Transition metal oxide-based materials have mainly been studied as electrodes for energy storage devices designed to meet essential energy demands. Among transition metal oxide-based materials, hydrated vanadium pentoxide (V2O5 ‧ nH2O), a vanadium oxide material, has demonstrated great electrochemical performance in the electrodes of energy storage devices. Graphene oxide (GO), a carbon-based material with high surface area and high electrical conductivity, has been added to V2O5 ‧ nH2O to compensate for its low electrical conductivity and structural instability. Here, V2O5 ‧ nH2O/GO nanobelts are manufactured with water without adding acid to ensure that the GO is uniformly dispersed, using a microwave-assisted hydrothermal synthesis. The resulting V2O5 ‧ nH2O/GO nanobelts exhibited a high specific capacitance of 206 F/g and more stable cycling performance than V2O5 ‧ nH2O without GO. The drying conditions of the carbon paper electrodes also resulted in more stable cycling performance when conducted at high vacuum and high temperature, compared with low vacuum and room temperature conditions. The improvement in electrochemical performance due to the addition of GO and the drying conditions of carbon paper electrodes indicate their great potential value as electrodes in energy storage devices.
VRFB에 사용되는 막의 수송 능력은 배터리 성능에 필수적인 요소이다. 탁월한 배터리 성능을 위해서는 높은 양 성자 전도도와 낮은 바나듐 이온 투과도가 달성되어야 한다. 하지만 양성자 전도도와 바나듐 이온 투과도 사이에는 상충관계 가 존재한다. 따라서 이 상충관계를 해결하는 것이 VRFB의 발전에 필수적이다. 또한 높은 쿨롱 효율, 전압 효율 및 에너지 효율을 유지하는 것이 고성능 VRFB를 위해 필수적이다. 최근 복합막과 SPEEK 막을 중심으로 나피온 막의 기존 한계를 극 복하기 위한 다양한 시도가 이루어지고 있다. VRFB은 이 논문에서 검토하는 복합막에서 충전식 배터리의 필수 등급이다.
전 바나듐 레독스 흐름 전지(VRFB)는 유망한 대용량 에너지 저장 기술 중 하나이다. 이온교환막은 VRFB의 충⋅ 방전 성능 및 내구성을 좌우하는 핵심 구성 요소이다. 본 연구에서는 기존 탄화수소계 이온교환막의 단점을 보완하기 위해 우수한 물리적 및 화학적 안정성을 갖는 다공성 폴리테트라플루오로에틸렌(PTFE) 지지체의 세공에 불소부가 포함된 탄화수 소계 이오노머를 충진하는 방식으로 세공충진 음이온교환막(PFAEMs)을 제조하였다. 얇은 다공성 PTFE 지지체의 사용으로 전기적 저항을 현저히 낮출 수 있었으며 PTFE 지지체의 사용과 더불어 충진 이오노머에 불소부를 도입함으로써 막의 산화 안정성을 크게 향상시킬 수 있었다. 충⋅방전 성능 평가 결과, PFAEM에 불소부의 함량이 증가할수록 높은 전류 효율을 나타내었으며 낮은 전기적 저항으로 상용막 대비 우수한 전압 효율 및 에너지 효율을 보였다. 또한, 산화 안정성 및 충⋅방전 성능의 관점에서 소수성 PTFE 지지체의 사용이 더 바람직함을 확인하였다.
메타바나듐산 암모늄으로 제조한 전해액과 양이온교환막인 Nafion117을 활용하는 바나듐 레독스 흐름 전지 (vanadium redox flow battery, VRFB)의 전기화학적 성능을 평가하였다. VRFB의 전기화학적 성능은 전류밀도 60 mA/cm2에 서 측정하였다. 메타바나듐산 암모늄으로 제조된 전해액을 사용한 VRFB의 평균 전류효율은 94.9%, 평균 전압효율은 82.2%, 평균 에너지효율은 78.0%를 보였다. 그리고 메타바나듐산 암모늄으로 제조된 전해액을 사용한 VRFB의 각 효율은 바나딜 설 페이트(VOSO4)로 제조된 전해액을 사용한 VRFB의 각 효율과 비교하여 거의 동등한 값을 갖는다는 것을 확인하였다.
Well-crystallized vanadium pentoxide V2O5 thin films are fabricated on MgO single crystal substrates by using pulsed-laser deposition technique. The linear optical transmission spectra are measured and found to be in a wavelength range from 300 to 800 nm; the data are used to determine the linear refractive index of the V2O5 films. The value of linear refractive index decreases with increasing wavelength, and the relationship can be well explained by Wemple’s theory. The third-order nonlinear optical properties of the films are determined by a single beam z-scan method at a wavelength of 532 nm. The results show that the prepared V2O5 films exhibit a fast third-order nonlinear optical response with nonlinear absorption coefficient and nonlinear refractive index of 2.13 × 10−10 m/W and 2.07 × 10−15 cm2/kW, respectively. The real and imaginary parts of the nonlinear susceptibility are determined to be 3.03 × 10−11 esu and 1.12 × 10−11 esu, respectively. The enhancement of the nonlinear optical properties is discussed.
