• Title/Summary/Keyword: Electrode degradation

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Enhancement of Electrochemical Activity of Ni-rich LiNi0.8Mn0.1Co0.1O2 by Precisely Controlled Al2O3 Nanocoatings via Atomic Layer Deposition

  • Ramasamy, Hari Vignesh;Sinha, Soumyadeep;Park, Jooyeon;Gong, Minkyung;Aravindan, Vanchiappan;Heo, Jaeyeong;Lee, Yun-Sung
    • Journal of Electrochemical Science and Technology
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    • v.10 no.2
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    • pp.196-205
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    • 2019
  • Ni-rich layered oxides $Li(Ni_xCo_yMn_z)O_2$ (x + y + z = 1) have been extensively studied in recent times owing to their high capacity and low cost and can possibly replace $LiCoO_2$ in the near future. However, these layered oxides suffer from problems related to the capacity fading, thermal stability, and safety at high voltages. In this study, we use surface coating as a strategy to improve the thermal stability at higher voltages. The uniform and conformal $Al_2O_3$ coating on prefabricated electrodes using atomic layer deposition significantly prevented surface degradation over prolonged cycling. Initial capacity of 190, 199, 188 and $166mAh\;g^{-1}$ is obtained for pristine, 2, 5 and 10 cycles of ALD coated samples at 0.2C and maintains 145, 158, 151 and $130mAh\;g^{-1}$ for high current rate of 2C in room temperature. The two-cycle $Al_2O_3$ modified cathode retained 75% of its capacity after 500 cycles at 5C with 0.05% capacity decay per cycle, compared with 46.5% retention for a pristine electrode, at an elevated temperature. Despite the insulating nature of the $Al_2O_3$ coating, a thin layer is sufficient to improve the capacity retention at a high temperature. The $Al_2O_3$ coating can prevent the detrimental surface reactions at a high temperature. Thus, the morphology of the active material is well-maintained even after extensive cycling, whereas the bare electrode undergoes severe degradation.

A Study on Irreversible Degradation through OCV Reduction and Recovery Behavior in the Electrochemical Degradation Process of PEMFC Polymer Membrane (PEMFC 고분자 막의 전기화학적 열화과정에서 OCV 감소 및 회복 거동을 통한 비가역적 열화 연구)

  • Yoo, Donggeun;Park, Kwon-Pil
    • Korean Chemical Engineering Research
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    • v.60 no.2
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    • pp.217-222
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    • 2022
  • It is very important to analyze the OCV change behavior during the open circuit potential holding (OCV holding) process, which accelerates the evaluation of the electrochemical durability of the PEMFC membrane. In this study, an empirical formula using the experimental data of three MEAs with different durability was created and compared. The durability evaluation time of the reinforced membrane MEA without radical scavenger inside the membrane was 383 h, and the durability evaluation time of the reinforced membrane MEA with radical scavenger inside the membrane was 1,000 and 1,650 h, respectively. The degradation of the membrane was divided into the reversible degradation that can be recovered by activation and the irreversible degradation that is not recovered. The irreversible degradation of the membrane was indicated by an increase in hydrogen permeability, and the change in hydrogen permeability was similar to the irreversible degradation constant c of all three MEAs. The initiation of irreversible deterioration without recovery is indicated by an increase in hydrogen permeability, and the OCV is not recovered due to an increase in hydrogen permeability, so the slope of the OCV recovery line (ORL) decreases, which can be confirmed by an increase in the constant c value of the empirical formula.

