Won-Hee Ryu

Bifunctional Composite Catalysts Using Co3O4 Nanofibers Immobilized on Nonoxidized Graphene Nanoflakes for High-Capacity and Long-Cycle Li–O2 Batteries

Designing a highly efficient catalyst is essential to improve the electrochemical performance of Li-O2 batteries for long-term cycling. Furthermore, these batteries often show significant capacity fading due to the irreversible reaction characteristics of the Li2O2 product. To overcome these limitations, we propose a bifunctional composite catalyst composed of electrospun one-dimensional (1D) Co3O4 nanofibers (NFs) immobilized on both sides of the 2D nonoxidized graphene nanoflakes (GNFs) for an oxygen electrode in Li-O2 batteries. Highly conductive GNFs with noncovalent functionalization can facilitate a homogeneous dispersion in solution, thereby enabling simple and uniform attachment of 1D Co3O4 NFs on GNFs without restacking. High first discharge capacity of 10 500 mAh/g and superior cyclability for 80 cycles with a limited capacity of 1000 mAh/g were achieved by (i) improved catalytic activity of 1D Co3O4 NFs with large surface area, (ii) facile electron transport via interconnected GNFs functionalized by Co3O4 NFs, and (iii) fast O2 diffusion through the ultrathin GNF layer and porous Co3O4 NF networks.

Selective Diagnosis of Diabetes Using Pt-Functionalized WO3 Hemitube Networks As a Sensing Layer of Acetone in Exhaled Breath

Thin-walled WO(3) hemitubes and catalytic Pt-functionalized WO(3) hemitubes were synthesized via a polymeric fiber-templating route and used as exhaled breath sensing layers for potential diagnosis of halitosis and diabetes through the detection of H(2)S and CH(3)COCH(3), respectively. Pt-functionalized WO(3) hemitubes with wall thickness of 60 nm exhibited superior acetone sensitivity (R(air)/R(gas) = 4.11 at 2 ppm) with negligible H(2)S response, and pristine WO(3) hemitubes showed a 4.90-fold sensitivity toward H(2)S with minimal acetone-sensing characteristics. The detection limit (R(air)/R(gas)) of the fabricated sensors with Pt-functionalized WO(3) hemitubes was 1.31 for acetone of 120 ppb, and pristine WO(3) hemitubes showed a gas response of 1.23 at 120 ppb of H(2)S. Long-term stability tests revealed that the remarkable selectivity has been maintained after aging for 7 months in air. The superior cross-sensitivity and response to H(2)S and acetone gas offer a potential platform for application in diabetes and halitosis diagnosis.

Development of Omniphobic Desalination Membranes Using a Charged Electrospun Nanofiber Scaffold

In this study, we present a facile and scalable approach to fabricate omniphobic nanofiber membranes by constructing multilevel re-entrant structures with low surface energy. We first prepared positively charged nanofiber mats by electrospinning a blend polymer-surfactant solution of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) and cationic surfactant (benzyltriethylammonium). Negatively charged silica nanoparticles (SiNPs) were grafted on the positively charged electrospun nanofibers via dip-coating to achieve multilevel re-entrant structures. Grafted SiNPs were then coated with fluoroalkylsilane to lower the surface energy of the membrane. The fabricated membrane showed excellent omniphobicity, as demonstrated by its wetting resistance to various low surface tension liquids, including ethanol with a surface tension of 22.1 mN/m. As a promising application, the prepared omniphobic membrane was tested in direct contact membrane distillation to extract water from highly saline feed solutions containing low surface tension substances, mimicking emerging industrial wastewaters (e.g., from shale gas production). While a control hydrophobic PVDF-HFP nanofiber membrane failed in the desalination/separation process due to low wetting resistance, our fabricated omniphobic membrane exhibited a stable desalination performance for 8 h of operation, successfully demonstrating clean water production from the low surface tension feedwater.

Structural enhancement of Na3V2(PO4)3/C composite cathode materials by pillar ion doping for high power and long cycle life sodium-ion batteries

Structurally stabilized Na3V2(PO4)3/C composite cathode materials with excellent electrochemical performance can be obtained by incorporating functional pillar ions into the structure. As pillar ions, K-ions have a larger ionic radius compared to Na-ions, and play an important role in enlarging the Na-ion diffusion pathway and in increasing the lattice volume by elongating the c-axis, thereby improving the rate performance. Furthermore, since the incorporated K-ions rarely participate in the electrochemical extraction/insertion reactions, they can stabilize the Na3V2(PO4)3 structure by suppressing significant lattice volume changes or structural distortion, even in a wide range of voltage windows accompanying multiple transitions of V ions and phase distortions. We investigated how the K-ion doping level affected the crystal structure and electrochemical properties of Na3V2(PO4)3 cathode materials for Na-ion batteries.

Fabrication of Graphene Embedded LiFePO4 Using a Catalyst Assisted Self Assembly Method as a Cathode Material for High Power Lithium-Ion Batteries

We have designed a unique microstructure of graphene embedded LiFePO4 by a catalyst assisted self assembly method as a cathode material for high power lithium-ion batteries. The stable amide bonds between LiFePO4 and graphene were formed by the catalyst assisted self assembly. High conductive graphene provides a fast electron transfer path, and many pores inside the structure facilitate the lithium-ion diffusion. The graphene embedded LiFePO4 fabricated by the novel method shows enhanced cycling performance and rate-capability compared with that of carbon coated LiFePO4 as a cathode material for high power lithium-ion batteries.