In this study, three kinds of bainitic steels are fabricated by controlling the contents of vanadium and boron. High vanadium steel has a lot of carbides and nitrides, and so, during the cooling process, acicular ferrite is well formed. Carbides and nitrides develop fine grains by inhibiting grain growth. As a result, the low temperature Charpy absorbed energy of high vanadium steel is higher than that of low vanadium steel. In boron added steel, boron segregates at the prior austenite grain boundary, so that acicular ferrite formation occurs well during the cooling process. However, the granular bainite packet size of the boron added steel is larger than that of high vanadium steel because boron cannot effectively suppress grain growth. Therefore, the low temperature Charpy absorbed energy of the boron added steel is lower than that of the low vanadium steel. HAZ (heat affected zone) microstructure formation affects not only vanadium and boron but also the prior austenite grain size. In the HAZ specimen having large prior austenite grain size, acicular ferrite is formed inside the austenite, and granular bainite, bainitic ferrite, and martensite are also formed in a complex, resulting in a mixed acicular ferrite region with a high volume fraction. On the other hand, in the HAZ specimen having small prior austenite grain size, the volume fraction of the mixed acicular ferrite region is low because granular bainite and bainitic ferrite are coarse due to the large number of prior austenite grain boundaries.
Silicon heterojunction solar cells can achieve high conversion efficiency with a simple structure. In this study, we investigate the passivation characteristics of VOx thin films as a hole-selective contact layer using ALD (atomic layer deposition). Passivation characteristics improve with iVoc (implied open-circuit voltage) of 662 mV and minority carrier lifetime of 73.9 μs after post-deposition annealing (PDA) at 100 oC. The improved values are mainly attributed to a decrease in carbon during the VOx thin film process after PDA. However, once it is annealed at temperatures above 250 oC the properties are rapidly degraded. X-ray photoelectron spectroscopy is used to analyze the chemical states of the VOx thin film. As the annealing temperature increases, it shows more formation of SiOx at the interface increases. The ratio of V5+ to V4+, which is the oxidation states of vanadium oxide thin films, are 6:4 for both as-deposition and annealing at 100 oC, and 5:5 for annealing at 300 oC. The lower the carbon content of the ALD VOx film and the higher the V5+ ratio, the better the passivation characteristics.
기존의 바나듐 레독스 흐름전지(vanadium redox flow battery, VRFB)에서 사용하고 있는 과불소계이오노머인 나피 온(Nafion)은 전해질에 존재하는 바나듐 이온의 투과도가 높아, 바나듐 이온이 분리막을 투과하여 반대쪽 전해질로 교차 이동 하는 문제를 갖고 있다. VRFB에서 바나듐 이온의 투과는 서로 다른 산화수를 갖는 바나듐 이온이 부반응을 일으켜 충전, 방전 용량의 감소를 야기하고, 장기적인 성능 감소를 일으키는 원인이 된다. 이러한 문제를 해결하기 위해 본 연구에서는 SiO2에 3-aminopropyl group이 도입된 나노입자(fS)를 Nafion에 분산시켜 바나듐 이온의 투과를 감소시키고, VRFB의 장기적인 성능 의 향상을 도모하고자 하였다. SiO2에 붙어 있는 아민기(-NH2)가 Nafion의 술폰산 음이온(SO3 -)과 이온결합을 형성함과 동시 에, 암모늄 양이온(-NH3 +)의 양전하가 바나듐 이온에 대해 Gibbs-Donnan 효과를 나타내어 낼 것이라고 기대하였다. fS를 섞은 Nafion 용액의 pH와 Nafion-fS 막의 IEC 측정을 통해 암모늄 양이온과 술폰산 음이온의 이온결합이 존재하는 것을 확인하였고, fS의 양이 많아질수록 바나듐 이온의 투과도가 감소하는 것을 확인하였다. VRFB 단위 전지에 제조한 복합막을 도입하였을 때, 150 mA/cm2의 전류밀도에서 충방전 사이클을 200회 반복 진행하여도 방전용량을 최대 80%까지 유지할 수 있었다.
