Practical Challenges Associated with Catalyst Development for the Commercialization of Li-air Batteries

Park, Myounggu,Kim, Ka Young,Seo, Hyeryun,Cheon, Young Eun,Koh, Jae Hyun,Sun, Heeyoung,Kim, Tae Jin The Korean Electrochemical Society 2014 Journal of electrochemical science and technology Vol.5 No.1

Li-air cell is an exotic type of energy storage and conversion device considered to be half battery and half fuel cell. Its successful commercialization highly depends on the timely development of key components. Among these key components, the catalyst (i.e., the core portion of the air electrode) is of critical importance and of the upmost priority. Indeed, it is expected that these catalysts will have a direct and dramatic impact on the Li-air cell's performance by reducing overpotentials, as well as by enhancing the overall capacity and cycle life of Li-air cells. Unfortunately, the technological advancement related to catalysts is sluggish at present. Based on the insights gained from this review, this sluggishness is due to challenges in both the commercialization of the catalyst, and the fundamental studies pertaining to its development. Challenges in the commercialization of the catalyst can be summarized as 1) the identification of superior materials for Li-air cell catalysts, 2) the development of fundamental, material-based assessments for potential catalyst materials, 3) the achievement of a reduction in both cost and time concerning the design of the Li-air cell catalysts. As for the challenges concerning the fundamental studies of Li-air cell catalysts, they are 1) the development of experimental techniques for determining both the nano and micro structure of catalysts, 2) the attainment of both repeatable and verifiable experimental characteristics of catalyst degradation, 3) the development of the predictive capability pertaining to the performance of the catalyst using fundamental material properties. Therefore, under the current circumstances, it is going to be an extremely daunting task to develop appropriate catalysts for the commercialization of Li-air batteries; at least within the foreseeable future. Regardless, nano materials are expected to play a crucial role in this field.

폐 RHDS 촉매재생 후 메탈 코로게이트 지지체상에서 워시코팅에 의한 NOx 저감 SCR 촉매에 관한 연구

나우진,차은지,강대환,고영주,조예지,최은영,박해경 한국응용과학기술학회 2020 한국응용과학기술학회지 Vol.37 No.4

The spent RHDS (Residue HydroDeSulfurization) catalyst is deactivated mainly by deposition of various contaminants such as coke, sulfur and vanadium on the surface of catalyst. To eliminate those contaminants, the following remanufacturing process was conducted. The first, heavy oil on the surface of the spent RHDS catalyst was removed by kerosene and dehydrated. The second, the high temperature incineration was carried out to eliminate coke and sulfur components deposited on the surface of spent RHDS catalyst. The third, the excessive quantity of Vanadium deposited on the surface of catalyst was removed by leaching process as follows: ultrasonic agitation was carried out at 50℃, for 10 seconds with 0.5% and 1% oxalic acid solution. The purpose of this process is to find out regenerated RHDS catalyst can be used as SCR catalyst for NOx reduction by controlling the vanadium residual content of the regenerated RHDS catalyst through leaching process. The composition of regenerated RHDS catalyst was analyzed by XRF and the NOx reduction efficiency was also measured by continuous catalytic fixed bed reactor. As the result, regenerated catalyst, with 0.5% oxalic acid, ultrasonic agitation in 10 seconds, showed the most stable NOx reduction efficiency. Also, in comparison with commercial SCR catalyst, the NOx reduction performance of regenerated catalyst was similar to that of commercial SCR catalyst at the temperature 375℃ and higher whereas was lower than commercial SCR catalyst at the temperature range between 200∼250℃. Therefore, it was confirmed that the regenerated catalyst as powder form wash coated on the surface of metal corrugated substrate can be used for commercial SCR catalyst.

