• Korean Journal of Materials Research
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• v.34 no.4
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• pp.208-214
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• 2024

To fabricate intermetallic nanoparticles with high oxygen reduction reaction activity, a high-temperature heat treatment of 700 to 1,000 ℃ is required. This heat treatment provides energy sufficient to induce an atomic rearrangement inside the alloy nanoparticles, increasing the mobility of particles, making them structurally unstable and causing a sintering phenomenon where they agglomerate together naturally. These problems cannot be avoided using a typical heat treatment process that only controls the gas atmosphere and temperature. In this study, as a strategy to overcome the limitations of the existing heat treatment process for the fabrication of intermetallic nanoparticles, we propose an interesting approach, to design a catalyst material structure for heat treatment rather than the process itself. In particular, we introduce a technology that first creates an intermetallic compound structure through a primary high-temperature heat treatment using random alloy particles coated with a carbon shell, and then establishes catalytic active sites by etching the carbon shell using a secondary heat treatment process. By using a carbon shell as a template, nanoparticles with an intermetallic structure can be kept very small while effectively controlling the catalytically active area, thereby creating an optimal alloy catalyst structure for fuel cells.

• Korean Chemical Engineering Research
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• v.53 no.1
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• pp.11-15
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• 2015

Sodium borohydride, $NaBH_4$, shows a number of advantages as hydrogen source for portable proton exchange membrane fuel cells(PEMFCs). Properties of $NaBH_4$ hydrolysis reaction using unsupported Co-B, Co-P-B catalyst were studied. BET surface area of catalyst, yield of hydrogen, effect of $NaBH_4$ concentration and durability of catalyst were measured. The BET surface area of unsupported Co-B catalyst was $75.7m^2/g$ and this value was 18 times higher than that of FeCrAlloy supported Co-B catalyst. The hydrogen yield of $NaBH_4$ hydrolysis reaction by unsupported catalysts using 20~25 wt% $NaBH_4$ solution was 97.6~98.5% in batch reactor. The hydrogen yield decrease to 95.3~97.0% as the concentration of $NaBH_4$ solution increase to 30 wt%. The loss of unsupported catalyst was less than that of FeCrAlloy supported catalyst during $NaBH_4$ hydrolysis reaction and the loss increased with increasing of $NaBH_4$ concentration. In continuous reactor, hydrogen yield of $NaBH_4$ hydrolysis was 90% using 1.2 g of unsupported Co-P-B catalyst with $3{\ell}/min$ hydrogen generation rate.

• Korean Chemical Engineering Research
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• v.56 no.5
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• pp.641-646
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• 2018

Sodium borohydride, $NaBH_4$, shows a number of advantages as hydrogen source for portable proton exchange membrane fuel cells (PEMFCs). Properties of $NaBH_4$ hydrolysis reaction using activated carbon supported Co-B/C, Co-P-B/C catalyst were studied. BET surface area of catalyst, yield of hydrogen, effect of $NaBH_4$ concentration and durability of catalyst were measured. The BET surface area of carbon supported catalyst was over $500m^2/g$ and this value was 2~3 times higher than that of unsupported catalyst. Hydrogen generation of activated carbon supported catalyst was more stable than that of unsupported catalyst. The activation energy of Co-P-B/C catalyst was 59.4 kJ/mol in 20 wt% $NaBH_4$ and 14% lower than that of Co-P-B/FeCrAlloy catalyst. Catalyst loss on activated carbon supported catalyst was reduced to about 1/3~1/2 compared with unsupported catalyst, therefore durability was improved by supporting catalyst on activated carbon.

• Korean Chemical Engineering Research
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• v.57 no.6
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• pp.758-762
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• 2019

Sodium borohydride,$NaBH_4$, has many advantages as hydrogen source for portable proton exchange membrane fuel cells (PEMFC). When PEMFC is used for marine use, $NaBH_4$ hydrolysis using seawater is economical. Therefore, in this study, hydrogen was generated by using seawater instead of distilled water in the process of hydrolysis of $NaBH_4$. Properties of $NaBH_4$ hydrolysis reaction using activated carbon supported Co-B/C catalyst were studied. The yield of hydrogen decreased as $NaBH_4$ concentration and NaOH concentration were increased during $NaBH_4$ hydrolysis using sea water. At higher concentrations of $NaBH_4$ and NaOH, byproducts adhered to the surface of the catalyst after hydrolysis reaction using sea water, reduced hydrogen yield compared to distilled water. The activation energy of $NaBH_4$ hydrolysis is 59.3, 74.4 kJ/mol for distilled water and sea water, respectively. In order to increase the hydrogen generation rate in seawater as high as distilled water, the reaction temperature has to be increased by $80^{\circ}C$ or more.

• Korean Chemical Engineering Research
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• v.61 no.1
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• pp.58-61
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• 2023

The activation process is essential for PEMFC to improve initial performance. The most commonly used activation method is a voltage change (load change) method, which may accompany degradation of the electrode catalyst if excessively performed. In many activation processes, the voltage change range is activated in a wide range from 0.4 V to OCV, and research is needed to reduce the voltage change range in order to prevent electrode catalyst degradation and shorten the activation time. Therefore, in this study, when the activation voltage range was 0.4~0.6 V, 0.4~0.8 V, and 0.4~OCV, we tried to research and develop an effective activation method by analyzing the performance and characteristics of the electrode and polymer membrane. The performance improvement was the lowest in the activation with a wide voltage range from 0.4 V to the highest OCV, and the performance decreased by 10% when activated for 56 cycles. The 0.4~0.6 V activation cycle showed the highest performance improvement up to 20% and the smallest decrease in performance due to overactivation, indicating that it is optimal method.