Durability of MEA Using sPEEK Membrane Reinforced with Poly Imide in PEMFC (고분자전해질연료전지에서 폴리이미드 강화 sPEEK막 MEA의 내구성)

  • Lee, Hye-Ri;Na, Il-Chai;Oh, Sung-Jun;Park, Kwon-Pil
    • Korean Chemical Engineering Research
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    • v.55 no.3
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    • pp.296-301
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    • 2017
  • Recently, there are many efforts focused on development of more economical non-fluorinated membranes for PEMFCs (Proton Exchange Membrane Fuel Cells). In this study, sulfonated poly (ether ether ketone) (sPEEK) membrane reinforced with poly imide was made to enhance of membrane durability. In order to test durability of single (un-reinforced) membrane and reinforced membrane MEA (Membrane and Electrode Assembly), degradation accelerated stress test was used. Before and after degradation, I-V polarization curve, hydrogen crossover current, electrochemical surface area, membrane resistance and charge transfer resistance were measured. As a result of experiments, hydrogen crossover current of reinforced MEA was lower than that of single MEA, therefor durability of reinforced MEA was higher than that of single MEA. There was not especially short phenomena in reinforced MEA after degradation accelerated stress test.

Electrochromic Properties of Li+-Modified Prussian Blue (리튬이온이 첨가된 프루시안 블루의 전기변색 특성 연구)

  • Yoo, Sung-Jong;Lim, Ju-Wan;Park, Sun-Ha;Won, Ho-Youn;Sung, Yung-Eun
    • Journal of the Korean Electrochemical Society
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    • v.10 no.2
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    • pp.126-131
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    • 2007
  • The durability problem of Prussian blue in non-aqueous $Li_+$-based electrolytes has been due to the degradation of the Prussian blue electrode matrix during the insertion/extraction processes by $Li_+$. In this work, we designed and synthesised the Prussian blue without reducing the electrochromic performance in non-aqueous $Li_+$-based electrolytes. Prussian blue was electrodeposited on a glass which has ITO coating, and the coating solution is a mixture solution of $FeCl_3\;and\;K_3Fe(CN)_6$ with deionized water added HCl, KCl, and LiCl, respectively. The durability of Prussian blue was evaluated by an in-situ transmittance measurement during a continuous and pulse potential cycling test, and measured by electroactive layer thickness due to evaluating the degradation.

Performance Degradation of Dead-end Type PEMFC by Startup and Shutdown Cycles (시동/정지 반복에 의한 데드엔드형 고분자전해질 연료전지의 성능 감소)

  • Jeong, Jaehyeun;Jeong, Jaejin;Song, Myunghyun;Chung, Hoibum;Na, Ilchai;Lee, Ho;Park, Kwonpil
    • Korean Chemical Engineering Research
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    • v.51 no.5
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    • pp.540-544
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    • 2013
  • During start up and shut down of a proton exchange membrane fuel cells (PEMFC), the performance and lifetime of PEMFC were reduced. In this study, effect of startup and shutdown were investigated in dead-end type PEMFC using oxygen as a cathode gas with polarization curve, impedance spectroscopy (EIS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Dummy load which eliminates residual hydrogen and oxygen during startup and shutdown operation should be applied to mitigated the degradation of PEMFC performance. At 50% relative humidity (RH) under the repetitive on/off cycling, the cell performance decayed faster than at 100% RH because of corrosion of the cathode carbon support. Water suppling into cell reduced the degradation rate of dead-end type PEMFC during start up and shut down cycling at 50% RH.

Electrochemical Detection of Hydroxychloroquine Sulphate Drug using CuO/GO Nanocomposite Modified Carbon Paste Electrode and its Photocatalytic Degradation

