Heeman Choe

Self-assembled Fe3O4 nanoparticle clusters as high-performance anodes for lithium ion batteries via geometric confinement.

Although different kinds of metal oxide nanoparticles continue to be proposed as anode materials for lithium ion batteries (LIBs), their cycle life and power density are still not suitable for commercial applications. Metal oxide nanoparticles have a large storage capacity, but they suffer from the excessive generation of solid-electrolyte interphase (SEI) on the surface, low electrical conductivity, and mechanical degradation and pulverization resulted from severe volume expansion during cycling. Herein we present the preparation of mesoporous iron oxide nanoparticle clusters (MIONCs) by a bottom-up self-assembly approach and demonstrate that they exhibit excellent cyclic stability and rate capability derived from their three-dimensional mesoporous nanostructure. By controlling the geometric configuration, we can achieve stable interfaces between the electrolyte and active materials, resulting in SEI formation confined on the outer surface of the MIONCs.

Ordered macroporous platinum electrode and enhanced mass transfer in fuel cells using inverse opal structure

Three-dimensional, ordered macroporous materials such as inverse opal structures are attractive materials for various applications in electrochemical devices because of the benefits derived from their periodic structures: relatively large surface areas, large voidage, low tortuosity and interconnected macropores. However, a direct application of an inverse opal structure in membrane electrode assemblies has been considered impractical because of the limitations in fabrication routes including an unsuitable substrate. Here we report the demonstration of a single cell that maintains an inverse opal structure entirely within a membrane electrode assembly. Compared with the conventional catalyst slurry, an ink-based assembly, this modified assembly has a robust and integrated configuration of catalyst layers; therefore, the loss of catalyst particles can be minimized. Furthermore, the inverse-opal-structure electrode maintains an effective porosity, an enhanced performance, as well as an improved mass transfer and more effective water management, owing to its morphological advantages.

3D macroporous electrode and high-performance in lithium-ion batteries using SnO2 coated on Cu foam.

A three-dimensional porous architecture makes an attractive electrode structure, as it has an intrinsic structural integrity and an ability to buffer stress in lithium-ion batteries caused by the large volume changes in high-capacity anode materials during cycling. Here we report the first demonstration of a SnO2-coated macroporous Cu foam anode by employing a facile and scalable combination of directional freeze-casting and sol-gel coating processes. The three-dimensional interconnected anode is composed of aligned microscale channels separated by SnO2-coated Cu walls and much finer micrometer pores, adding to surface area and providing space for volume expansion of SnO2 coating layer. With this anode, we achieve a high reversible capacity of 750 mAh g−1 at current rate of 0.5 C after 50 cycles and an excellent rate capability of 590 mAh g−1 at 2 C, which is close to the best performance of Sn-based nanoscale material so far.

Facile and Gram-scale Synthesis of Metal-free Catalysts: Toward Realistic Applications for Fuel Cells

Although numerous reports on nonprecious metal catalysts for replacing expensive Pt-based catalysts have been published, few of these studies have demonstrated their practical application in fuel cells. In this work, we report graphitic carbon nitride and carbon nanofiber hybrid materials synthesized by a facile and gram-scale method via liquid-based reactions, without the use of toxic materials or a high pressure-high temperature reactor, for use as fuel cell cathodes. The resulting materials exhibited remarkable methanol tolerance, selectivity, and stability even without a metal dopant. Furthermore, these completely metal-free catalysts exhibited outstanding performance as cathode materials in an actual fuel cell device: a membrane electrode assembly with both acidic and alkaline polymer electrolytes. The fabrication method and remarkable performance of the single cell produced in this study represent progressive steps toward the realistic application of metal-free cathode electrocatalysts in fuel cells.

Iron Oxide Photoelectrode with Multidimensional Architecture for Highly Efficient Photoelectrochemical Water Splitting

Nanostructured metal oxide semiconductors have shown outstanding performances in photoelectrochemical (PEC) water splitting, but limitations in light harvesting and charge collection have necessitated further advances in photoelectrode design. Herein, we propose anodized Fe foams (AFFs) with multidimensional nano/micro-architectures as a highly efficient photoelectrode for PEC water splitting. Fe foams fabricated by freeze-casting and sintering were electrochemically anodized and directly used as photoanodes. We verified the superiority of our design concept by achieving an unprecedented photocurrent density in PEC water splitting over 5 mA cm-2 before the dark current onset, which originated from the large surface area and low electrical resistance of the AFFs. A photocurrent of over 6.8 mA cm-2 and an accordingly high incident photon-to-current efficiency of over 50 % at 400 nm were achieved with incorporation of Co oxygen evolution catalysts. In addition, research opportunities for further advances by structual and compositional modifications are discussed, which can resolve the low fill factoring behavior and improve the overall performance.

