• Journal of the Korean Electrochemical Society
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• v.17 no.2
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• pp.119-123
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• 2014

Here I report on how Fourier Transform Electrochemical Impedance Spectroscopy (FTEIS) overcomes the potential-current linearity problem encountered in the impedance calculation process. FTEIS was first invented to solve the time-related drawback of the conventional impedance technique. The dramatic time reduction of FTEIS enabled the real-time impedance measurement but brought about the linearity problem at the same time. While the conventional method circumvents the problem using the steady-state made by a sufficiently long measurement time, FTEIS cannot because of its real-time function. However, according to the mathematical development reported in this article, the potential step used in FTEIS is proved to avoid the linearity problem. During the step period, the potential and the current are linearized by the electrochemical impedance. Also, Fourier transform of the differentiated potential and current is proved to give the same result of the original ones.

• Membrane Journal
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• v.9 no.4
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• pp.230-239
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• 1999

Perchlorate ion-selective electrodes in PVC membranes that respond linearly to concentration 106 M were developed by incorporating the quaternary phosphonium salts as a canier. The effects of the chemical structure, the contents of canier, the kind of plasticizer and the membrane thickness on electrode characteristics such as the electrode slope, the linear respone range and the detection limit were studied. With this results, the detectable pH range, selectivity coefficients and AC impedance characteristics were compared and investigated. The perchlorate ion substituents of the quaternary phosphonium salts like tetraoctylphosphonium perchlorate (TOPP) , tetraphenylphosphonium perchlorate(TPPP), and tetrabutylphosphonium perchlorate(TBPP) as a canier were used. The electrode characteristics were better in the ascending order of TBPP < TPPP < TOPP, with the increase of carbon chain length of the alkyl group. Dioctylsebacate(OOS) was best as a plasticizer, the canier contents were better with 11.76 wt% and the optimum membrane thickness was 0.19 mm. Under the above condition, the electrode slope was 56.58 mV/$^P{ClO}_4$,the linear response range was $10^{-1}$\times$10^{-6}$ M, the detection limit was 9.66 x $10^{-7}$ M. The performance of electrode was better than Orion electrode. The electrode potential was stable within the pH range from 3 to 11. The order of the selectivity coefficients for the perchlorate ion was sol < F < Br < 1. With the result of impedance spectrum, it was found that the equivalent circuit for the electrode could be expressed by a series combination of solution resistance, parallel circuit consisting of the double layer capacitance and bulk resistance and Warburg impedance. And solution resistance was almost not appeared and Warburg impedance was highly appeared by diffusion. Then Warburg coefficient was 1.32$\times$$10^74 $\Omega$ $\cdot$ ${cm}^2/s^{1/2}$.

• Journal of the Korean Electrochemical Society
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• v.3 no.3
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• pp.131-135
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• 2000

In order to investigate the origin of capacity fading with charge/discharge cycling in $LiMn_2O_4$ thin film battery, impedance studies have been performed with increasing cycling in $LiMn_2O_4/1M\;LiClO_4-PC/Li$ cells. The fitted values obtained from impedance data show good agreements with the experimental results. Especially, the element of charge transfer resistance of $LiMn_2O_4/liquid$ electrolyte interface initially increased, and then saturated with increasing the charge/discharge cycles, which could explain the cause of initial abrupt capacity fading of $LiMn_2O_4$ thin film with cycling due to interfacial reaction. The steady capacity fading is caused by the increasing of Warburg resistance. The chemical diffusion coefficient of Li ions decreased from $5.15\times10^{-11}cm^2/sec$ at 1st cycles to $6.3\times10^{-12}cm^2/sec$ at 800th cycles, which attributed to the Jahn-Teller distortion/Mn dissolution which diminishes tetra hedral sites necessary for Li diffusion in $LiMn_2O_4$.

