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Fabrication of Shape-conformable Batteries with 3D-Printing
(from left: Dr. Bok Yeop Ahn, Dr. Chanhoon Kim, Professor Il-Doo Kim and Professor Jennifer A. Lewis) Flexible, wireless electronic devices are rapidly emerging and have reached the level of commercialization; nevertheless, most of battery shapes are limited to either spherical and/or rectangular structures, which results in inefficient space use. Professor Il-Doo Kim’s team from the Department of Materials Science at KAIST has successfully developed technology to significantly enhance the variability of battery design through collaboration research with Professor Jennifer A. Lewis and her team from the School of Engineering and Applied Sciences at Harvard University. Most of the battery shapes today are optimized for coin cell and/or pouch cells. Since the battery as an energy storage device occupies most of the space in microelectronic devices with different designs, new technology to freely change the shape of the battery is required. The KAIST-Harvard research collaboration team has successfully manufactured various kinds of battery shapes, such as ring-type, H, and U shape, using 3D printing technology. And through the research collaboration with Dr. Youngmin Choi at the Korea Research Institute of Chemical Technology (KRICT), 3D-printed batteries were applied to small-scale wearable electronic devices (wearable light sensor rings). The research group has adopted environmentally friendly aqueous Zn-ion batteries to make customized battery packs. This system, which uses Zn2+ instead of Li+ as charge carriers, is much safer compared with the conventional lithium rechargeable batteries that use highly inflammable organic electrolytes. Moreover, the processing conditions of lithium-ion batteries are very complicated because organic solvents can ignite upon exposure to moisture and oxygen. As the aqueous Zn-ion batteries adopted by the research team are stable upon contact with atmospheric moisture and oxygen, they can be fabricated in the ambient air condition, and have advantages in packaging since packaged plastic does not dissolve in water even when plastic packaging is applied using a 3D printer. To fabricate a stable cathode that can be modulated in various forms and allows high charge-discharge, the research team fabricated a carbon fiber current collector using electrospinning process and uniformly coated electrochemically active polyaniline conductive polymer on the surface of carbon fiber for a current collector-active layer integrated cathode. The cathode, based on conductive polyaniline consisting of a 3D structure, exhibits very fast charging speeds (50% of the charge in two minutes) and can be fabricated without the detachment of active cathode materials, so various battery forms with high mechanical stability can be manufactured. Prof. Kim said, “Zn-ion batteries employing aqueous electrolytes have the advantage of fabrication under ambient conditions, so it is easy to fabricate the customized battery packs using 3D printing.” “3D-printed batteries can be easily applied for niche applications such as wearable, personalized, miniaturized micro-robots, and implantable medical devices or microelectronic storage devices with unique designs,” added Professor Lewis. With Dr. Chanhoon Kim in the Department of Materials Science and Engineering at KAIST and Dr. Bok Yeop Ahn School of Engineering and Applied Sciences at Harvard University participating as equally contributing first authors, this work was published in the December issue of ACS Nano. This work was financially supported by the Global Research Laboratory (NRF-2015K1A1A2029679) and Wearable Platform Materials Technology Center (2016R1A5A1009926). Figure 1.Fabrication of shape-conformable batteries based on 3D-printing technology and the application of polyaniline carbon nanofiber cathodes and wearable electronic devices Figure 2.Fabricated shape-conformable batteries based on a 3D-printing method Meanwhile, Professor Il-Doo Kim was recently appointed as an Associate Editor of ACS Nano, a highly renowned journal in the field of nanoscience. Professor Kim said, “It is my great honor to be an Associate Editor of the highly renowned journal ACS Nano, which has an impact factor reaching 13.709 with 134,596 citations as of 2017. Through the editorial activities in the fields of energy, I will dedicate myself to improving the prominence of KAIST and expanding the scope of Korea’s science and technology. I will also contribute to carrying out more international collaborations with world-leading research groups.” (Associate Editor of ACS Nano Professor Il-Doo Kim)
