R. Kalai Selvan

Electric double layer capacitor and its improved specific capacitance using redox additive electrolyte

Halogen (iodide, I−) added aqueous electrolyte facilitates the capacitive behaviour of biomass derived activated carbon based electric double layer capacitors. To produce economically viable electrodes in large scale for supercapacitors (SCs), the activated carbons (ACs) prepared from Eichhornia crassipes (common water hyacinth) by ZnCl2 activation. The prepared ACs were characterized by XRD, Raman, FT-IR and surface area, pore size and pore volume analysis. The electrochemical properties of the SCs were studied using cyclic voltammetry (CV), galvanostatic charge–discharge (GCD), electrochemical impedance spectroscopy (EIS) and cycling stability. The 3I−/I3−, 2I−/ I2, 2I3−/3I2 and I2/IO3− pairs produce redox peaks in CV and a large Faradaic plateau in charge–discharge curves. Similarly, I− ions improves the good ionic conductivity (lower charge transfer resistance) at the electrode/electrolyte interface which was identified through EIS studies. The calculated specific capacitance and energy density was 472 F g−1 and 9.5 W h kg−1 in aqueous solution of 1 M H2SO4. Interestingly, nearly two-fold improved specific capacitance and energy density of 912 F g−1 and 19.04 W h kg−1 were achieved when 0.08 M KI was added in 1 M H2SO4 electrolyte with excellent cycle stability over 4000 cycles. Subsequently, this improved specific capacitance and energy density was compared with 0.08 M KBr added to 1 M H2SO4 (572 F g−1, 11.6 W h kg−1) and 0.08 M KI added to 1 M Na2SO4 (604 F g−1, 12.3 W h kg−1) as electrolytes.

Redox additive/active electrolytes: a novel approach to enhance the performance of supercapacitors

Currently, supercapacitors (SCs) are a promising field in the area of energy storage devices. In the last few decades, different types of carbon based materials with suitable surface modifications, metal oxides, metal hydroxides, conducting polymers and their various composites have been used as electrodes to improve the energy performance of SCs. In addition, different technologies like asymmetric and hybrid systems have also been introduced. Interestingly, another alternative approach has been proposed recently by a few research groups, wherein electrolytes (liquid and polymer) can enhance the performance of the SCs via redox reactions at the electrode–electrolyte interface, by introducing redox additives or mediators in the electrolytes. The main advantage of this new technique is its simple and safe preparation method, along with cost effectiveness compared to the preparation of some active electrode materials. Hence it is believed that identification of suitable redox additives or species in electrolytes will be a hotspot in the field of SCs in the coming years.

Redox additive aqueous polymer gel electrolyte for an electric double layer capacitor

A hydroquinone mediated PVA–H2SO4 gel electrolyte (PHHQ) and activated carbon from bio-waste were prepared for supercapacitor fabrication. PHHQ delivered a higher capacitance (941 F g−1 at 1 mA cm−2) and energy density (20 Wh kg−1 at 0.33 W g−1) than the PVA–H2SO4 gel electrolyte (425 F g−1 at 1 mA cm−2, 9 Wh kg−1 at 0.33 W g−1).

Improved performance of electric double layer capacitor using redox additive (VO2+/VO2+) aqueous electrolyte

Electric double layer capacitors (EDLCs) were fabricated using biomass derived porous activated carbon as electrode material with 1 M H2SO4 and VOSO4 added 1 M H2SO4 as electrolytes. Here, VOSO4 was used as redox additive to improve the overall performance of EDLC. As expected, the VOSO4 electrolyte showed ∼43% of improved specific capacitance of 630.6 F g−1 at 1 mA cm−2 compared to pristine 1 M H2SO4 (440.6 F g−1) due to the contribution of VO2+/VO2+ redox reaction at the electrode–electrolyte interface. Possible redox reaction mechanism of VO2+/VO2+ pair is also briefly illustrated. The good cycling performance of 97.57% capacitance retention was observed even after 4000 cycles. For comparison, the polymer gel electrolyte (PVA/VOSO4/H2SO4) was also prepared and then the performance of the fabricated EDLCs was studied. Overall, these findings could open up a simple and cost effective way to improve the performance of EDLCs significantly.