Recent trends in vanadium-based SCR catalysts for NOx reduction in industrial applications: stationary sources

Ye Bora,정보라,Lee Myeung-jin,Kim Tae Hyeong,Park Sam-Sik,Jung Jaeil,이승현,Kim Hong-Dae 나노기술연구협의회 2022 Nano Convergence Vol.9 No.51

Vanadium-based catalysts have been used for several decades in ammonia-based selective catalytic reduction (NH3-SCR) processes for reducing NOx emissions from various stationary sources (power plants, chemical plants, incinerators, steel mills, etc.) and mobile sources (large ships, automobiles, etc.). Vanadium-based catalysts containing various vanadium species have a high NOx reduction efficiency at temperatures of 350–400 °C, even if the vanadium species are added in small amounts. However, the strengthening of NOx emission regulations has necessitated the development of catalysts with higher NOx reduction efficiencies. Furthermore, there are several different requirements for the catalysts depending on the target industry and application. In general, the composition of SCR catalyst is determined by the components of the fuel and flue gas for a particular application. It is necessary to optimize the catalyst with regard to the reaction temperature, thermal and chemical durability, shape, and other relevant factors. This review comprehensively analyzes the properties that are required for SCR catalysts in different industries and the development strategies of high-performance and low-temperature vanadium-based catalysts. To analyze the recent research trends, the catalysts employed in power plants, incinerators, as well as cement and steel industries, that emit the highest amount of nitrogen oxides, are presented in detail along with their limitations. The recent developments in catalyst composition, structure, dispersion, and side reaction suppression technology to develop a high-efficiency catalyst are also summarized. As the composition of the vanadium-based catalyst depends mostly on the usage in stationary sources, various promoters and supports that improve the catalyst activity and suppress side reactions, along with the studies on the oxidation state of vanadium, are presented. Furthermore, the research trends related to the nano-dispersion of catalytically active materials using various supports, and controlling the side reactions using the structure of shaped catalysts are summarized. The review concludes with a discussion of the development direction and future prospects for high-efficiency SCR catalysts in different industrial fields.

Grubbs` Catalyst의 열안정성 및 자가치료제와의 반응성 평가

윤성호 ( Sung Ho Yoon ),( Ya Long Shi ),( Jun Feng ),장세용 ( Se Yong Jang ) 한국복합재료학회 2015 Composites research Vol.28 No.6

본 연구에서는 자가손상보수에 적용되는 Grubbs’ catalyst의 열안정성과 자가치료제와의 반응성을 조사하였다. 이를 위해 제조사에서 공급된 4종류를 고려하였으며 제조사에서 공급받은 상태와 기계적으로 분쇄시킨 상태로 시험하였다. 자가치료제는 Dicyclopentadiene (DCPD)과 5-ethylidene-2-norbonene (ENB)을 적절한 비율로 혼합한 4종류를 고려하였다. 촉매의 열안정성을 조사하기 위해 시차주사 열량측정장치를 통해 온도에 따른 열흐름변화를 측정하였다. 자가치료제와의 반응성을 평가하기 위해 촉매와 혼합된 자가치료제의 반응열을 측정하였다. 이때 촉매는 자가치료제와 반응할 때의 최대온도와 최대온도 도달시간을 고려하여 Fluka Chemika Grubbs’ catalyst를 적용하였다. 연구결과에 따르면 촉매는 제조사에 따라 다른 형상을 나타내며 입자의 크기가 작은 촉매가 자가 치료제와 높은 반응성을 나타내었다. ENB의 혼합비가 높은 자가치료제가 촉매와 혼합되면 최대온도는 증가하고 최대온도 도달시간은 빨라졌다. 또한 촉매의 양이 많을수록 최대온도는 높아지고 최대온도 도달시간은 빨라졌다. 촉매의 열안정성과 자가치료제와의 반응성을 고려할 때 0.5 wt% 촉매와 D3E1 자가치료제가 자가손상보수를 위한 최적 조건임을 알 수 있었다. 마지막으로 노출된 분위기 온도에 따라 촉매에 열분해가 발생할 수 있기 때문에 촉매가 열안정성을 갖는 온도보다 높은 온도에 노출되지 않도록 하여야 한다. This study investigated the thermal stability of Grubbs’ catalyst and its reactivity with self-healing agents for self-healing damage repair. Four types of Grubbs’ catalyst supplied by manufacturers were considered and each catalyst was tested in as-received and grinded conditions. Four types of self-healing agents were prepared by varying the mixing ratio of dicyclopentadiene (DCPD) and 5-ethylidene-2-norbonene (ENB). Heat flows as a function of temperature were measured through a differential scanning calorimetry (DSC) to determine the thermal stability of catalysts. Reaction heats of self-healing agents with the catalyst were measured to evaluate the reactivity of the catalyst. For this evaluation, Fluka Chemika Grubbs’ catalyst was used based on the maximum temperature and the time to reach the maximum temperature. According to the results, catalysts had different shapes depending on the manufacturer and the results showed that the smaller the size of the catalyst the higher the reactivity with self-healing agents. As the ENB ratio in self-healing agents increased, the maximum temperature increased, and the time to reach the maximum temperature decreased. As the amount of the catalyst increased, the maximum temperature increased, and the time to reach the maximum temperature decreased. Considering the thermal stability of the catalyst and its reactivity with the self-healing agent, combination of 0.5 wt% catalyst and the D3E1 self-healing agent was optimal for self-healing damage repair. Finally, as the thermal decomposition may occur depending on the environmental temperature, the catalyst must not be exposed to temperature higher than that is necessary to maintain the thermal stability of the catalyst.