Ultra-Fast and Ultra-Sensitive Hydrogen Sensor
(From left: Professor Kim, Ph.D. candidate Koo, and Professor Penner) A KAIST team made an ultra-fast hydrogen sensor that can detect hydrogen gas levels under 1% in less than seven seconds. The sensor also can detect hundreds of parts per million levels of hydrogen gas within 60 seconds at room temperature. A research group under Professor Il-Doo Kim in the Department of Materials Science and Engineering at KAIST, in collaboration with Professor Reginald M. Penner of the University of California-Irvine, has developed an ultra-fast hydrogen gas detection system based on a palladium (Pd) nanowire array coated with a metal-organic framework (MOF). Hydrogen has been regarded as an eco-friendly next-generation energy source. However, it is a flammable gas that can explode even with a small spark. For safety, the lower explosion limit for hydrogen gas is 4 vol% so sensors should be able to detect the colorless and odorless hydrogen molecule quickly. The importance of sensors capable of rapidly detecting colorless and odorless hydrogen gas has been emphasized in recent guidelines issued by the U.S. Department of Energy. According to the guidelines, hydrogen sensors should detect 1 vol% of hydrogen in air in less than 60 seconds for adequate response and recovery times. To overcome the limitations of Pd-based hydrogen sensors, the research team introduced a MOF layer on top of a Pd nanowire array. Lithographically patterned Pd nanowires were simply overcoated with a Zn-based zeolite imidazole framework (ZIF-8) layer composed of Zn ions and organic ligands. ZIF-8 film is easily coated on Pd nanowires by simple dipping (for 2–6 hours) in a methanol solution including Zn (NO3)2·6H2O and 2-methylimidazole. (This cover image depicts lithographically-patterned Pd nanowires overcoated with a Zn-based zeolite imidazole framework (ZIF-8) layer.) As synthesized ZIF-8 is a highly porous material composed of a number of micro-pores of 0.34 nm and 1.16 nm, hydrogen gas with a kinetic diameter of 0.289 nm can easily penetrate inside the ZIF-8 membrane, while large molecules (> 0.34 nm) are effectively screened by the MOF filter. Thus, the ZIF-8 filter on the Pd nanowires allows the predominant penetration of hydrogen molecules, leading to the acceleration of Pd-based H2 sensors with a 20-fold faster recovery and response speed compared to pristine Pd nanowires at room temperature. Professor Kim expects that the ultra-fast hydrogen sensor can be useful for the prevention of explosion accidents caused by the leakage of hydrogen gas. In addition, he expects that other harmful gases in the air can be accurately detected through effective nano-filtration by using of a variety of MOF layers. This study was carried out by Ph.D. candidate Won-Tae Koo (first author), Professor Kim (co-corresponding author), and Professor Penner (co-corresponding author). The study has been published in the online edition of ACS Nano, as the cover-featured image for the September issue. Figure 1. Representative image for this paper published in ACS Nano, August, 18. Figure 2. Images of Pd nanowire array-based hydrogen sensors, scanning electron microscopy image of a Pd nanowire covered by a metal-organic framework layer, and the hydrogen sensing properties of the sensors. Figure 3. Schematic illustration of a metal-organic framework (MOF). The MOF, consisting of metal ions and organic ligands, is a highly porous material with an ultrahigh surface area. The various structures of MOFs can be synthesized depending on the kinds of metal ions and organic ligands.
