• Journal of Electrochemical Science and Technology
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• 제12권1호
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• pp.126-136
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• 2021

The electrochemical performance of all-solid-state cells (ASSCs) based on sulfide electrolytes is critically affected by the undesirable interfacial reactions between oxide cathodes and sulfide electrolytes because of the high reactivity of sulfide electrolytes. Based on the concept that the interfacial reactions are highly dependent on the type of sulfide electrolyte, the electrochemical properties of the ASSCs prepared using three types of sulfide electrolytes were observed and compared. The Li2MoO4-LiI coating layer was also introduced to suppress the interfacial reactions. The cells using argyrodite electrolyte exhibited a higher capacity and Coulombic efficiency than the cells using 75Li2S-22P2S5-3Li2SO4 and Li7P3S11 electrolytes, indicating that the argyrodite electrolyte is less reactive with cathodes than other electrolytes. Moreover, the introduction of Li2MoO4-LiI coating on the cathode surface significantly enhanced the electrochemical performance of ASSCs because of the protection of coating layer. Pulverization of argyrodite electrolyte is also effective in increasing the capacity of cells because the smaller size of electrolyte particles improved the contact stability between the cathode and the sulfide electrolyte. The cyclic performance of cells was also enhanced by pulverized electrolyte, which is also associated with improved contact stability at the cathode/electrolyte. These results show that the introduction of Li2MoO4-LiI coating and the use of pulverized sulfide electrolyte can exhibit a synergic effect of suppressed interfacial reaction by the coating layer and improved contact stability owing to the small particle size of electrolyte.

• Journal of Electrochemical Science and Technology
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• 제9권3호
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• pp.176-183
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• 2018

In this study, a $Li_2ZrO_3$ coated $Li[Ni_{0.8}Co_{0.15}Al_{0.05}]O_2$ (NCA) cathode was applied to an all-solid-state cell employing a sulfide-based solid electrolyte. Sulfide-based solid electrolytes are preferable for all-solid-state cells because of their high ionic conductivity and good softness and elasticity. However, sulfides are very reactive with oxide cathodes, and this reduces the stability of the cathode/electrolyte interface of all-solid-state cells. $Li_2ZrO_3$ is expected to be a suitable coating material for the cathode because it can suppress the undesirable reactions at the cathode/sulfide electrolyte interface because of its good stability and high ionic conductivity. Cells employing $Li_2ZrO_3$ coated NCA showed superior capacity to those employing pristine NCA. Analysis by X-ray photoelectron spectroscopy and electron energy loss spectroscopy confirmed that the $Li_2ZrO_3$ coating layer suppresses the propagation of S and P into the cathode and the reaction between the cathode and the sulfide solid electrolyte. These results show that $Li_2ZrO_3$ coating is promising for reducing undesirable side reactions at the cathode/electrolyte interface of all-solid-state-cells.

• Journal of Electrochemical Science and Technology
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• 제11권4호
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• pp.411-420
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• 2020

Undesirable interfacial reactions between the cathode and sulfide electrolyte deteriorate the electrochemical performance of all-solid-state cells based on sulfides, presenting a major challenge. Surface modification of cathodes using stable materials has been used as a method for reducing interfacial reactions. In this work, a precursor-based surface modification method using Zr and Mo was applied to a LiNi_0.6Co_0.2Mn_0.2O₂ cathode to enhance the interfacial stability between the cathode and sulfide electrolyte. The source ions (Zr and Mo) coated on the precursor-surface diffused into the structure during the heating process, and influenced the structural parameters. This indicated that the coating ions acted as dopants. They also formed a homogenous coating layer, which are expected to be layers of Li-Zr-O or Li-Mo-O, on the surface of the cathode. The composite electrodes containing the surface-modified LiNi_0.6Co_0.2Mn_0.2O₂ powders exhibited enhanced electrochemical properties. The impedance value of the cells and the formation of undesirable reaction products on the electrodes were also decreased due to surface modification. These results indicate that the precursor-based surface modification using Zr and Mo is an effective method for suppressing side reactions at the cathode/sulfide electrolyte interface.