Transition metal/carbon nanoparticle composite catalysts as platinum substitutes for bioelectrochemical hydrogen production using microbial electrolysis cells

Choi, Mi-Jin,Yang, Euntae,Yu, Hye-Weon,Kim, In S.,Oh, Sang-Eun,Chae, Kyu-Jung Elsevier 2019 INTERNATIONAL JOURNAL OF HYDROGEN ENERGY - Vol.44 No.4

<P><B>Abstract</B></P> <P>Various metal nanoparticle catalysts supported on Vulcan XC-72 and carbon-nanomaterial-based catalysts were fabricated and compared and assessed as substitutes of platinum in microbial electrolysis cells (MECs). The metal-nanoparticle-loaded cathodes exhibited relatively better hydrogen production and electrochemical properties than cathodes coated with carbon nanoparticles (CNPs) and carbon nanotubes (CNTs) did. Catalysts containing Pt (alone or mixed with other metals) most effectively produced hydrogen in terms of overall conversion efficiency, followed by Ni alone or combined with other metals in the order: Pt/C (80.6%) > PtNi/C (76.8%) > PtCu/C (72.6%) > Ni/C (73.0%) > Cu/C (65.8%) > CNPs (47.0%) > CNTs (38.9%) > plain carbon felt (38.7%). Further, in terms of long-term catalytic stability, Ni-based catalysts degraded to a lesser extent over time than did the Cu/C catalyst (which showed the maximum degradation). Overall, the hydrogen generation efficiency, catalyst stability, and current density of the Ni-based catalysts were almost comparable to those of Pt catalysts. Thus, Ni is an effective and inexpensive alternative to Pt catalysts for hydrogen production by MECs.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Various metal- and carbon-based nanomaterial catalysts were tested in MEC. </LI> <LI> Metal-based catalysts showed higher performance than the carbon-based catalyst did. </LI> <LI> Ni-based catalysts showed comparable H<SUB>2</SUB> production and stability to Pt catalysts. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

PEMFC 전극촉매 Pt/C와 PtCo/C의 촉매 지지체 열화비교

오소형,한유한,정민철,유동근,박권필,Sohyeong Oh,Yoohan Han,Minchul Chung,Donggeun Yoo,Kwonpil Park 한국화학공학회 2023 Korean Chemical Engineering Research(HWAHAK KONGHA Vol.61 No.3

In PEMFC, PtCo/C alloy catalysts are widely used because of good performance and durability. However, few studies have been reported on the durability of carbon supports of PtCo/C evaluated at high voltages (1.0~1.5 V). In this study, the durability of PtCo/C catalysts and Pt/C catalysts were compared after applying the accelerated degradation protocol of catalyst support. After repeating the 1.0↔1.5V voltage change cycles, the mass activity, electrochemical surface area (ECSA), electric double layer capacitance (DLC), Pt dissolution and the particle growth were analyzed. After 2,000 cycles of voltage change, the current density per catalyst mass at 0.9V decreased by more than 1.5 times compared to the Pt/C catalyst. This result was because the degradation rate of the carbon support of the PtCo/C catalyst was higher than that of the Pt/C catalyst. The Pt/C catalyst showed more than 1.5 times higher ECSA reduction than the PtCo/C catalyst, but the corrosion of the carbon support of the Pt/C catalyst was small, resulting in a small decrease in I-V performance. In order to improve the high voltage durability of the PtCo/C catalyst, it was shown that improving the durability of the carbon support is essential.