3D interconnected SnO2-coated Cu foam as a high-performance anode for lithium-ion battery applications

A SnO2-coated Cu foam with 3D interconnected scaffold was fabricated by a simple sol–gel method for use as a self-supporting anode for lithium-ion batteries. The binder- and carbon-free electrode integrated with a current collector exhibits a high reversible capacity, excellent rate capability, and stable cycle retention by preserving its structural integrity.

Next-Generation Polymer-Electrolyte-Membrane Fuel Cells Using Titanium Foam as Gas Diffusion Layer

In spite of their high conversion efficiency and no emission of greenhouse gases, polymer electrolyte membrane fuel cells (PEMFCs) suffer from prohibitively high cost and insufficient life-span of their core component system, the membrane electrode assembly (MEA). In this paper, we are proposing Ti foam as a promising alternative electrode material in the MEA. Indeed, it showed a current density of 462 mA cm(-2), being ca. 166% higher than that with the baseline Toray 060 gas diffusion layer (GDL) (278 mA cm(-2)) with 200 ccm oxygen supply at 0.7 V, when used as the anode GDL, because of its unique three-dimensional strut structure promoting highly efficient catalytic reactions. Furthermore, it exhibits superior corrosion resistance with almost no thickness and weight changes in the accelerated corrosion test, as opposed to considerable reductions in the weight and thickness of the conventional GDL. We believe that this paper suggests profound implications in the commercialization of PEMFCs, because the metallic Ti foam provides a longer-term reliability and chemical stability, which can reduce the loss of Pt catalyst and, hence, the cost of PEMFCs.

Mechanical behavior and microstructure of compressed Ti foams synthesized via freeze casting.

Pure Ti and Ti-5%W foams were prepared via freeze casting. The porosity and grain size of both the materials were 32-33% and 15-17µm, respectively. The mechanical behavior of the foams was investigated by uniaxial compression up to a plastic strain of ~0.26. The Young׳s moduli of both foams were ~23GPa, which was in good agreement with the value expected from their porosity. The Young׳s moduli of the foams were similar to the elastic modulus of cortical bones, thereby eliminating the osteoporosis-causing stress-shielding effect. The addition of W increased the yield strength from ~196MPa to ~235MPa. The microstructure evolution in the grains during compression was studied using electron backscatter diffraction (EBSD) and X-ray line profile analysis (XLPA). After compression up to a plastic strain of ~0.26, the average dislocation densities increased to ~3.4×10(14)m(-2) and ~5.9×10(14)m(-2) in the Ti and Ti-W foams, respectively. The higher dislocation density in the Ti-W foam can be attributed to the pinning effect of the solute tungsten atoms on dislocations. The experimentally measured yield strength was in good agreement with the strength calculated from the dislocation density and porosity. This study demonstrated that the addition of W to Ti foam is beneficial for biomedical applications, because the compressive yield strength increased while its Young׳s modulus remained similar to that of cortical bones.

Tribological properties of biocompatible Ti–10W and Ti–7.5TiC–7.5W

This study investigates and compares the microstructure, biocompatibility, and tribological properties of two different Ti-based composites, Ti-10W and Ti-7.5TiC-7.5W, with those of pure Ti for their potential use in biomedical applications. In particular, cold and hot isostatic-pressing and arc-melting methods were utilized and compared for the microstructure of the composites. Nano-scratch measurements and pin-on-disk wear tests were employed to understand their tribological behavior. As compared to pure Ti, Ti-10W and Ti-7.5TiC-7.5W showed significantly improved nano-scratch resistance (by 85 and 77%, respectively) and wear resistance (by 64 and 66%, respectively), in good agreement with hardness measurements. For biocompatibility examination, both microculture tetrazolium test (MTT) and water soluble tetrazolium (WST-1) test were used to quantify the cell viability of human osteoblasts and mouse fibroblasts on the materials. Both of the Ti-based composites showed acceptable biocompatibility in comparison with the pure Ti control.

Study of the compression and wear-resistance properties of freeze-cast Ti and Ti‒5W alloy foams for biomedical applications

Ti and Ti‒5wt% W alloy foams were produced by freeze-casting process and their mechanical behaviors were compared. The Ti‒5W alloy foam showed a typical acicular Widmanstätten α/β structure with most of the W dissolved in the β phase. An electron-probe microanalysis revealed that approximately 2wt% W was uniformly dissolved in the Ti matrix of Ti‒5W alloy foam with few partially dissolved W particles. The compressive-yield strength of Ti‒5W alloy foam (~323MPa) was approximately 20% higher than that of the Ti foam (~256MPa) owing to the solid-solution-strengthening effect of W in the Ti matrix, which also resulted in a dramatic improvement in the wear resistance of Ti‒5W alloy foam. The compressive behaviors of the Ti and Ti‒5W alloy foams were predicted by analytical models and compared with the experimental values. Compared with the Gibson-Ashby and cellular-lattice-structure-in-square-orientation models of porous materials, the orientation-averaging method provided prediction results that are much more accurate in terms of both the Youngs modulus and the yield strength of the Ti and Ti‒5W alloy foams.