Synthesis of ZnFe2O4 nanoparticles and their asymmetric configuration with Ni(OH)2 for a pseudocapacitor

Nanosized zinc ferrite (ZnFe2O4) particles are prepared by a simple aspartic acid assisted combustion method at three different pH conditions. X-ray diffraction analysis (XRD) is used to identify the single phase formation of ZnFe2O4 and its crystal system. The particle size and shape are revealed through transmission electron microscopy (TEM) images and the particles are in the size range between 20–30 nm. The valence states of zinc, iron and oxygen are determined through X-ray photoelectron spectroscopy (XPS). The electrochemical performances of the individual electrodes and fabricated cells are studied using cyclic voltammetry (CV), galvanostatic charge–discharge analysis (GCD) and impedance spectroscopy (EIS) analysis. A maximum specific capacitance of 1235 F g−1 at 1 mA cm−2 is obtained for ZnFe2O4 prepared at pH 10. Furthermore an asymmetric supercapacitor (ASC) is fabricated using ZnFe2O4 as the negative electrode and Ni(OH)2 as the positive electrode. Interestingly, this assembled ASC delivers good energy and power densities of 33 W h kg−1 and 68 W kg−1, respectively.

Electrochemical performances of CoFe2O4 nanoparticles and a rGO based asymmetric supercapacitor

CoFe2O4 nanoparticles were prepared using a polyethylene glycol (PEG) assisted solution combustion method. The X-ray diffraction pattern, Fourier transform infrared and Raman spectra revealed the single phase formation of CoFe2O4 particles. Transmission electron microscopy (TEM) images revealed nanosized particles less than 10 nm in size. The calculated voltammetry specific capacitance of the CoFe2O4 electrode was 195 F g−1 at 1 mV s−1. The Powers law suggests the capacitive mechanism is dominant over an intercalation mechanism, while the maximum number of charges accommodated in the inner surface of the electrode, is given by the Trasatti plot. The fabricated rGO based hybrid supercapacitor (CoFe2O4‖rGO) provides a good specific capacitance (38 F g−1) and energy density (12.14 W h kg−1) at 3 mA with good cycle life, and the serially connected asymmetric supercapacitor device powers the light emitting diode for 10 minutes.

Effect of pH on the sonochemical synthesis of BiPO4 nanostructures and its electrochemical properties for pseudocapacitors.

Using sonochemical method, BiPO4 nanocrystals were prepared at different pH conditions (pH-1, 3, 5, 7, 9 & 12) for the possible applications of pseudocapacitor electrodes. The prepared BiPO4 nanocrystals belong to monoclinic structure with P21 space group. The SEM image revealed that the particles changed from irregular coarse shape into rod like structure (pH-1 to 7) which finally collapsed into irregular aggregates (pH-9 to pH-12). The observed spot patterns from SAED inferred the polycrystalline nature of the material. The electrochemical performance of the synthesized BiPO4 in various ultrasound irradiation conditions such as irradiation time (30min, 1h, 2h and 3h) and ultrasonication power (40%, 50%, 60% and 70% of instrumental power) was studied. A maximum specific capacitance of 1052F/g (pH-7 at 2mV/s) was observed for the BiPO4 prepared in the ultrasonication reaction condition of 2h with 60% power. Also the obtained specific capacitance was high compared with the conventional precipitation method (623F/g at 2mV/s) that revealed the prominence of sonication method. Similarly, BiPO4 prepared at pH-7 delivered a maximum specific capacitance of 302F/g at 2mA/cm(2) calculated from galvanostatic charge-discharge (GCD) method than the other pH conditions. However, the cycling stability of BiPO4 (pH-7) was not appreciable even for 200 cycles. So, attempts were taken to enhance the cycling stability of the material by employing various carbon matrices such as acetylene black, activated carbon and MWCNT instead of carbon black during electrode preparation. BiPO4 material with activated carbon delivered good capacitance retention compared with other carbon matrices. This enhanced electrochemical performance of BiPO4 (pH-7) using activated carbon matrix inferred that it could be utilized as efficient negative electrode material for pseudocapacitors.