Exsolution-based Co/Ni bimetallic Catalysts for Dry Reforming of Methane

Dong Hyun Kim(김동현),Ahmed Al-Shahat Eissa(아흐메드 알사하트 이사),Kyubock Lee(이규복) 한국에너지기후변화학회 2021 한국에너지기후변화학회 학술대회 Vol.2021 No.11

Ni-based catalysts are widely used for dry reforming of methane (DRM), due to their high catalytic activity and low-cost. However, Ni-based catalysts suffer from deactivation, especially under long-term operating conditions, because of carbon deposition and catalyst sintering. As a result, the design of efficient noble-metal-free catalysts for the DRM still a great challenge. Incorporating another element with Ni has been reported to promote the catalytic activity and coke resistance of catalyst. In this study, we report a facile strategy for fabricating CoNi/MgAl₂O₄ catalyst by one-pot evaporation induced self-assembly combine with exsolution method. During the reduction process, the active metals were successfully exsolved on the catalyst surface, and it was confirmed that CoNi alloy was formed. Our results demonstrate that the formation of a stable exsolved CoNi alloy is an important factor for maintaining the catalyst durability under long-term DRM reaction conditions, and the catalytic activity varies greatly depending on the nickel content. At Co:Ni ratio of 1:4, the catalyst showed a surface area of 175 ㎡/g, and particles size of 12 - 14 nm. When applied for the DRM reaction at 800 ℃ and gas hourly space velocity of 36,000 h<SUP>-1</SUP>, it exhibited CO₂ and CH₄ conversions of 98 and 92%, respectively. After serving for the DRM reaction for 100 h, the catalyst displayed CO₂ and CH₄ conversions of 94 and 85%, respectively, indicating the excellent durability of the herein synthesized catalyst. In addition, a small amount of carbon (3.1%) was deposited on the catalyst’s surface after the long-term reaction test. The insights obtained from this study may have broad applications in developing highly stable CoNi bimetallic catalysts for methane reforming reactions.

알칼리 및 알칼리 토금속에 의한 SCR 촉매 비활성 거동

한승윤,신민철,이희수,Han, Seungyun,Shin, Min-Chul,Lee, Heesoo 한국결정성장학회 2016 한국결정성장학회지 Vol.26 No.6

알칼리(토)금속이 SCR(Selective Catalytic Reduction) 촉매 비활성화에 미치는영향을 미세구조, 촉매 비표면적, 기공 부피 변화, 탈질 성능 분석을 통해 규명하였다. 신촉매를 $350^{\circ}C$에서 6시간 동안 $H_3PO_4$, $K_2CO_3$, $Na_2CO_3$, $Ca(CH_3COO)_2{\cdot}H_2O$, $C_4H_6MgO_4{\cdot}4H_2O$ 수용액을 분사 시켜, 모사 피독된 SCR 촉매를 제조하였다. 피독 촉매 표면의 미세구조는 신촉매와 거의 유사한 형태를 보이지만, 비표면적과 기공 부피 변화를 신촉매와 비교하였을 때, Na < Mg < K < Ca < P 순으로 감소하는 것으로 나타났다. 특히 Na에 의해 피독된 촉매는 비표면적은 $10.20m^2/g$, 기공부피는 $0.061cm^2/g$ 정도 감소하였다. $150{\sim}450^{\circ}C$에서 신촉매 및 피독 촉매의 탈질성능을 평가한 결과, 알칼리 금속(K, Na)에 피독된 SCR 촉매가 가장 낮은 탈질효율을 보였으며, 알칼리 토금속(Ca, Mg)에 피독된 SCR 촉매는 알칼리 금속(K, Na)에 피독된 촉매에 비해 상대적으로 높은 탈질 효율을 보였으며, 인(P)에 의해 피독된 촉매는 SCR 신촉매와 거의 유사한 탈질 성능을 나타내는 것을 확인하였다. 이러한 결과는 SCR 촉매 비표면적이나 기공 부피 감소에 따른 물리적인 비활성화가 SCR 촉매 탈질 성능에 영향을 미치는 것으로 보인다. The effect of the alkali, alkali earth metal elements on selective catalytic reduction(SCR) catalyst deactivation behavior were investigated in terms of microstructure, surface area, pore volume and De-NOx test. Poisoned SCR catalyst were manufactured by injection of $K_2CO_3$, $Na_2CO_3$, $Ca(CH_3COO)_2{\cdot}H_2O$, $C_4H_6MgO_4{\cdot}4H_2O$, $H_3PO_4$ solutions in the new SCR catalyst at $350^{\circ}C$ for 6 hours. New and poisoned catalysts surface were similar. But specific surface area, pore volume decrease from Na, Mg, K, Ca, P compared to new SCR catalyst. Especially, Na poisoned catalyst surface area and pore size extremely decreased by $10.20m^2/g$, $0.061cm^2/g$. De-NOx test results of new and poisoned catalysts at $150{\sim}450^{\circ}C$ indicated that alkali metal (K, Na) poisoned SCR catalysts have the lowest De-NOx efficiency, alkali earth metal poisoned SCR catalysts (Ca, Mg) De-NOx efficiency are higher than alkali metal poisoned SCR catalysts. P poisoned SCR catalyst De-NOx efficiency is similar new SCR catalyst. It were considered that physical deactivation of SCR catalyst was affected by SCR catalyst surface area and pore volume change.

