate methods to produce the PANI electrodes are also suggested. The electrodes respond to concentration changes of hydroquinone (H₂O), Fe²⁺/Fe³⁺, and [Fe(CN)₆]^4–/[Fe(CN)₆]^3– in HCL electrolytes, and the potential variation with concentration follows the Nernst relationship. Under identical experimental conditions, the response time of the PANI/SS, PANI/MS, and Pt electrodes for a change in concentration of Fe³⁺ in a mixed electrolyte of Fe²⁺ and Fe³⁺ is found to be about 20 s. Neutralization reaction of HC1 versus NaOH, redox reaction of Fe²⁺ and Ce⁴⁺, and redox reaction of Fe²⁺ and KMnO₄ in several concentrations in the range from 1 mM to 100 mM are carried out using the PANI/SS, PANI/MS, and Pt indicator electrodes. The performance of the PANI/SS and PANI/MS electrodes is as good as that of the Pt at all concentration levels of the titrations. The electrodes can be reused for several titrations by storing them in an acid electrolyte for a long period of time. Thus, the conventional inert Pt or Au can be substituted for by using a PANI-deposited nonplatinum reactive metal as a potentiometric sensor for redox titrations.     

AC impedance and state-of-charge analysis of a sealed lithium-ion rechargeable battery

A 7.2 V, 1.25 Ah sealed lithium-ion rechargeable battery has been studied for estimating its state-of-charge (SOC) by AC impedance. The dispersion of impedance data over the frequency range between 100 kHz and 25 mHz comprises an inductive part and two capacitive parts. As the inductive behaviour of the battery is attributed to the porous nature of the electrodes, only the capacitive components have been examined. The data obtained at several SOC values of the battery have been analyzed by a non-linear least-squares fitting procedure. The presence of two depressed semicircles in the capacitive region of the Nyquist plots necessitated the use of an electrical equivalent circuit containing constant phase elements instead of capacitances. The impedance parameters corresponding to the low-frequency semicircle have been found useful for predicting the SOC of the battery, mainly because the magnitude of these parameters and their variations are more significant than those of the high-frequency semicircle. The frequency maximum (f _max) of the semicircle, the resistive component (Z′) corresponding to f _max, the phase angle (φ) in the 5.0 Hz–0.1 Hz frequency range, the equivalent series resistance (R _s) and the equivalent series capacitance (C _s) have been identified as suitable parameters for predicting the SOC values of the lithium-ion battery. Received: 23 September 1998 / Accepted: 22 February 1999     

A note on overpotential dependence of AC impedance data

Charge-transfer resistance [R _ct = (dη/di)_{η = 0}] and Tafel plots of current density (i) versus overpotential (η) data are generally known to yield values of the energy-transfer coefficient (α) and exchange current density (i _o) of an electrochemical reaction. In the present investigation, the resistance (dη/di)_η≠0 that could be calculated by differentiating a wide range of i−η curves was also shown to provide the values of α and i _o, by plotting ln(dη/di)_η≠0 against η. Since α and i _o could also be evaluated directly from the experimental DC polarization data, the procedure was not of significant importance. Nevertheless, it was considered important in evaluating α and i _o from AC impedance data, because the procedure was based on data analysis, which was much simpler than that reported in the literature. A cobalt electrode prepared from fine metal powder was used in 1 M KOH electrolyte and the hydrogen evolution reaction was studied by AC impedance at several potentials. The resistance values measured from the complex plane impedance diagram were plotted against the potential, and the values of α and i _o were evaluated. Received: 8 October 1998 / Accepted: 11 January 1999     

Ageing of magnesium /manganese dioxide primary cells

Mg/MnO₂ primary cells which were more than a decade old were investigated for their discharge capacity, a.c. impedance behaviour, delay time, effect of added water into the cell and effect of temperature. Although the cells were aged for a long duration, they were electrochemically active and yielded good discharge capacity, thus suggesting an extraordinary long shelf-life. There was a marginal increase in cell capacity subsequent to injection of 2 ml of water into a CD-size Mg/MnO₂ cell. The a.c. impedance of a partially discharged cell included the contributions of surface passive film on the Mg anode and corrosion of the Mg metal. The internal resistance of the cell was found to increase with storage time, suggesting that the resistance of a fresh cell also could similarly increase. By increasing the cell temperature, the impedance decreased considerably and also the delay time. These results suggested that the increase of temperature had favourable effects on the performance of the aged Mg/MnO₂ cells. Received: 24 August 1999 / Accepted: 2 December 1999     

Effect of non-stoichiometry on the charge storage capacity of NiO conversion anodes in Li-ion batteries

Conversion anodes comprising non-stoichiometric black NiO suffer severe capacity fading in Li-ion batteries despite having a high Li⁺ ion diffusion coefficient. We attribute this capacity fading to (i) its small crystallite size (~?8 nm) and (ii) high charge transfer resistance (R_ct ~?60–180 Ω cm²). Small crystallites enhance grain boundaries which promote Li⁺ ion diffusion without efficient material utilization. In contrast, the stoichiometric green NiO anodes deliver a stable capacity of 280 mAh g^?1 over 50 charge-discharge cycles. The comparatively higher capacity of green NiO can be explained from its (i) large crystallite size (~?104 nm) and (ii) negligible R_ct values.     

