Improvement of electrochemical and thermal stability of LiFePO4@C batteries by depositing amorphous silicon film

Amorphous silicon (α-Si) films are deposited on LiFePO₄@C electrode by using vacuum thermal evaporation deposition technique and the effect of α-Si film on electrochemical performance of LiFePO₄@C cells is investigated systematically by the charge–discharge testing, cyclic voltammograms and AC impedance spectroscopy, respectively. The results reveal that the present of α-Si film on electrode surface could remarkably improve the electrochemical performance at high charge/discharge rate, especially at elevated temperature. This enhancement may be attributed to the amelioration of the electrochemical dynamics on the electrode/electrolyte interface resulting from the beneficial effects of α-Si film, which might significantly suppress the rise of both of the surface film resistance and charge transfer resistance.     

A comparison of charge transport behavior in functionalized and non-functionalized poly 3,4-(ethylenedioxythiophene) films

Poly 3,4-(ethylenedioxythiophene) (PEDOT) films electropolymerized from an aqueous micellar solution containing sodium dioctyl sulfosuccinate and the monomer were functionalized with 1-fluoro-2-nitro-4-azidobenzene (FNAB) molecules by a photochemical nitrene insertion reaction. The variation in redox activity and the changes in the charge transfer and diffusion (through bulk) behavior of the functionalized and the non-functionalized PEDOT films have been followed by electrochemical impedance spectroscopy and cyclic voltammetry. While the functionalized film allows a reversible insertion and extraction of guest cations and anions, the non-functionalized film is capable of exchanging only anions. The higher level of oxidation attained in the functionalized film is also reflected in the longer diffusion length (l_D) observed for the ions in this film. In both films the barrier to charge transfer is resistive rather than capacitive. Both charge transfer and diffusion resistance (R_CT and R_D) are lower for the functionalized film, a consequence of a higher surface roughness and a more nodular morphology and therefore higher optical contrast and faster color-bleach kinetics are achieved in this film. For the functionalized and the non-functionalized films, both R_CT and R_D are greatly enhanced during reduction than for oxidation. In particular, in the low frequency regime, the hindered diffusion-controlled extraction of anions from the bulk of the film is also evident from the larger R_D as compared to R_CT and the difference in their magnitudes is more pronounced for the functionalized film thus confirming that functionalization is a useful method for controlling the redox response of conducting polymer films.     

Kinetic study on the role of an LSGMC5 interlayer in improving the performance of Sm0.5Sr0.5CoO3-La0.8Sr0.2Ga0.8Mg0.15Co0.05O3 (LSGMC5)/LSGMC5 interface

The kinetics of oxygen reduction over various Sm_0.5Sr_0.5CoO₃(SSC)-La_0.8Sr_0.2Ga_0.8Mg_0.15Co_0.05O₃(LSGMC5)/LSGMC5 (interlayer)/LSGMC5 (electrolyte) assemblies were studied, which were essential to find the role of an interlayer in improving the performance of an electrode/electrolyte interface. Two major arcs were identified in the impedance spectra at near equilibrium conditions. The reciprocal of the electrode resistance corresponding to the high frequency arc showed a PO₂ dependency about 0.5 at 1073 K and decreased to one-fourth at 873 K, suggesting that the rate-determining step (rds) changed from the dissociative adsorption of oxygen or diffusion of adsorbed oxygen atoms to charge transfer. The reciprocal of the electrode resistance corresponding to the low frequency arc showed a PO₂ dependency about 1, suggesting an rds involving the gas diffusion of oxygen. DC polarization curves of various assemblies agreed well with the Butler-Volmer equation. Both the cathodic and anodic charge transfer coefficients were about 1, and the PO₂ dependencies of the exchange current densities were about 0.25, especially at low temperatures. The characteristics under polarization corresponded to a charge transfer process. The introduction of an LSGMC5 interlayer between the SSC-LSGMC5 electrode and LSGMC5 electrolyte did not change the reaction mechanism, and the role of the interlayer was to increase the number of active sites for oxygen reduction.     

Polyaniline nanofiber/carbon film as flexible counter electrodes in platinum-free dye-sensitized solar cells

Efficient transfer of charges from a counter electrode to an electrolyte is a key process during the operation of dye-sensitized solar cells. Here, we develop a flexible counter electrode by electrochemical deposition of polyaniline nanofibers on graphitized polyimide carbon films for use in a tri-iodide reduction. As determined by the electrochemical impedance spectroscopy, the flexible counter electrode exhibited very low charge transfer resistance and series resistance. These results are due to the high electrocatalytic activity of the polyaniline nanofibers and the high conductivity of the flexible graphitized polyimide film. In combination with a dye-sensitized TiO₂ photoelectrode and electrolyte, the photovoltaic device with the polyaniline counter electrode shows an energy conversion efficiency of 6.85% under 1 sun illumination. Short-term stability tests indicate that the photovoltaic device with the polyaniline counter electrode almost maintains its initial performance.     