Innovative Nanosensor for Disease Diagnosis
(Figure 1. Sensing Device) (Figure 2. Protein templating route) Breath pattern recognition is a futuristic diagnostic platform. Simple characterizing target gas concentrations of human exhaled breath will lead to diagnose of the disease as well as physical condition. A research group under Prof. Il-Doo Kim in the Department of Materials Science has developed diagnostic sensors using protein-encapsulated nanocatalysts, which can diagnose certain diseases by analyzing human exhaled breath. This technology enables early monitoring of various diseases through pattern recognition of biomarker gases related to diseases in human exhalation. The protein-templated catalyst synthesis route is very simple and versatile for producing not only a single component of catalytic nanoparticles, but also diverse heterogeneous intermetallic catalysts with sizes less than 3 nm. The research team has developed ever more sensitive and selective chemiresistive sensors that can potentially diagnose specific diseases by analyzing exhaled breath gases. The results of this study, which were contributed by Dr. Sang-Joon Kim and Dr. Seon-Jin Choi as first authors were selected as the cover-featured article in the July issue of 'Accounts of Chemical Research,' an international journal of the American Chemical Society. In human breath, diverse components are found including water vapor, hydrogen, acetone, toluene, ammonia, hydrogen sulfide, and carbon monoxide, which are more excessively exhaled from patients. Some of these components are closely related to diseases such as asthma, lung cancer, type 1 diabetes mellitus, and halitosis. Breath analysis for disease diagnosis started from capturing exhaled breaths in a Tedlar bag and subsequently the captured breath gases were injected into a miniaturized sensor system, similar to an alcohol detector. It is possible to analyze exhaled breath very rapidly with a simple analyzing process. The breath analysis can detect trace changes in exhaled breath components, which contribute to early diagnosis of diseases. However, technological advances are needed to accurately analyze gases in the breath, which occur at very low levels, from 1 ppb to 1 ppm. In particular, it has been a critical challenge for chemiresistive type chemical sensors to selectively detect specific biomarkers in thousands of interfering gases including humid vapor. Conventionally, noble metallic catalysts such as platinum and palladium have been functionalized onto metal oxide sensing layers. However, the gas sensitivity was not enough to detect ppb-levels of biomarker species in exhaled breath. To overcome the current limitations, the research team utilized nanoscale protein (apoferritin) in animals as sacrificial templates. The protein templates possess hollow nanocages at the core site and various alloy catalytic nanoparticles can be encapsulated inside the protein nanocages. The protein nanocages are advantageous because a nearly unlimited number of material compositions in the periodic table can be assembled for the synthesis of heterogeneous catalytic nanoparticles. In addition, intermetallic nanocatalysts with a controlled atomic ratio of two different elements can be achieved using the protein nanocages, which is an innovative strategy for finding new types of catalysts. For example, highly efficient platinum-based catalysts can be synthesized, such as platinum-palladium (PtPd), platinum-nickel (PtNi), platinum-ruthenium (PtRu), and platinum-yttrium (PtY). The research team developed outstanding sensing layers consisting of metal oxide nanofibers functionalized by the heterogeneous catalysts with large and highly-porous surface areas, which are especially optimized for selective detection of specific biomarkers. The biomarker sensing performance was improved approximately 3~4-fold as compared to the conventional single component of platinum and palladium catalysts-loaded nanofiber sensors. In particular, 100-fold resistance transitions toward acetone (1 ppm) and hydrogen sulfide (1 ppm) were observed in exhaled breath sensors using the heterogeneous nanocatalysts, which is the best performance ever reported in literature. The research team developed a disease diagnosis platform that recognizes individual breathing patterns by using a multiple sensor array system with diverse sensing layers and heterogeneous catalysts, so that the people can easily identify health abnormalities. Using a 16-sensor array system, physical conditions can be continuously monitored by analyzing concentration changes of biomarkers in exhaled breath gases. Prof. Kim said, “New types of heterogeneous nanocatalysts were synthesized using protein templates with sizes around 2 nm and functionalized on various metal oxide nanofiber sensing layers. The established sensing libraries can detect biomarker species with high sensitivity and selectivity.” He added, “the new and innovative breath gas analysis platform will be very helpful for reducing medical expenditures and continuous monitoring of physical conditions” Patents related to this technology were licensed to two companies in March and June this year.
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