Synthesis and characterization of submicron size particles of LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> by microemulsion route

Among the various positive electrode materials investigated for Li-ion batteries, spinel LiMn₂O₄ is one of the most important materials. Small particles of the active materials facilitate high-rate capability due to large surface to mass ratio and small diffusion path length. The present work involves the synthesis of submicron size particles of LiMn₂O₄ in a quaternary microemulsion medium. The precursor obtained from the reaction is heated at different temperatures in the range from 400 to 900 °C. The samples heated at 800 and 900 °C are found to possess pure spinel phase with particle size <200 nm, as evidenced from XRD, SEM, and TEM studies. The electrochemical characterization studies provide discharge capacity values of about 100 mAh g⁻¹ at C/5 rate, and there is a moderate decrease in capacity by increasing the rate of charge–discharge cycling. Studies also include charge–discharge cycling and ac impedance studies in temperature range from −10 to 40 °C. Impedance data are analyzed with the help of an equivalent circuit and a nonlinear least squares fitting program. From temperature dependence of charge-transfer resistance, a value of 0.62 eV is obtained for the activation energy of Mn³⁺/Mn⁴⁺ redox process, which accompanies the intercalation/deintercalation of the Li⁺ ion in LiMn₂O₄.     

Co<Subscript>2</Subscript>(OH)<Subscript>3</Subscript>Cl xerogels with 3D interconnected mesoporous structures as a novel high-performance supercapacitor material

Co₂(OH)₃Cl xerogel interconnected mesoporous structures have been prepared by a facile one pot sol-gel process and heat treated at 200 and 400 °C. All samples are studied for their morphology, structure, and electrochemical stability upon cycling. The specific capacitance of the as-prepared Co₂(OH)₃Cl from single electrode study is 450 F/g, when the electrodes are cycled in 3 M KOH at a specific current 2 A/g. Interestingly, capacity retention after 500 and 1000 cycles is about 92 and 75 %, respectively. Sample heated at 200 °C exhibits 308 F/g at 2 A/g and that heated at 400 °C shows only 32 F/g at 0.2 A/g. With an increase in preparation temperature, amorphous Co₂(OH)₃Cl is converted to crystalline Co₃O₄ phases with lower electrochemical performance. In full cell study, as-prepared Co₂(OH)₃Cl showed a capacity of about 49 F/g as asymmetric capacitor and 32 F/g as symmetric capacitor at 2 A/g current density. Co₂(OH)₃Cl being a novel porous material with merits of homogeneous porosity, high surface area, and an interconnected three dimensional (3D) structure exhibits considerably high capacitance. With a significant specific capacity and electrochemical stability, the synthesized material is a novel potential candidate for supercapacitors.

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Porous,hollow Li<Subscript>1.2</Subscript>Mn<Subscript>0.53</Subscript>Ni<Subscript>0.13</Subscript>Co<Subscript>0.13</Subscript>O<Subscript>2</Subscript> microspheres as a positive electrode material for Li-ion batteries

A porous, hollow, microspherical composite of Li₂MnO₃ and LiMn_1/3Co_1/3Ni_1/3O₂ (composition: Li_1.2Mn_0.53Ni_0.13Co_0.13O₂) was prepared using hollow MnO₂ as the sacrificial template. The resulting composite was found to be mesoporous; its pores were about 20 nm in diameter. It also delivered a reversible discharge capacity value of 220 mAh g^?1 at a specific current of 25 mA g^?1 with excellent cycling stability and a high rate capability. A discharge capacity of 100 mAh g^?1 was obtained for this composite at a specific current of 1000 mA g^?1. The high rate capability of this hollow microspherical composite can be attributed to its porous nature.

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Effect of orientation on the reversible discharge capacity of electrodeposited Cu2O coatings as lithium-ion battery anodes

Journal of Solid State Electrochemistry - Electrodeposited Cu2O coatings with 111 out-of-plane orientation were found to have the lowest reversible discharge capacity as anodes for Li-ion cells....