• Journal of the Korean Chemical Society
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• v.42 no.6
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• pp.664-671
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• 1998

Poly pyrrole polymer(ppy) has an excellent electrical conductivity and can be easily polymerized on anode to give various morophology according to doped anion on electroactive sites. To improve the properties of brittleness, ageing and hydrophobisity, poly furan polymer(pfu) having a high initiation potential was anodically implanted in this porous ppy film matrix to get the Pt/ppy/pfu(x)type of polymer composite electrode. Cyclic voltammetry and electrochemical impedance methods were used to these electrode, where $PF_6^-,\; BF_4^-$, and $ClO_4^-$ ions were employed as dopants. The composition of the pfu(x) at the electrode was changed from 0 to 1.10, but the range was useful only at 0.1 to 0.2 as the redox electrode. The polymer composite electrode doped with $PF_6^-$ was better in charge transfer resistance by a factor of 40 times and in double layer capacitance by a factor of 20 times than others. The charge transfer in the polymer film of the electrode was influenced on frequency change and equivalent circuit of this electrode had Warburg impedance including mass transfer.

• Corrosion Science and Technology
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• v.2 no.6
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• pp.289-295
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• 2003

The corrosion behavior of Cr-N coated steels with different phases (${\alpha}-Cr$, CrN and $Cr_2N$) deposited by cathodic arc deposition on Hl3 steel was investigated in 3.5% NaCl solution at ambient temperature. Potentiodynamic polarization test, electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM) were the techniques applied to characterize the corrosion behavior. It was found that the CrN coating had a lower current density from potentiodynamic polarization test than others. The porosity, corresponding to the ratio of the polarization resistance of the uncoated and the coated substrate, was higher in the $Cr_2N$ coating than in the other Cr-N coated steels. EIS measurements showed, for the most of Cr-N coated steels, that the Bode plot presented two time constants. Also, the $Cr_2N$ coating represents the characteristic of Warburg behavior after 72hr of immersion. The coating morphologies were examined in planar view and cross-section by SEM analyses and the results were compared with those of the electrochemical measurement. The CrN coating had a dense, columnar grain-sized microstructure with minor intergranular porosity. From the above results, the CrN coating provided a better corrosion protection than the other Cr-N coated steels.

• Corrosion Science and Technology
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• v.17 no.4
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• pp.166-175
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• 2018

In this study, the electrochemical properties of CP-Ti (commercially pure titanium) and Ti-64 (Ti-6Al-4V) were evaluated and the effect of hydrofluoric acid on corrosion resistance and electrochemical properties was elucidated. Additive manufactured materials were made by DMT (Directed Metal Tooling) method. Samples were heat-treated for 1 hour at $760^{\circ}C$ and then air cooled. Surface morphologies were studied by optical microscope and SEM. Electrochemical properties were evaluated by anodic polarization method and AC-impedance measurement. The oxide film formed on the surface was analyzed using an XPS. The addition of HF led to an increase in the passive current density and critical current density and decreased the polarization resistance regardless of the alloys employed. Based on the composition of the oxide film, the compositional difference observed by the addition of HF was little, regardless of the nature of alloys. The Warburg impedance obtained by AC-impedance measurement indicates the dissolution of the constituents of CP-Ti and Ti-64 through a porous oxide film.

• Journal of the Korean Ceramic Society
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• v.55 no.3
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• pp.244-260
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• 2018

Issues in the electrical characterization of semiconducting photoanodes in a photoelectrochemical (PEC) cell, such as the cell geometry dependence, scan rate dependence in DC measurements, and the frequency dependence in AC measurements, are addressed, using the example of a $TiO_2$ photoanode. Contrary to conventional constant phase element (CPE) modeling, the capacitive behavior associated with Mott-Schottky (MS) response was successfully modeled by a Havriliak-Negami (HN) capacitance function-which allowed the determination of frequency-independent Schottky capacitance parameters to be explained by a trapping mechanism. Additional polarization can be successfully described by the parallel connection of a Bisquert transmission line (TL) model for the diffusion-recombination process in the nanostructured $TiO_2$ electrode. Instead of shunt CPEs generally employed for the non-ideal TL feature, TL models with ideal shunt capacitors can describe the experimental data in the presence of an infinite-length Warburg element as internal interfacial impedance - a characteristic suggested to be a generic feature of many electrochemical cells. Fully parametrized impedance spectra finally allow in-depth physicochemical interpretations.