본 연구에서는 전 바나듐 레독스 흐름전지(VRFB)에 적용하기 위한 세공충진 음이온교환막의 최적 설계 조건을 도출하고자 하였다. 실험결과를 통해 VRFB 충방전 성능에 가장 지대한 영향을 미치는 막 설계인자는 이온교환용량, 지지체의 기공율 및 가교도임을 확인할 수 있었다. 즉, 상기 인자들에 의해 VRFB의 ohmic loss와 활물질의 crossover가 결정되었다. 또 한 세공충진 음이온교환막의 제조 시 낮은 가교도에서 이온교환용량을 감소시키는 것과 높은 이온교환용량에서 가교도를 증 가시키는 두 가지 방안을 검토하였다. 그 결과 충분히 높은 이온교환용량에서 가교도를 최적화 하는 것이 VRFB 충방전 성능 관점에서 바람직한 것으로 판단되었다.
In the present work, spheroidization of angular vanadium powders using a radio frequency (RF) thermal plasma process is investigated. Initially, angular vanadium powders are spheroidized successfully at an average particle size of 100 μm using the RF-plasma process. It is difficult to avoid oxide layer formation on the surface of vanadium powder during the RF-plasma process. Titanium/vanadium/stainless steel functionally graded materials are manufactured with vanadium as the interlayer. Vanadium intermediate layers are deposited using both angular and spheroidized vanadium powders. Then, 17-4PH stainless steel is successfully deposited on the vanadium interlayer made from the angular powder. However, on the surface of the vanadium interlayer made from the spheroidized powder, delamination of 17-4PH occurs during deposition. The main cause of this phenomenon is presumed to be the high thickness of the vanadium interlayer and the relatively high level of surface oxidation of the interlayer.
In the present study, vanadium oxide(V2O5) films for electrochromic(EC) application are fabricated using sol-gel spin coating method. In order to optimize the EC performance of the V2O5 films, we adjust the amounts of polyvinylpyrrolidone(PVP) added to the solution at 0, 5, 10, and 15 wt%. Due to the effect of added PVP on the V2O5 films, the obtained films show increases of film thickness and crystallinity. Compared to other samples, optimum weight percent(10 wt%) of PVP led to superior EC performance with transmittance modulation(45.43 %), responding speeds(6.0 s at colored state and 6.2 s at bleached state), and coloration efficiency(29.8 cm2/C). This performance improvement can be mainly attributed to the enhanced electrical conductivity and electrochemical activity due to the increased crystallinity and thickness of the V2O5 films. Therefore, V2O5 films fabricated with optimized amount of PVP can be a promising EC material for high-performance EC devices.
Owing to their scalability, flexible operation, and long cycle life, vanadium redox flow batteries (VRFBs) have gained immense attention over the past few years. However, the VRFBs suffer from significant polarization, which decreases their cell efficiency. The activation polarization occurring during vanadium redox reactions greatly affects the overall performance of VRFBs. Therefore, it is imperative to develop electrodes with numerous catalytic sites and a long cycle life. In this study, we synthesized heteroatom-rich carbon-based freestanding papers (H-CFPs) by a facile dispersion and filtration process. The H-CFPs exhibited high specific surface area (~820 m2 g–1) along with a number of redox-active heteroatoms (such as oxygen and nitrogen) and showed high catalytic activity for vanadium redox reactions. The H-CFP electrodes showed excellent electrochemical performance. They showed low anodic and cathodic peak potential separation (ΔEp) values of ~120 mV (positive electrolyte) and ~124 mV (negative electrolyte) in cyclic voltammetry conducted at a scan rate of 5 mV s–1. Hence, the H-CFP-based VRFBs showed significantly reduced polarization.
Polyphenylene sulfide(PPS) is a hydrocarbon polymer which has resistance to heat, chemicals and generality due to its low cost. To produce cationic exchange polymer, PPS was blended with sulfonation process and Polyvinylidenedifluoride(PVdF) was also applied for membrane-flexibility. After production of sulfonated-PPS (sPPS)/PVdf blend membrane, membrane property evaluation is concomitant. Water uptake and Dimensional change were highly enhanced by the incorporation of PVdF in blend membrane. Also stability of sPPS/PVdF blend membrane in VO2+ solution was highly improved. When the amount of PVdF is increasing, however, proton conductivity shows a slightly downward tendency. Consequently, the optimization of PVdF Content in sPPS/PVdf blend membrane is an important factor for the realization of VRFB system.
Recently, the most commonly used membrane in vanadium redox flow battery (VRFB) is hydrocarbon-based cation exchange membrane. However, hydrophilic blocks or hydrophilic moieties have been considered as the main reason on degradation of hydrocarbon-based ionomers, while the significance of hydrophobic moiety has been neglected in ionomers. Herein, the poly(p-phenylene)s-based cation conducting polymeric membrane materials with different hydrophobic block structures were successfully synthesized by Ni(0)-catalyzed coupling polymerization for investigating the effect of the hydrophobic block structure on durability of membrane in VRFB.