Rise of atomically dispersed metal catalysts: Are they a new class of catalysts?

김재형,주상훈 대한화학회 2024 Bulletin of the Korean Chemical Society Vol.45 No.4

Atomically dispersed metal catalysts or single‐atom catalysts have made great strides during the past decade in the catalysis field. While an initial vision of atomically dispersed metal catalysts was to combine the advantages of homogeneous and heterogeneous catalysts, their unexpected potentials continue to be discovered. In this account, we introduce historical backgrounds underpinning the emergence of atomically dispersed metal catalysts. Next, we illustrate some recent examples demonstrating the unusual reactivities of atomically dispersed metal catalysts, which are hard to realize by homogeneous or heterogeneous catalysts. We conclude the account by suggesting the remaining challenges in this exciting field. Atomically dispersed metal catalysts or single-atom catalysts have made great strides during the past decade in the catalysis field. While an initial vision of atomically dispersed metal catalysts was to combine the advantages of homogeneous and heterogeneous catalysts, their unexpected potentials continue to be discovered. In this account, we introduce historical backgrounds underpinning the emergence of atomically dispersed metal catalysts. Next, we illustrate some recent examples demonstrating the unusual reactivities of atomically dispersed metal catalysts, which are hard to realize by homogeneous or heterogeneous catalysts. We conclude the account by suggesting the remaining challenges in this exciting field.

Optimization of bi‑metallic (Fe–Co) catalyst on kaolin support for carbon nanofiber growth in a CVD reactor

K. Y. Mudi,A. S. Abdulkareem,O. S. Azeez,A. S. Kovo,J. O. Tijani,E. J. Eterigho 한국탄소학회 2019 Carbon Letters Vol.29 No.3

This study focused on the development of Fe–Co/kaolin catalyst by a wet impregnation method. Response surface methodology was used to study the influence of operating variables such as drying temperature, drying time, mass of support and stirring speed on the yield of the catalyst. The catalyst composite at best synthesis conditions was then calcined in an oven at varied temperature and time using 22 factorial design of experiment. The catalyst with optimum surface area was then utilized to grow carbon nanofiber (CNF) in a chemical vapour deposition (CVD) reactor. Both the catalyst and CNF were characterized using high-resolution scanning electron microscopy, high-resolution transmission electron microscopy, thermogravimetric analysis (TGA), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy. On the influence of operating variables on the yield of catalyst, the results showed that an optimum yield of 96.51% catalyst was obtained at the following operating conditions: drying time (10 h), drying temperature (110 °C), stirring speed (100 rpm) and mass of support (9 g). Statistical analysis revealed the existence of significant interactive effects of the variables on the yield of the catalyst. The HRSEM/XRD/BET/TGA analysis revealed that the particles are well dispersed on the support, with high surface area (376.5 m2/g) and thermally stable (330.88 °C). The influence of operating parameters on the yield of CNF was also investigated and the results revealed an optimum yield of 348% CNF at the following operating conditions: reaction temperature (600 °C), reaction time (40 min), argon flow rate (1416 mL/min) and acetylene/hydrogen flow rate (1416 mL/ min). It was found from statistical analysis that the reaction temperature and acetylene/hydrogen flow rates exerted significant effect on the CNF yield than the other factors. The contour and surface plots bi-factor interaction indicated functional relationship between the response and the experimental factors. The characterization results showed that the synthesized CNF is thermally stable, twisted and highly crystalline and contain surface functional groups. It can be inferred from the results of various analyses that the developed catalyst is suitable for CNF growth in a CVD reactor.