• 한국수소및신에너지학회논문집
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• 제33권6호
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• pp.803-807
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• 2022

In this study, the battery performance change according to the change of electrolyte flow rate. With increase of electrolyte flow rate the energy efficiency showed tendency of decrease. The electrochemical impedance spectroscopy results showed the increased resistance.

• 센서학회지
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• 제32권5호
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• pp.290-294
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• 2023

Among various types of harmful gases, hydrogen sulfide is a strong toxic gas that is mainly generated during spillage and wastewater treatment at industrial sites. Hydrogen sulfide can irritate the conjunctiva even at low concentrations of less than 10 ppm, cause coughing, paralysis of smell and respiratory failure at a concentration of 100 ppm, and coma and permanent brain loss at concentrations above 1000 ppm. Therefore, rapid detection of hydrogen sulfide among harmful gases is extremely important for our safety, health, and comfortable living environment. Most hydrogen sulfide gas sensors that have been reported are electrical resistive metal oxide-based semiconductor gas sensors that are easy to manufacture and mass-produce and have the advantage of high sensitivity; however, they have low gas selectivity. In contrast, the electrochemical sensor measures the concentration of hydrogen sulfide using an electrochemical reaction between hydrogen sulfide, an electrode, and an electrolyte. Electrochemical sensors have various advantages, including sensitivity, selectivity, fast response time, and the ability to measure room temperature. However, most electrochemical hydrogen sulfide gas sensors depend on imports. Although domestic technologies and products exist, more research is required on their long-term stability and reliability. Therefore, this study includes the processes from electrode material synthesis to sensor fabrication and characteristic evaluation, and introduces the sensor structure design and material selection to improve the sensitivity and selectivity of the sensor. A sensor case was fabricated using a 3D printer, and an Ag reference electrode, and a Pt counter electrode were deposited and applied to a Polytetrafluoroethylene (PTFE) filter using PVD. The working electrode was also deposited on a PTFE filter using vacuum filtration, and an electrochemical hydrogen sulfide gas sensor capable of measuring concentrations as low as 0.6 ppm was developed.

• Journal of Ceramic Processing Research
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• 제19권5호
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• pp.413-418
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• 2018

All-solid-state lithium batteries (ASSBs) using inorganic sulfide-based solid electrolytes are considered prospective alternatives to existing liquid electrolyte-based batteries owing to benefits such as non-flammability. However, it is difficult to form a favorable solid-solid interface among electrode constituents because all the constituents are solid particles. It is important to form an effective electron conduction network in composite cathode while increasing utilization of active materials and not blocking the lithium ion path, resulting in excellent cell performance. In this study, a mixture of fibrous VGCF and spherical nano-sized Super P was used to improve rate performance by fabricating valid conduction paths in composite cathodes. Then, composite cathodes of ASSBs containing 70% and 80% active materials ($LiNi_{0.6}Co_{0.2}Mn_{0.2}O_2$) were prepared by a solution-based process to achieve uniform dispersion of the electrode components in the slurry. We investigated the influence of binary carbon additives in the cathode of all-solid-state batteries to improve rate performance by constructing an effective electron conduction network.

• Journal of Ceramic Processing Research
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• 제13권spc1호
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• pp.110-113
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• 2012

Ge-S and Li-Ge-S powders were synthesized via solution-based process in order to employ chalcogenide-based solid electrolyte for use in Li secondary batteries. GeCl4 and thioacetamide in combination result in Ge-S powders of which major crystalline phase becomes GeS2 where the tetragonal and orthorhombic phases coexist after heat treatment. A chemical treatment using NaOH brings about the reduction of chlorine in the powders obtained. However, the heat treatment at 300 ℃ is more effective in minimizing the chlorine content. When lithium chloride is used as the precursor of Li ions, the LiCl powders are agglomerated with an inhomogeneous distribution. When Li2S is used, the Li-Ge-S powders are distributed more uniformly and the orthorhombic GeS2 phase dominates in the powders.