  • G. S. Shaila;Dinesh Patil;Naeemakhtar Momin;J. Manjanna
    • Journal of the Korean Electrochemical Society
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    • v.27 no.1
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    • pp.15-31
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    • 2024
  • The antimalarial drug hydroxychloroquine sulphate (HCQ) has taken much attention during the first COVID-19 pandemic phase for the treatment of severe acute respiratory infection (SARI) patients. Hence it is interest to study the electrochemical properties and photocatalytic degradation of the HCQ drug. Copper oxide (CuO) nanoparticles, graphene oxide (GO) and CuO/GO NC (nanocomposite) modified carbon paste electrodes (MCPE) are used for the detection of HCQ in an aqueous medium. Electrochemical behaviour of HCQ (20 μM) was observed using CuO/MCPE, GO/MCPE and CuO/GO NC/MCPE in 0.1 M phosphate buffer at pH 7 with a scan rate of 20 to 120 mV s-1 by cyclic voltammetry (CV). Differential pulse voltammetry (DPV) of HCQ was performed for 0.6 to 16 μM HCQ. The CuO/GO NC/MCPE showed a reasonably good sensitivity of 0.33 to 0.44 μA μM cm-2 with LOD of 69 to 92 nM for HCQ. Furthermore, the CuO/GO NC was used as a catalyst for the photodegradation of HCQ by monitoring its UV-Vis absorption spectra. About 98% was degraded in about 34 min under visible light and after 4 cycles it was 87%. The improved photocatalytic activity may be attributed to decrease in bandgap energy and enhanced ability for the electrons to migrate. Thus, CuO/GO NC showed good results for both sensing and degradation applications as well as reproducibility.

Effect of Firing Temperature on Microstructure and the Electrical Properties of a ZnO-based Multilayered Chip Type Varistor(MLV) (소성온도에 따른 ZnO계 적층형 칩 바리스터의 미세구조와 전기적 특성의 변화)

  • Kim, Chul-Hong;Kim, Jin-Ho
    • Journal of the Korean Ceramic Society
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    • v.39 no.3
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    • pp.286-293
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    • 2002
  • Microstructure and the electrical porperties of a ZnO-based multilayered chip-type varistor(abbreviated as MLV) with Ag/Pd(7:3) inner electrode have been studied as a function of firing of temperature. At 1100$^{\circ}$C, inner electrode layers began to show nonuniform thickness and small voids, which resulted in significant disappearance of the electrode pattern and delamination at 1100$^{\circ}$C. MLVs fired at 950$^{\circ}$C showed large degradation in leakage current, probably due to incomplete redistribution of liquid and transition metal elements in pyrochlore phase decomposition. Those fired at 1100$^{\circ}$C and above, on the other hand, revealed poor varistor characteristics and their reproductibility, which are though to stem from the deformation of inner electrode pattern, the reaction between electrode materials and ZnO-based ceramics, and the volatilization of $Bi_2O_3$. Throughout the firing temperature range of 950∼1100$^{\circ}$C, capacitance and leakage current increased while breakdown voltage and peak current decreased with the increase of firing temperature, but nonlinear coefficient and clamping ratio kept almost constant at ∼30 and 1.4, respectively. In particular, those fired between 1000$^{\circ}$C and 1050$^{\circ}$C showed stable varistor characteristics with high reproducibility. It seems that Ag/Pd(7:3) alloy is one of the electrode materials applicable to most ZnO-based MLVs incorporating with $Bi_2O_3$ when cofired up to 1050$^{\circ}$C.

Effect of RuO$_2$ Thin Film Microstructure on Characteristics of Thin Film Micro-supercapacitor ($RuO_2$박막의 미세 구조가 박막형 마이크로 슈퍼캐패시터의 특성에 미치는 영향)

