Moon Jeong Park

Synthesis of three-dimensionally interconnected sulfur-rich polymers for cathode materials of high-rate lithium–sulfur batteries

Elemental sulfur is one of the most attractive cathode active materials in lithium batteries because of its high theoretical specific capacity. Despite the positive aspect, lithium–sulfur batteries have suffered from severe capacity fading and limited rate capability. Here we report facile large-scale synthesis of a class of organosulfur compounds that could open a new chapter in designing cathode materials to advance lithium–sulfur battery technologies. Porous trithiocyanuric acid crystals are synthesized for use as a soft template, where the ring-opening polymerization of elemental sulfur takes place along the thiol surfaces to create three-dimensionally interconnected sulfur-rich phases. Our lithium–sulfur cells display discharge capacity of 945 mAh g−1 after 100 cycles at 0.2 C with high-capacity retention of 92%, as well as lifetimes of 450 cycles. Particularly, the organized amine groups in the crystals increase Li+-ion transfer rate, affording a rate performance of 1210, mAh g−1 at 0.1 C and 730 mAh g−1 at 5 C.

Enhanced proton transport in nanostructured polymer electrolyte/ionic liquid membranes under water-free conditions

Proton exchange fuel cells (PEFCs) have the potential to provide power for a variety of applications ranging from electronic devices to transportation vehicles. A major challenge towards economically viable PEFCs is finding an electrolyte that is both durable and easily passes protons. In this article, we study novel anhydrous proton-conducting membranes, formed by incorporating ionic liquids into synthetic block co-polymer electrolytes, poly(styrenesulphonate-b-methylbutylene) (S(n)MB(m)), as high-temperature PEFCs. The resulting membranes are transparent, flexible and thermally stable up to 180 °C. The increases in the sulphonation level of S(n)MB(m) co-polymers (proton supplier) and the concentration of the ionic liquid (proton mediator) produce an overall increase in conductivity. Morphology effects were studied by X-ray scattering and electron microscopy. Compared with membranes having discrete ionic domains (including Nafion 117), the nanostructured membranes revealed over an order of magnitude increase in conductivity with the highest conductivity of 0.045 S cm(-1) obtained at 165 °C.

Fast low-voltage electroactive actuators using nanostructured polymer electrolytes

Electroactive actuators have received enormous interest for a variety of biomimetic technologies ranging from robotics and microsensors to artificial muscles. Major challenges towards practically viable actuators are the achievement of large electromechanical deformation, fast switching response, low operating voltage and durable operation. Here we report a new electroactive actuator composed of self-assembled sulphonated block copolymers and ionic liquids. The new actuator demonstrated improvements in actuation properties over other polymer actuators reported earlier, large generated strain (up to 4%) without any signs of back relaxation. In particular, the millimetre-scale displacements obtained for the actuators, with rapid response (<1 s) at sub-1-V conditions over 13,500 cycles in air, have not been previously reported in the literature. The key to success stems from the evolution of the unique hexagonal structure of the polymer layer with domain size gradients beneath the cathode during actuation, which promotes the bending motion of the actuators.

Colorimetric and Resistive Polymer Electrolyte Thin Films for Real-time Humidity Sensors

We have developed fast responsive, colorimetric and resistive-type polymeric humidity sensors from a series of self-assembled poly(styrenesulfonate-methylbutylene) (PSS-b-PMB) block copolymers with tailored hygroscopic properties. In dry state, the PSS-b-PMB films exhibit hexagonal cylindrical morphology where hydrophobic PMB cylinders are dispersed within a PSS matrix. Under levels of humidity, the PSS-b-PMB thin films self-displayed discernible reflective color changes, covering almost entire visible light regions from violet (RH = 20%) to red (RH = 95%). The sensors also revealed a few orders of magnitude changes in impedance with exposure to humid air by taking advantages of strong polymer electrolytes characteristics. Remarkably, the time to complete the changes in the signals was only a few seconds, as rationalized by good connectivity of the PSS domains and short water diffusion pathways in nanometer scales. Repeated hydration/dehydration tests demonstrated reliable sensor properties, which is in sharp contrast to the poor stability of PSS homopolymer sensors lacking organization.