Enhanced photoelectrochemistry and interactions in cadmium selenide-functionalized multiwalled carbon nanotube composite films

Cadmium selenide-functionalized multiwalled carbon nanotube (CdSe-f-MWCNT) composite films have been synthesized by the percolation of a f-MWCNT dispersion through the macropores of electrodeposited CdSe thin films during electrophoretic deposition. Evidence for efficient charge transfer from CdSe to f-MWCNTs was obtained by photoluminescence quenching and proof for strong interactions was provided by X-ray photoelectron spectroscopy analyses, which revealed a significant decrease in the reduced Se²⁻ content and evolution of new signals due to oxidized Se, and high resolution transmission electron microscopy and atomic force microscopy images of CdSe decorated f-MWCNTs in the composite film. Sputter depth profiling of the composite confirmed a homogeneous mixing of nanoparticulate CdSe and f-MWCNTs. A quasi solid-state photoelectrochemical cell fabricated by coupling the composite film with an ionic liquid based gel polymer electrolyte containing the I₃/I⁻ redox pair not only showed larger photocurrents, photovoltage and incident photon to current conversion efficiency as compared to the analogous CdSe cell but also showed a remarkably enhanced stability to photoerosion. The ability of f-MWCNTs to mediate fast charge transfer and retard charge recombination rate in the composite was also evident from electrochemical impedance spectroscopy (EIS) results. Cell degradation upon exposure was also reflected in the altered EIS parameters such as increased charge transfer resistance and the reduced ease of charge transport through the composite.     

Effect of state of charge on impedance spectrum of sealed cells Part I: Ni-Cd cells

Alternating current impedance spectroscopy (ACIS) was performed on commercial sealed Ni-Cd cells. A method previously developed in the literature was modified to determine the state of charge of sealed Ni-Cd cells by obtaining the impedance spectrum in a wide frequency range. The impedance parameters were sensitive to state of charge at low frequencies. A modified Randles' circuit was used to fit the impedance data. Appropriate modifications were made to account for an additional high frequency arc or a low frequency finite diffusion element. The effect of the state of charge on the equivalent circuit parameters was determined.List of symbols R ohmic resistance of battery (ohms) - C _dl double layer capacitance (F) - Q ₁ constant phase element representing double layer capacitance - Q ₂ constant phase element representing Warburg diffusion - O finite diffusion element - R _t charge transfer resistance () - R _s,R _p equivalent series and parallel resistance () - C _s,C _p equivalent series and parallel capacitance (F)     

Impedance study of the passive film on stainless steel 304 in pH 8 carbonate solution

The effects of applied d.c. potential and polarization time on the passivation of stainless steel 304 (SS304) were investigated in deaerated 1 M NaHCo₃ aqueous solutions at pH 8. Electrochemical impedance spectroscopy was used in conjunction with a rotating disc electrode. The data were analysed by considering an equivalent circuit. The changes in impedance parameters at applied d.c. potential signal changes in the properties of passive films on SS304 and allow to distinguish the parameters at low potential (–0.6 to 0.3 V vs SCE) from a different one at high potential (0.5 to 0.8 V vs SCE). The oxidation reactions were controlled by both charge transfer and mass transfer processes. Diffusional resistance was high for both passive films and was considered to represent the resistance to movement of ions or vacancies through the surface layer of oxide films. It is deduced that the passive film present in the low potential region is partially dissolved at 0.4 V vs SCE and that a new passive film is formed in the higher potential region. The equivalent circuit used to obtain the best fit and the fitting parameters was dependent on the electrode potential and the polarization time. The reproducibility of the impedance spectra at constant potentials demonstrate that the passive film formation is highly irreversible process. No traces of localized corrosion were detected but, for a high potential and long polarization time, the electrode surface coloration to a uniform gold colour confirms the film thickening.     