Heterogeneous WSx/WO3 Thorn-Bush Nanofiber Electrodes for Sodium-Ion Batteries

Heterogeneous electrode materials with hierarchical architectures promise to enable considerable improvement in future energy storage devices. In this study, we report on a tailored synthetic strategy used to create heterogeneous tungsten sulfide/oxide core-shell nanofiber materials with vertically and randomly aligned thorn-bush features, and we evaluate them as potential anode materials for high-performance Na-ion batteries. The WSx (2 ≤ x ≤ 3, amorphous WS3 and crystalline WS2) nanofiber is successfully prepared by electrospinning and subsequent calcination in a reducing atmosphere. To prevent capacity degradation of the WSx anodes originating from sulfur dissolution, a facile post-thermal treatment in air is applied to form an oxide passivation surface. Interestingly, WO3 thorn bundles are randomly grown on the nanofiber stem, resulting from the surface conversion. We elucidate the evolving morphological and structural features of the nanofibers during post-thermal treatment. The heterogeneous thorn-bush nanofiber electrodes deliver a high second discharge capacity of 791 mAh g(-1) and improved cycle performance for 100 cycles compared to the pristine WSx nanofiber. We show that this hierarchical design is effective in reducing sulfur dissolution, as shown by cycling analysis with counter Na electrodes.

Cobalt(II) monoxide nanoparticles embedded in porous carbon nanofibers as a highly reversible conversion reaction anode for Li-ion batteries

CoO nanoparticles embedded in porous carbon nanofibers (CNFs), which are used as a novel conversion reaction anode electrode, are successfully synthesized via one-step electrospinning and subsequent calcination in an Ar atmosphere. High capacity, excellent cyclability, and superior rate capability are achieved by a highly reversible conversion reaction of CoO nanoparticles and facile electron transport through highly conductive CNFs.

Synergistic effects of various morphologies and Al doping of spinel LiMn2O4 nanostructures on the electrochemical performance of lithium-rechargeable batteries

Nanostructured electrodes have recently received great attention as components in lithium rechargeable batteries, especially because of the high power produced by the fast kinetic properties of these unique structures. Here, we report the successful synthesis of various nanostructured morphologies of spinel lithium manganese oxide electrodes (nanorod, nanothorn sphere, and sphere) from a similarly shaped manganese dioxide precursor that was controlled with different aluminium contents by the hydrothermal method. Among these structures, nanothorn sphere structured LiAl0.02Mn1.98O4 produces the highest discharge capacity of 129.8 mA h g−1, excellent rate capability (94.6 mA h g−1 at 20 C, 72% of 0.2 C-rate discharge capacity) and stable cyclic retention for 50 cycles. The excellent kinetic properties of the nanothorn sphere structure are not only due to the nanothorn sphere electrode having high surface area but also because the critical amount of Al in the nanothorn sphere electrode was located at the Mn site (16d) instead of the Li site (8a).

A Mesoporous Catalytic Membrane Architecture for Lithium–Oxygen Battery Systems

Controlling the mesoscale geometric configuration of catalysts on the oxygen electrode is an effective strategy to achieve high reversibility and efficiency in Li-O2 batteries. Here we introduce a new Li-O2 cell architecture that employs a catalytic polymer-based membrane between the oxygen electrode and the separator. The catalytic membrane was prepared by immobilization of Pd nanoparticles on a polyacrylonitrile (PAN) nanofiber membrane and is adjacent to a carbon nanotube electrode loaded with Ru nanoparticles. During oxide product formation, the insulating PAN polymer scaffold restricts direct electron transfer to the Pd catalyst particles and prevents the direct blockage of Pd catalytic sites. The modified Li-O2 battery with a catalytic membrane showed a stable cyclability for 60 cycles with a capacity of 1000 mAh/g and a reduced degree of polarization (∼ 0.3 V) compared to cells without a catalytic membrane. We demonstrate the effects of a catalytic membrane on the reaction characteristics associated with morphological and structural features of the discharge products via detailed ex situ characterization.

Morphological Evolution of Carbon Nanofibers Encapsulating SnCo Alloys and Its Effect on Growth of the Solid Electrolyte Interphase Layer

Two distinctive one-dimensional (1-D) carbon nanofibers (CNFs) encapsulating irregularly and homogeneously segregated SnCo nanoparticles were synthesized via electrospinning of polyvinylpyrrolidone (PVP) and polyacrylonitrile (PAN) polymers containing Sn-Co acetate precursors and subsequent calcination in reducing atmosphere. CNFs synthesized with PVP, which undergoes structural degradation of the polymer during carbonization processes, exhibited irregular segregation of heterogeneous alloy particles composed of SnCo, Co3Sn2, and SnO with a size distribution of 30-100 nm. Large and exposed multiphase SnCo particles in PVP-driven amorphous CNFs (SnCo/PVP-CNFs) kept decomposing liquid electrolyte and were partly detached from CNFs during cycling, leading to a capacity fading at the earlier cycles. The closer study of solid electrolyte interphase (SEI) layers formed on the CNFs reveals that the gradual growth of fiber radius due to continuous increment of SEI layer thickness led to capacity fading. In contrast, SnCo particles in PAN-driven CNFs (SnCo/PAN-CNFs) showed dramatically reduced crystallite sizes (<10 nm) of single phase SnCo nanoparticles which were entirely embedded in dense, semicrystalline, and highly conducting 1-D carbon matrix. The growth of SEI layer was limited and saturated during cycling. As a result, SnCo/PAN-CNFs showed much improved cyclability (97.9% capacity retention) and lower SEI layer thickness (86 nm) after 100 cycles compared to SnCo/PVP-CNFs (capacity retention, 71.9%; SEI layer thickness, 593 nm). This work verifies that the thermal behavior of carbon precursor is highly responsible for the growth mechanism of SEI layer accompanied with particles detachment and cyclability of alloy particle embedded CNFs.