  • Kim, Han-Ki;Yoon, Young-Soo;Lim, Jae-Hong;Cho, Won-Il;Seong, Tae-Yeon;Shin, Young-Hwa
    • Korean Journal of Materials Research
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    • v.11 no.8
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    • pp.671-678
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    • 2001
  • All solid-state thin film micro supercapacitor, which consists of $RuO_2$/LiPON/$RuO_2$ multi layer structure, was fabricated on Pt/Ti/Si substrate using a $RuO_2$ electrode. Bottom $RuO_2$ electrode was grown by dc reactive sputtering system with increasing $O_2/[Ar+O_2]$ ratio at room temperature, and a LiPON electrolyte film was subsequently deposited on the bottom $RuO_2$ electrode at pure nitrogen ambient by rf reactive sputtering system. Room temperature charge-discharge measurements based on a symmetric $RuO_2$/LiPON/$RuO_2$ structure clearly demonstrates the cyclibility dependence on the microstructure of the $RuO_2$ electrode. Using both glancing angle x-ray diffraction (GXRD) and transmission electron microscopy (TEM) analysis, it was found that the microstructure of the $RuO_2$ electrode was dependent on the oxygen flow ratio. In addition, x- ray photoelectron spectroscopy(XPS) examination shows that the Ru-O binding energy is affected by increasing oxygen flow ratio. Furthermore, TEM and AES depth profile analysis after cycling demonstrates that the interface layer formed by interfacial reaction between LiPON and $RuO_2$ act as a main factor in the degradation of the cyclibility of the thin film micro-supercapacitor.

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Discharge Luminous Phenomena Caused Between ZnO Surge Arrester Block and Electrodes (산화아연 피뢰기 소자와 전극사이에 발생하는 방전광 현상)

  • Lee, Bok-Hee;Park, Keon-Young;Kang, Sung-Man
    • Journal of the Korean Institute of Illuminating and Electrical Installation Engineers
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    • v.19 no.3
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    • pp.44-50
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    • 2005
  • This paper deals with the characteristics and reduction methods of the plasma luminosity caused between the ZnO surge arrester block and metal electrodes. In this study, the impulse current generator that can generate $8/20[{\mu}s]$ impulse currents with a peak short-circuit of 10[kA] is designed and fabricated. Plasma luminosity phenomena for fine and used ZnO blocks were observed as a function of the contact states between the ZnO block and electrodes and the polarity of applied impulse voltages. As a result, discharge luminous events are produced near the contact edges between the ZnO block and metal electrodes. The discharge plasma luminosity between the ZnO surge arrester block and low potential electrode is more intensive than that between the ZnO surge arrester block and high potential electrode. Surface flashover of ZnO blocks are mainly caused by plasma generation near the edge of metal electrode. Also, plasma luminosity for the fine ZnO blocks is less than that for the used ZnO blocks. Plasma luminosity at the contact of the ZnO block and ring-type electrode is more intensive than that at the contact of ZnO block and disk electrode. It is desirable to use the disk electrode with the proper contact area to reduce the plasma luminosity caused at the contact point between the ZnO block and electrodes.

Generation of Chemically Active Species in Hybrid Gas-Liquid Discharges (기체-액체 혼합 방전에 의한 화학적 활성종 생성 특성)

  • Chung, Jae-Woo;Locke, Bruce R.
    • Journal of Korean Society of Environmental Engineers
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    • v.29 no.5
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    • pp.556-563
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    • 2007
  • We carried out a laboratory scale experiment about the characteristics of chemically active species produced in hybrid gas-liquid discharges. The electrode configuration which had high voltage electrode in the gas phase and ground electrode in the liquid was utilized while high voltage electrode has been typically positioned in the liquid in other studies. Our electrode was configured in such a way as to increase the energy efficiency of chemical reactions by creating a higher electrical field strength and a narrower pulse width than the typical electrode configuration. The highest ozone concentration was obtained at 45 kV which was the medium value in operating voltages. The decrease of solution conductivity increased the resistance of liquid phase and the electric field strength through the gas phase, so ozone gene-ration rate was enhanced. The increase of voltage promoted the production rate of hydrogen peroxide by increasing the electric field strength. In a lower voltage, the increase of solution conductivity increased the degradation rate of $H_2O_2$, so the $H_2O_2$ generation rate decreased. On the other hand, the effects of UV radiation, shock waves etc. increased the $H_2O_2$ generation rate as the solution conductivity increased. A higher rate of $H_2O_2$ generation can be achieved by mixing argon to oxygen which generates a stronger and more stable discharges.