• Applied Chemistry for Engineering
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• v.9 no.6
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• pp.870-877
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• 1998

With impedance spectrum measurements, impedance was studied in the interface between sample solutions for $K^+-ion$ selective PVC membrane electrode containing neutral carriers [dibenzo-18-crown-6 (D18Cr6) and valinomycine (Val)]. Response characteristics of electrode were examined by measuring AC impedance spectra that were resulted from the chemical structure and the content of carrier, variation of plasticizer, membrane thickness, doping of base electrolytes, and concentration variation of sample solution. Transport characteristics of PVC membrane electrode were also studied. It was found that the equivalent circuit for the membrane in $K^+$ solution could be expressed by a series combination of solution resistance and a parallel circuit consisting of the bulk resistance and geometric capacitance of the membrane system. But the charge transfer resistance and Warburg resistance were overlapped a little in the low concentration and low frequency ranges. The carrier, D18Cr6 was best for electrode and impedance characteristics, and ideal electrode characteristics were appeared especially in case of doping of the base electrolyte[potassium tetraphenylborate(TPB)]. The optimum carrier content was about 3.23 wt% in case of D18Cr6 and Val. DBP was best as a plasticizer. As membrane thickness decreased the impedance characteristics was improved, but electrode characteristics were lowered for membrane thickness below the optimum. In the case of D18Cr6, the selectivity coefficients by the mixed solution method for the $K^+$ ion were the order of $NH_4{^+}>Ca^{2+}>Mg^{2+}>Na^+$.

• Corrosion Science and Technology
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• v.17 no.1
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• pp.20-29
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• 2018

Ti and its alloys show the excellent corrosion resistance to chloride environments, but they show less corrosion resistance in HCl, $H_2SO_4$, NaOH, $H_3PO_4$, and especially HF environments at high temperature and concentration. In this study, we used the commercially pure titanium and Ti-6Al-4V alloy, and evaluated the effect of the manufacturing process on the electrochemical properties. We used commercial products of rolled and forged materials, and made additive manufactured materials by DMT (Directed Metal Tooling) method. We annealed each specimen at $760^{\circ}C$ for one hour and then air cooled. We performed anodic polarization test, AC impedance measurement, and Mott-Schottky plot to evaluate the electrochemical properties. Despite of the difference of its microstructure of CP-Ti and Ti-6Al-4V alloys by the manufacturing process, the anodic polarization behavior was similar in 20% sulfuric acid. However, the addition of 0.1% hydrofluoric acid degraded the electrochemical properties. Among three kinds of the manufacturing process, the electrochemical properties of additive manufactured CP-Ti, and Ti-6Al-4V alloys were the lowest. It is noted that the test materials showed a Warburg impedance in HF acid environments.

• Journal of the Korean Ceramic Society
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• v.48 no.6
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• pp.549-558
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• 2011

Application of a generalized equivalent circuit including the electrode condition for the Hebb-Wagner polarization in the frequency domain proposed by Jamnik and Maier can provide a consistent set of material parameters, such as the geometric capacitance, partial conductivities, chemical capacitance or diffusivity, as well as electrode characteristics. Generalization of the shunt capacitors for the chemical capacitance by the constant phase elements (CPEs) was applied to a model mixed conducting system, $Ag_2S$, with electron-blocking AgI electrodes and ion-blocking Pt electrodes. While little difference resulted for the electron-blocking cell with almost ideal Warburg behavior, severely non-ideal behavior in the case of Pt electrodes not only necessitates a generalized transmission line model with shunt CPEs but also requires modelling of the leakage in the cell approximately proportional to the cell conductance, which then leads to partial conductivity values consistent with the electron-blocking case. Chemical capacitance was found to be closer to the true material property in the electron-blocking cell while excessively high chemical capacitance without expected silver activity dependence resulted in the electron-blocking cell. A chemical storage effect at internal boundaries is suggested to explain the anomalies in the respective blocking configurations.