Kinetics and mechanism of the magnesium electrode reaction in molten magnesium chloride

Using electrochemical impedance spectroscopy (EIS) and relaxation method with galvanostatic perturbation (RM) the kinetics and mechanism of the magnesium electrode reaction in pure molten M9Cl₂ have been determined at several temperatures. A three-step electrode process has been found, the high frequency process being pure charge transfer with the low frequency process showing mixed charge transfer-diffusion character. The low frequency step has also been treated as a preceding chemical reaction followed by charge transfer. On the basis of the corresponding exchange current densities and Warburg diffusion impedance, a mechanism of the overall electrode reaction in this melt is proposed.     

Electrochemical impedance spectroscopy of lead(II) ion-selective solid-state membranes

Silver sulphide/lead sulphide membranes were studied using electrochemical impedance spectroscopy. The influence of the electrolyte concentration and the membrane thickness were evaluated. The complex impedance plots have shown two capacitive loops: one at high frequency range, related with the charge transfer resistance at the interface membrane-Ag and a second one at low frequency range, associated with the diffusion process through the membrane. A simple model was used to take into account the experimental results: the changes of the potential with the time and the electrolyte concentration; the changes of the charge transfer resistance and the diffusion resistance with the electrolyte concentration. An empirical equation was used to calculate the diffusion coefficient of Ag⁺ inside the membrane.     

Testing of PEM fuel cell performance by electrochemical impedance spectroscopy: Optimum condition for low relative humidification cathode

Electrochemical impedance spectroscopy (EIS) was used to investigate the influence of several parameters on the performance of PEMFC. The applied frequency was in the range of 50 mHz–10 kHz. The experiment was designed by using a 2 ^k factorial design to identify the effects of various parameters including cell voltage, flow rates of gaseous fuels and cell temperature at the saturated humidification in anode and 60% relative humidity cathode. The results indicated that the cell temperature, cell voltage and interactions of cell voltage, flow rate of H₂ and O₂ had a significant effect on the cell performance. In addition, the flow rate of O₂ had a strong effect on the ohmic resistance and the charge transfer resistance in the system. Models describing the relationship between previous parameters and ohmic resistance, charge transfer resistance and capacitance were also developed.     

Electrochemical and structural characterization of AZ63 alloy surface film in MgSO4 solution

The formation and growth of surface film on AZ63 (Mg–6Al–3Zn) magnesium alloys were studied in 2 M MgSO₄ aqueous solution using electrochemical methods. Surface examinations were carried out using scanning electron microscopy, energy-dispersive X-ray spectroscopy, and microscopic Fourier transform infrared spectroscopy. Experimental results show that the corrosion current decreases with prolonged immersion time, the three stages of hydrogen evolution rate correspond with the growth processes of the surface film on AZ63 magnesium alloys, and charge transfer resistance increases with the accumulation of corrosion products. A layer of MgO with sulfate salt grains underneath seems smooth at first. However, a few surface micro-cracks caused by inner stress appear on the smooth base film after 5 h of immersion, followed by the aggregation of spherical grains and the formation of cracks after 12 h. It is suggested that sulfate salt, carbonate salt, and hydroxide of magnesium should be the main composition of the surface film.     

Study on charge transfer reactions at multilayers of polyoxometalates clusters and poly(allylamine hydrochloride) (Grotthuss-018)

Multilayers of anionic phosphotungstic acid (PTA) clusters and positively charged protonated poly(allylamine hydrochloride) (PAH) were assembled by layer-by-layer self-assembled method on Au electrode modified by 3-mercaptopropionic acid (3-MPA). The effect of the charge of the surface of the multilayer assembly on the kinetics of the charge transfer reaction was studied by using the redox probes [Fe(CN)₆]^3−/4− and [Ru(NH₃)₆]^2+/3+. The cyclic voltammetry experiments showed that the peak currents and peak-to-peak potential differences changed after assembling different layers on the electrode surface indicating that the charge of the surface has a significant effect on the kinetics of the studied charge transfer reactions. These reactions were studied in more detail by electrochemical impedance spectroscopy. When [Fe(CN)₆]^3−/4− was used as the redox label, multilayers that terminated with negatively charged PTA showed a high charge transfer resistance but multilayers that terminated with positively charged PAH showed lower charge transfer resistance. With [Ru(NH₃)₆]^2+/3+ as the redox label, the charge transfer resistance at multilayers that terminated with positively charged PAH was much higher than at the multilayer terminated by the negatively charged PTA. The charge transfer resistances also increased with the addition of number of layers indicating that the entire thickness of the multilayer assembly has also an effect on the kinetics of the studied charge transfer reactions and not only the electrostatic attraction or repulsion between the surface and the redox probes. The ohmic resistance of the multilayer assembly increased non-linearly with the number of layers. Assembling a layer of PAH increased the resistance more than assembling a layer of PTA.     