Studies on the electrochemical intercalation/de-intercalation mechanism of NiMn2O4 for high stable pseudocapacitor electrodes

Sub-micron sized polyhedral shaped NiMn2O4 particles were successfully prepared by a glycine assisted solution combustion method. The phase purity and the presence of functional groups in NiMn2O4 were revealed through X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR), respectively. The formation of polyhedral shaped particles was inferred by field emission scanning electron microscopy (FE-SEM). The negative temperature coefficient of resistance (NTCR) behaviour of NiMn2O4 was observed using a solid state impedance analyser in the measured temperature range between 30 and 180 °C. Further, electrochemical studies revealed that NiMn2O4 stores the charge through intercalation rather than by a capacitive mechanism. The electrode stores 91% of the specific capacitance by intercalation and 9% by a capacitive mechanism. Also, NiMn2O4 possesses a specific capacitance of 202 F g−1 at 0.5 mA cm−2 in 1 M Na2SO4 electrolyte and exhibits excellent cyclic stability over 15 000 cycles. Similarly, the fabricated asymmetric device (FeVO4‖NiMn2O4) also delivers good specific capacitance (50 F g−1 at 1 mV s−1) and cyclic stability.

Effect of carbon coating on the electrochemical properties of Co2SnO4 for negative electrodes in Li-ion batteries

Co2SnO4 particles were synthesized by a sonochemical method under different pH conditions, followed by carbon coating by a hydrothermal method. The thermal stability and compound formation temperature were identified through thermogravimetric analysis (TGA). The X-ray diffraction (XRD) pattern elucidated the compound formation of Co2SnO4 with cubic structure. Co2SnO4 encapsulated with carbon was confirmed through the TEM and HRTEM analysis and the approximate thickness of carbon was around 20 nm. The pristine-Co2SnO4 and carbon coated Co2SnO4 provided a discharge capacity of 777 mA h g−1 and 780 mA h g−1 at the current density of 40 mA g−1 with the capacity retention of 67% and 81% respectively in the 20th cycle. The charge transfer resistance of carbon coated Co2SnO4 was low when compared to pristine Co2SnO4 which lead to good reversibility of the material. The electrochemical study revealed the excellent electrochemical performance of the carbon coated Co2SnO4 particles with superior cycling stability and electronic conductivity.

Sonochemical synthesis, structural, magnetic and grain size dependent electrical properties of NdVO4 nanoparticles

NdVO4 nanoparticles are successfully synthesized by efficient sonochemical method using two different structural directing agents like CTAB and P123. The phase formation and functional group analysis are carried out using X-ray diffraction (XRD) and fourier transform infra red (FT-IR) spectra, respectively. Using Scherrer equation the calculated grain sizes are 27 nm, 24 nm and 20 nm corresponding to NdVO4 synthesized by without surfactant, with CTAB and P123, respectively. The TEM images revealed that the shape of NdVO4 particles is rice-like and rod shaped particles while using CTAB and P123 as surfactants. The growth mechanism of NdVO4 nanoparticles is elucidated with the aid of TEM analysis. From electrical analysis, the conductivity of NdVO4 nanoparticles synthesized without surfactant showed a higher conductivity of 5.5703 × 10(-6) S cm(-1). The conductivity of the material depends on grain size and increased with increase in grain size due to the grain size effect. The magnetic measurements indicated the paramagnetic behavior of NdVO4 nanoparticles.