• Korean Chemical Engineering Research
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• v.61 no.4
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• pp.517-522
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• 2023

A chemical/mechanical durability test of polymer membrane evaluation method is used in which air and hydrogen are supplied to the proton exchange membrane fuel cell (PEMFC) and wet/dry is repeated in the open circuit voltage (OCV) state. In this protocol, when wet/dry is repeated, voltage increase/decrease is repeated, resulting in electrode degradation. When the membrane durability is excellent, the number of voltage changes increases and the evaluation is terminated due to electrode degradation, which may cause a problem that the original purpose of membrane durability evaluation cannot be performed. In this study, the same protocol as the department of energy (DOE) was used, but oxygen was used instead of air as the cathode gas, and the wet/dry time and flow rate were also increased to increase the chemical/mechanical degradation rate of the membrane, thereby shortening the durability evaluation time of the membrane to improve these problems. The durability test of the Nafion 211 membrane electrode assembly (MEA) was completed after 2,300 cycles by increasing the acceleration by 2.6 times using oxygen instead of air. This protocol also accelerated degradation of the membrane and accelerated degradation of the electrode catalyst, which also had the advantage of simultaneously evaluating the durability of the membrane and the electrode.

• Korean Chemical Engineering Research
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• v.62 no.1
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• pp.7-12
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• 2024

The durability of the catalyst support has a significant effect on the durability of proton exchange membrane fuel cells (PEMFC). The accelerated durability evaluation of the catalyst support is performed at a high voltage (1.0 to 1.5 V), and the catalyst and ionomer binder in the catalyst layer are also deteriorated, hindering the evaluation of the durability of the support. The existing protocol (DOE protocol) was improved to find conditions in which the support, which is a durability evaluation target, deteriorates further. A protocol (MDOE) was developed in which the relative humidity was lowered by 35% and the number of voltage changes was reduced. After repeating the 1.0 ↔ 1.5 V voltage change cycle, the catalyst mass activitiy (MA), electrochemical active area (ECSA), electrical double layer capacity (DLC), Pt dissolution and particle growth were analyzed. Reaching 40% reduction in mass activity, the MDOE protocol took only 500 cycles, reducing the number of voltage changes compared to the DOE method and increasing the degradation of the carbon support by 50% compared to the DOE protocol.

• Korean Chemical Engineering Research
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• v.61 no.1
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• pp.45-51
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• 2023

In order to improve the durability of the PEMFC(Proton Exchange Membrane Fuel Cells) polymer membrane, a radical scavenger and a support are used. In this study, the durability of membranes containing fucoidan extracted from seaweeds and tannic acid serving as a crosslinking agent is evaluated to improve chemical and physical durability. Physical durability is evaluated by measuring tensile strength, and chemical durability is measured by Fenton experiment. Membrane and electrode assembly (MEA) is prepared and mechanical and chemical durability are measured through accelerated durability evaluation in the cell. The tensile strength measurement showed that fucoidan and tannic acid can improve the mechanical durability of the membrane by improving the strain rate and yield strength. It is shown in Fenton experiment that fucoidan acts as a radical scavenger. As a result of the accelerated durability test in the unit cell, fucoidan improved both chemical and mechanical durability, increasing the accelerated durability evaluation time by 38.1% compared to the additive-free membrane. When tannic acid is added, the durability of the polymer membrane is improved by 13.9% by improving the mechanical durability.

• Membrane Journal
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• v.17 no.4
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• pp.294-301
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• 2007

To improve oxidative stability of non-fluorinated styrene-based polymer electrolyte membranes, copolymerized membranes were prepared using styrene derivatives such as p-methylstyrene, t-butylstyrene, and ${\alpha}-methylstyrene$ by monomer sorption method. Prepared membrane was characterized by measurement of weight gain ratio, water content, ion-exchange capacity, proton conductivity, and oxidative stability under the accelerated condition. It was found that each step of monomer sorption method including sorption, polymerization and sulfonation could be affected by the properties and the structures of styrenederivatives. Due to difficulty of polymerization, ${\alpha}$-methylstyrene was copolymerized with styrene or p-methylstyrene. Prepared membrane using ${\alpha}-methylstyrene$ and styrene showed higher performance and stability comparing to copolymerized membrane with styrene. However, copolymerized membranes with ${\alpha}-methylstyrene$ did not showed much improved oxidative stability comparing to styrene membrane due to their lower molecular weight. The t-butylstyrene membrane showed a low performance due to substituted bulky-butyl group which prevents sorption and sulfonation reaction. However, copolymerized t-butylstyrene membranes with p-methylstyrene showed good performance and much improved stability than the styrene membranes.

• Korean Chemical Engineering Research
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• v.61 no.3
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• pp.356-361
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• 2023

In order to improve the durability of the proton exchange membrane fuel cell (PEMFC), it is important to accurately evaluate the durability of the polymer membrane in a short time. The test conditions for chemically accelerated durability evaluation of membranes are high voltage, high temperature, low humidity, and high gas pressure. It can be said that the protocol is developed by changing these conditions. However, the relative influence of each test condition on the degradation of the membrane has not been studied. In chemical accelerated degradation experiment of the membrane, the influence of 4 factors (conditions) was examined through the factor experiment method. The degree of degradation of the membrane after accelerated degradation was determined by measuring the hydrogen permeability and effluent fluoride ion concentration, and it was possible to determine the degradation order of the polymer membrane under 8 conditions by the difference in fluoride ion concentration. It was shown that the influence of the membrane degradation factor was in the order of voltage > temperature > oxygen pressure > humidity. It was confirmed that the degradation of the electrode catalyst had an effect on the chemical degradation of the membrane.