Enhanced cycling stability of Ni-MH battery by depositing amorphous carbon film on the Ti1.4V0.6Ni negative electrode

Amorphous carbon (a-C) films with various thicknesses depending on the reaction time are deposited on the surface of Ti_1.4V_0.6Ni alloy electrodes for Ni-MH (nickel-metal hydride) battery by radio frequency plasma enhanced chemical vapor deposition (RF-PECVD). With the increasing deposition time, the Raman spectra show a gradually disordered sp²-bonding change of the films and the changing trend of sp²/sp³ is obtained by X-ray photoelectron spectroscopy. The a-C film of depositing for 30 min with the thickness of 400 nm shows a favorable stability in alkaline electrolyte, the capacity is enhanced by 36.2% after 50 cycles than the bare electrode, and the charge voltage is 80 mV lower than the bare one. The a-C film with high sp²-bonded carbon content effectively reduces the charge transfer resistance, and as a coating layer, the dissolution of V of the alloy is also inhibited. In particular, to get a proper discharge voltage and a stable capacity simultaneously, covering completely and an appropriate thickness of the a-C film are crucial for an expected performance.     

Pulsed electrodeposition of microcrystalline chromium from trivalent Cr-DMF bath

Pulsed electrodeposition (PED) with square wave has successfully been applied to deposit microcrystalline chromium from Cr-dimethylformamide (DMF) bath. The influence of the duty cycle, on-time, off-time, frequency, and pulse peak current on thickness, current efficiency, and hardness were investigated. Based on the analysis of the microstructure, the corrosion behavior of both direct-current deposited (DCD) and pulse-current deposited (PED) chromium in 3.5% NaCl solution was studied using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The results indicated that both pulsed electrodeposits and direct-current deposits have high charge transfer resistance R _ct and very low I _corr compared with mild-steel substrate.     

Iron-carbon composites as electrode materials in lithium batteries

Iron-carbon composites have been prepared by adding Fe₂O₃ hematite to a petroleum vacuum residue as a carbon precursor. Iron contents and other synthesis parameters were varied to evaluate the evolution of the observed iron phases. XRD patterns and ⁵⁷Fe Mössbauer spectroscopy was used to monitor the reduction of the initial iron oxide to pyrrhotite (Fe₇S₈) intermediate, austenite (Fe_xC) and metallic iron as final reaction product when annealing temperature and time were high. Pyrrhotite has demonstrated to be electrochemically active and beneficial for the capacity retention in lithium test cells. Those samples with the higher pyrrhotite contribution have a good capacity retention achieving values close to 350 mAh/g after 30 cycles. AC measurements evidenced that iron species inhibit the increase of both the charge transfer resistance and the surface film resistance upon cycling.     

Electrochemical investigation of the effects of hydrogen on the stability of the passive film on iron

The effects of hydrogen on the stability of passive films on iron were investigated by electrochemical methods: open circuit potential decay, cathodic galvanostatic reduction, electrochemical impedance spectroscopy, and breakdown potential measurements. The results show that hydrogen decreases the final static open circuit potential, the cathodic charge for reduction and the charge transfer resistance of the passive film, indicating that hydrogen decreases the stability of the passive film. The charge transfer resistance of the passive film formed on the charged specimen does not change with increasing the film formation potentials, suggesting that increasing film formation potentials under hydrogen charging conditions cannot improve the stability of the passive film. Hydrogen decreases the breakdown potential of the passive film, especially at lower chloride ion concentrations, confirming that hydrogen promotes the susceptibility of the passive film on iron to pitting corrosion. The reasons why hydrogen decreases the stability of the passive film were discussed.     

Indirect charge transfer of holes via surface states in ZnO nanowires for photoelectrocatalytic applications

In this work, ZnO nanowires with high aspect ratio were obtained by fast and simple electrochemical anodization. Morphological, structural and photoelectrochemical characteristics of the synthesized ZnO nanowires were evaluated by using different techniques: field emission scanning electron microscopy, atomic force microscopy, high resolution transmission electron microscopy, Raman spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, UV–VIS spectroscopy, Mott-Schottky analysis and photoelectrochemical impedance spectroscopy. The synthesized ZnO nanowires presented high roughness and high crystallinity. Besides, surface defects were identified in the sample. The value of the donor density (N_D) was in the order of 10¹⁹ cm^?3 in the dark and 10²⁰ cm^?3 under illumination. In addition, the ZnO nanowires presented good photosensibility, with a photocurrent density response 85 times higher than a ZnO compact layer, and lower resistance to charge transfer. The charge transfer processes taking place at the ZnO/electrolyte interface were studied, since these processes strongly influence the photoelectrocatalytic efficiency of the material. According to the results, the charge transfer of holes in the synthesized ZnO nanowires occurs indirectly via surface states. In this regard, surface states may be an important feature for photoelectrocatalytic applications since they could provide lower onset voltages and higher anodic current densities.     

