• Journal of Electrochemical Science and Technology
• /
• v.12 no.1
• /
• pp.126-136
• /
• 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
• /
• v.9 no.3
• /
• pp.176-183
• /
• 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
• /
• v.11 no.4
• /
• pp.411-420
• /
• 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.

• Transactions of the Korean hydrogen and new energy society
• /
• v.33 no.6
• /
• pp.803-807
• /
• 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.

• Journal of Sensor Science and Technology
• /
• v.32 no.5
• /
• pp.290-294
• /
• 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
• /
• v.19 no.5
• /
• pp.413-418
• /
• 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
• /
• v.13 no.spc1
• /
• pp.110-113
• /
• 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
• /
• v.55 no.1
• /
• pp.107-114
• /
• 2017

The performance of polymer electrolyte membrane fuel cell (PEMFC) could be deteriorated when fuel contains contaminants such as carbon monoxide (CO) or hydrogen sulfide ($H_2S$). Generally, $H_2S$ is introduced in hydrogen by steam reforming of hydrocarbon which has mercaptan as odorant. $H_2S$ poisoning effect on PEMFC performance was examined on this study. Pure hydrogen injection, voltage cycling and water circulation methods were compared as performance recovery methods. The PEMFC performance was analyzed using electrochemical methods such as polarization curve, electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). Pure hydrogen injection and voltage cycling methods showed low recovery ratio, however, water circulation method showed high recovery ratio over 95%. Because anode was directly poisoned by $H_2S$, anode water circulation showed higher recovery ratio compared to the other methods. Water circulation method was developed to recover PEMFC performance from $H_2S$ poisoning. This method could contribute to PEMFC durability and commercialization.

• Transactions of the Korean hydrogen and new energy society
• /
• v.16 no.2
• /
• pp.103-110
• /
• 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.

• Journal of the Korean Applied Science and Technology
• /
• v.29 no.4
• /
• pp.594-598
• /
• 2012

Polymer electrolyte membrane fuel cell(PEMFC) performance degrades seriously when sulfur dioxide and hydrogen sulfide are contaminated in the fuel gas at anode and air source at cathode, respectively. This paper reveals the effect of the combined sulfur impurity poisoning on both PEMFC cathode and anode parts through measuring electrical performance on single FC operated under 1 ppm to 10 ppm impurity gases. The severity of $SO_2$ and $H_2S$ poisoning depended on concentrations of impurity gases under optimum operating conditions($65^{\circ}C$ of cell temperature and 100 % relative humidity). Sulfur adsorption occured on the surface of Pt catalyst layer on MEA. In addition, MEA poisoning by impurity gases were cumulative. After four consecutive poisonings with 1, 3, 5 to 10 ppm, the fuel cell performance of PEMFC was decrease upto 0.54 V(76 %) from 0.71 V.