• Korean Chemical Engineering Research
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• 제55권1호
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• pp.107-114
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• 2017

고분자전해질 연료전지(PEMFC: polymer electrolyte membrane fuel cell)는 일산화탄소(CO)나 황화수소($H_2S$)가 포함된 연료가 주입될 경우 성능이 저하된다. 일반적으로 멀캅탄 계열의 부취제가 첨가된 탄화수소를 개질하여 생성된 수소에는 미량의 황화수소가 포함되어 있다. 본 연구에서는 황화수소를 수소에 첨가하여 anode에 주입하였을 경우에 연료전지 성능에 미치는 영향을 파악하고, 3가지 다른 회복방법인 순수 수소 주입법, 전위 순환법과 물 순환법을 적용한 경우의 회복률을 비교하여 보았다. PEMFC의 성능은 전기화학적 방법인 polarization curve, electrochemical impedance spectroscopy (EIS)와 cyclic voltammetry (CV)를 사용하여 분석하였다. 피독에 대한 회복방법인 순수 수소 주입법과 전위 순환법을 사용한 경우에는 회복률이 적었고, 물 순환법을 사용한 경우에는 초기에 대비하여 약 95% 이상 성능이 회복된 것을 확인하였다. 직접적으로 피독에 노출된 anode에 물을 흘린 경우의 성능회복률이 높았으며, cathode에 흘린 경우에도 물의 crossover에 의한 효과로 전위 순환법보다 우수한 회복률을 보였다. 이러한 연구결과로부터 황화수소 피독에 대한 회복기법을 구축함으로서 연료전지의 내구성을 향상시킬 수 있고, 불순물이 미량 함유된 저가 수소의 사용을 가능하게 함으로서 연료전지 보급에도 기여할 수 있을 것이다.

• 한국수소및신에너지학회논문집
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• 제16권2호
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• pp.103-110
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• 2005

Proton conducting solid polymer electrolyte (SPE) membranes have been used in many energy technological applications such as water electolysis, fuel cells, redox-flow battery, and other electrochemical devices. The availability of stable membranes with good electrochemical characteristics as proton conductivity at high temperatures above 80 $^{\circ}C$ and low cost are very important for its applications. However, the presently available perfluorinated ionomers are not applicable because of high manufacturing cost and high temperature use to the decrease in the proton conductivity and mechanical strength. In order to make up for the weak points, the block copolymer (BPSf) of polysulfone and poly (phenylene sulfide sulfone) were synthesized and sulfonated. The electrolyte membranes were prepared with phosphotungstic acid (HPA)/sulfonated BPSf via solution blending. This study would be desirable to investigate the interaction between the HPA and sulfonated polysulfone. The results showed that the characteristics of SPSf/HPA blend membrane was a better than Nafion at high temperature, 100 $^{\circ}C$. These membranes proved to have a high proton conductivity, $6.29{\times}10-2$ S/cm, a water content, 23.9%, and a ion exchange capacity, 1.97 meq./g dry membrane. Moreover, some of the membranes kept their high thermal and mechanical stability.

• 한국응용과학기술학회지
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• 제29권4호
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• pp.594-598
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• 2012

고분자 전해질막 연료전지는 연료극의 연료와 공기극의 공기에 각각 $H_2S$와 $SO_2$이 포함되어 있을 때 그 성능이 심각하게 감소한다. 본 연구는 고분자전해질막 연료전지의 공기극과 연료극에 1 ppm에서 10 ppm의 불순물 가스를 공급하여 전기적 성능측정을 통해 복합적인 황불순물이 단위전지에 미치는 영향을 확인하였다. 최적의 운전조건에서 불순물가스를 피독하였을 때 $SO_2$와 $H_2S$의 농도가 증가할수록 성능이 급격히 감소하였다(단위전지 온도 $65^{\circ}C$, 상대습도 100%). 그리고 황의 흡착은 MEA의 백금 촉매층 표면서 일어나며, 불순물 가스가 MEA에 누적되는 것을 확인하였다. 1, 3, 5, 및 10 ppm 4회의 연속적인 피독 후 연료전지의 성능이 0.71 V에서 0.54 V(76 %)로 감소하였다.