Redox behavior and optical response of nanostructured poly(3,4-ethylenedioxythiophene) films grown in a camphorsulfonic acid based micellar solution

Poly(3,4-ethylenedioxythiophene) (PEDOT) films have been electropolymerized from an aqueous micellar solution comprising camphorsulfonic acid (CSA), lithium trifluoromethanesulfonate (LiCF₃SO₃) and EDOT. The inclusion of the dopants CS⁻ and CF₃SO₃⁻ in the polymer structure and an unusually high doping level of 0.54 have been ascertained by the X-ray photoelectron spectroscopy. Transmission electron microscopy and atomic force microscopy studies show that the micellar effect of CSA leads to a morphology wherein polymer particles link together to form elongated shapes and also endows the film with a surface roughness of 25-30 nm. These nanostructures permit a facile intercalation-deintercalation of anions in the film during redox cycling. Electrochemical impedance spectroscopy show that the charge transfer phenomenon at the PEDOT-electrolyte interface is dominant in the high frequency region and diffusion controlled ionic movement prevails in the low frequency regime. The use of these films as potential cathodes in electrochromic windows is rationalized not only on the basis of their high scalability and ease of processing but also due to their large coloration efficiency (123 cm² C⁻¹) and transmission modulation (50%) at a photopic wavelength of 550 nm. But further improvement in color-bleach kinetics and reproducibility of redox behavior is desirable to broaden their spectrum of utility.     

Optoelectronic properties of In-doped SnS thin films

Nanostructured un- and In-doped SnS thin films were deposited on fluorine-doped tin oxide (FTO) substrates via an electrochemical deposition technique. The deposited thin films were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), energy dispersive spectroscopy (EDS), atomic force microscopy (AFM), electrochemical impedance spectroscopy (EIS), photoluminescence (PL) spectroscopy and UV–visible spectroscopy. The XRD patterns demonstrated that all deposited thin films are made of polycrystalline SnS particles. The AFM images illustrated a distinct change in the surface topography of the SnS thin films due to In-doping. The PL spectra showed two blue emission peaks and a green emission peak for all samples. Also, they highlighted a PL peak for the In-doped thin films. The incorporation of In-dopant leads to enhance in the optical absorption of SnS lattice. The optical energy band gap (E_g) of the deposited thin films was estimated using UV–vis spectroscopy, which indicated that In-doping decreases the E_g value of SnS thin films by creating defect levels. The photocurrent results demonstrated a higher photocurrent response and photocurrent amplitude for the In-doped SnS samples relative to the un-doped SnS thin film. The Mott–Schottky analysis revealed p-type conductivity for all samples. In addition, the carrier concentration of SnS was increased after In doping. The EIS spectra declared that In-doping improves the rate of charge transfer for SnS thin films. The charge transfer resistance of In-doped SnS decreased compared to the undoped SnS thin film. Finally, according to the J-V characteristics, the conversion efficiency of the In-doped SnS thin films was higher than that of the un-doped SnS sample. Therefore, the optical and electrical performance of SnS thin films were improved due to In-doping.     

Effects of Ti ion deposition on corrosion resistance of WE43 alloy

Ti films with different thicknesses were successfully deposited on the surface of WE43 alloy by filtered cathode vacuum arc technology, and the microscopic morphology, structural composition, and corrosion resistance of the films were studied by means of X-ray diffractometer, X-ray photoelectron spectroscopy and scanning electron microscope. The results show that when the deposition time of Ti ions is 800 s, the thickness of the Ti film is 2.35 μm, the surface of the film is dense, and there are few defects. Meanwhile, Ti800 alloy has the best corrosion resistance among the four modified alloys. It has a corrosion current density (I_corr) of 2.9 μA·cm⁻², which is about 50 times lower than that of unmodified alloy. This conclusion is also confirmed by the complete film layer of Ti800 alloy and the tight bonding with the substrate after immersion experiments. Good corrosion resistance is attributed to a dense and relatively chemically stable TiO₂/Ti structure in simulated body fluid corrosive media.