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Hierarchical Porous Titanium Nitride Synthesized by Multiscale Phase Separation for LSBs
(from left: Professor Jinwoo Lee and PhD candidate Won-Gwang Lim) A KAIST research team developed ultra-stable, high-rate lithium-sulfur batteries (LSBs) by using hierarchical porous titanium nitride as a sulfur host, and achieved superior cycle stability and high rate performance for LSBs. The control of large amounts of energy is required for use in an electric vehicle or smart grid system. In this sense, the development of next-generation secondary batteries is in high demand. Theoretically, LSBs have an energy density seven times higher than commercial lithium ion batteries (LIBs). Also, their production cost can be reduced dramatically since sulfur can be obtained at a low price. Despite these positive aspects, there have been several issues impeding the commercialization of LSBs, such as the low electric conductivity of sulfur, the dissolution of active materials during operation, and sluggish conversion reactions. These issues decrease the cycle stability and rate capability of batteries. To tackle those issues, Professor Jinwoo Lee from the Department of Chemical and Biomolecular Engineering and his team synthesized a well-developed hierarchical macro/mesoporous titanium nitride as a host material for sulfur. The titanium nitride has a high chemical affinity for sulfur and high electrical conductivity. As a result, it prevents the dissolution of active materials and facilitates the charge transfer. Moreover, the synergistic effect of macropore and mesopore structures allows the stable accommodation of large amounts of sulfur and facilitates the electrolyte penetration. Previously reported polar inorganic materials have a high affinity for sulfur, but it was challenging to control the porous architecture suitable to the sulfur host. This work breaks such limitations by developing a synthetic route to easily control the porous architecture of inorganic materials, which led to obtaining superior cycle stability and high rate capabilities. Professor Lee said, “Some problems still remain in commercializing LSBs as next-generation batteries. Hence, there should be a continued research on this matter to solve the issues. Through this research, we secured a key technology for ultrastable, high-rate LSBs.” This research was led by PhD candidate Won-Gwang Lim and collaborated on by Jeong Woo Han from POSTECH. It was chosen as the cover article of Advanced Materials on January 15, 2019. Figure 1. Schematic illustration for the synthetic route of co-continuous h-TiN Figure 2. The hierarchical multiscale porous structure is still retained without any collapse after the conversion to h-TiN. The good retention of the porous structure is attributed to the thick pore wall of the h-TiO₂derived from the block copolymer self-assembly Figure 3. The cover page of Advanced Materials
Lifespan of Fuel Cells Maximized Using Small Amount of Metals
(Professor Jung (far right) and his team) Fuel cells are key future energy technology that is emerging as eco-friendly and renewable energy sources. In particular, solid oxide fuel cells composed of ceramic materials gain increasing attention for their ability to directly convert various forms of fuel such as biomass, LNG, and LPG to electric energy. KAIST researchers described a new technique to improve chemical stability of electrode materials which can extend the lifespan by employing a very little amount of metals. The core factor that determines the performance of solid oxide fuel cells is the cathode at which the reduction reaction of oxygen occurs. Conventionally, oxides with perovskite structure (ABO3) are used in cathodes. However, despite the high performance of perovskite oxides at initial operation, the performance decreases with time, limiting their long-term use. In particular, the condition of high temperature oxidation state required for cathode operation leads to surface segregation phenomenon, in which second phases such as strontium oxide (SrOx) accumulate on the surface of oxides, resulting in decrease in electrode performance. The detailed mechanism of this phenomenon and a way to effectively inhibit it has not been suggested. Using computational chemistry and experimental data, Professor WooChul Jung’s team at the Department of Materials Science and Engineering observed that local compressive states around the Sr atoms in a perovskite electrode lattice weakened the Sr-O bond strength, which in turn promote strontium segregation. The team identified local changes in strain distribution in perovskite oxide as the main cause of segregation on strontium surface. Based on these findings, the team doped different sizes of metals in oxides to control the extent of lattice strain in cathode material and effectively inhibited strontium segregation. Professor Jung said, “This technology can be implemented by adding a small amount of metal atoms during material synthesis, without any additional process.” He continued, “I hope this technology will be useful in developing high-durable perovskite oxide electrode in the future.” The study co-led by Professor Jung and Professor Jeong Woo Han at Department of Chemical Engineering, University of Seoul was featured as the cover of Energy and Environmental Science in the first issue of 2018. (Figure1.Correlation between the extent of lattice strain in electrode, strontium segregation, and electrode reaction.) (Figure 2. Cathode surface of solid oxide fuel cell stabilized using the developed technology)
Platinum Single Atom Catalysts for 'Direct Formic Acid Fuel Cells'
(Professor Hyunjoo Lee (left) and Ph.D. candidate Jiwhan Kim) A research team co-led by Professor Hyunjoo Lee at the Department of Chemical and Biomolecular Engineering at KAIST and Professor Jeong Woo Han from the University of Seoul synthesized highly stable high-Pt-content single atom catalysts for direct formic acid fuel cells. The amount of platinum can be reduced to 1/10 of that of conventional platinum nanoparticle catalysts. Platinum (Pt) catalysts have been used in various catalytic reactions due to their high activity and stability. However, because Pt is rare and expensive, it is important to reduce the amount of Pt used. Pt single atom catalysts can reduce the size of the Pt particles to the size of an atom. Thus, the cost of Pt catalysts can be minimized because all of the Pt atoms can participate in the catalytic reactions. Additionally, single atom catalysts have no ensemble site in which two or more atoms are attached, and thus, the reaction selectivity is different from that of nanoparticle catalysts. Despite these advantages, single atom catalysts are easily aggregated and less stable due to their low coordination number and high surface free energy. It is difficult to develop a single atom catalyst with high content and high stability, and thus, its application in practical devices is limited. Direct formic acid fuel cells can be an energy source for next-generation portable devices because liquid formic acid as a fuel is safer and easier to store and transport than high-pressure hydrogen gas. To improve the stability of Pt single atom catalysts, Professor Lee’s group developed a Pt-Sn single atom alloy structure on an antimony-doped tin oxide (ATO) support. This structure has been proven by computational calculations which show that Pt single atoms substitute antimony sites in the antimony-tin alloy structure and are thermodynamically stable. This catalyst has been shown to have a higher activity up to 50 times per weight of Pt than that of the commercial catalyst, Pt/C, in the oxidation of formic acid, and the stability of the catalyst was also remarkably high. Professor Lee’s group also used a single atomic catalyst in a 'direct formic acid fuel cell’ consisting of membranes and electrodes. It is the first attempt to apply a single atomic catalyst to a full cell. In this case, an output similar to that of the commercial catalyst could be obtained by using 1/10 of the platinum compared to the commercial Pt/C catalyst. Ph.D. candidate Jiwhan Kim from KAIST was the first author of the research. This research was published online on September 11 in Advanced Energy Materials. This research was carried out with the support of the Samsung Electronics Future Technology Development Center. (Figure 1. Concept photograph for Pt single atom catalysts.) (Figure 2. Pt single atom catalysts by HAADF-STEM analysis (bright white circles))
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