Temperature-dependent micellar structures in poly(styrene-b-isoprene) diblock copolymer solutions near the critical micelle temperature

The temperature dependence of the micelle structures formed by poly(styrene-b-isoprene) (SI) diblock copolymers in the selective solvents diethyl phthalate (DEP) and tetradecane (C14), which are selective for the PS and PI blocks, respectively, have been investigated by small angle neutron scattering (SANS). Two nearly symmetric SI diblock copolymers, one with a perdeuterated PS block and the other with a perdeuterated PI block, were examined in both DEP and C14. The SANS scattering length density of the solvent was matched closely to either the core or the corona block. The resulting core and corona contrast data were fitted with a detailed model developed by Pedersen and co-workers. The fits provide quantitative information on micellar characteristics such as aggregation number, core size, overall size, solvent fraction in the core, and corona thickness. As temperature increases, the solvent selectivity decreases, leading to substantial solvent swelling of the core and a decrease in the aggregation number and core size. Both core and corona chains are able to relax their conformations near the critical micelle temperature due to a decrease in the interfacial tension, even though the corona chains are always under good solvent conditions.

Minimization of focused ion beam damage in nanostructured polymer thin films.

Focused ion beam (FIB) instruments have proven to be an invaluable tool for transmission electron microscopy (TEM) sample preparation. FIBs enable relatively easy and site-specific cross-sectioning of different classes of materials. However, damage mechanisms due to ion bombardment and possible beam heating effects in materials limit the usefulness of FIBs. Materials with adequate heat conductivity do not suffer from beam heating during FIB preparation, and artifacts in materials such as metals and ceramics are primarily limited to defect generation and Ga implantation. However, in materials such as polymers or biological structures, where heat conductivity is low, beam heating can also be a problem. In order to examine FIB damage in polymers we have undertaken a systematic study by exposing sections of a PS-b-PMMA block copolymer to the ion beam at varying beam currents and sample temperatures. The sections were then examined by TEM and scanning electron microscopy (SEM) and analyzed using electron energy loss spectroscopy (EELS). Our empirical results show beam heating in polymers due to FIB preparation can be limited by maintaining a low beam current (≤100pA) during milling.

High-Conductivity Two-Dimensional Polyaniline Nanosheets Developed on Ice Surfaces†

A new method to develop two-dimensional PANI nanosheets using ice as a removable hard template is presented. Distinctly high current flows of 5.5 mA at 1 V and a high electrical conductivity of 35 S cm(-1) were obtained for the polyaniline (PANI) nanosheets, which marked a significant improvement from previously values on other PANIs reported over the past decades. These improved electrical properties of ice-templated PANI nanosheets were attributed to the long-range ordered edge-on π-stacking of the quinoid ring, ascribed to the ice surface-assisted vertical growth of PANI. The unprecedented advantages of the ice-templated PANI nanosheets are two-fold. First, the PANI nanosheet can be easily transferred onto various types of substrates via float-off from the ice surfaces. Second, PANI can be patterned into any shape using predetermined masks, and this is expected to facilitate the eventual convenient and inexpensive application of conducting polymers in versatile electronic device forms.

Nanotopography-Guided Migration of T Cells

T cells navigate a wide variety of tissues and organs for immune surveillance and effector functions. Although nanoscale topographical structures of extracellular matrices and stromal/endothelial cell surfaces in local tissues may guide the migration of T cells, there has been little opportunity to study how nanoscale topographical features affect T cell migration. In this study, we systematically investigated mechanisms of nanotopography-guided migration of T cells using nanoscale ridge/groove surfaces. The velocity and directionality of T cells on these nanostructured surfaces were quantitatively assessed with and without confinement, which is a key property of three-dimensional interstitial tissue spaces for leukocyte motility. Depending on the confinement, T cells exhibited different mechanisms for nanotopography-guided migration. Without confinement, actin polymerization-driven leading edge protrusion was guided toward the direction of nanogrooves via integrin-mediated adhesion. In contrast, T cells under confinement appeared to migrate along the direction of nanogrooves purely by mechanical effects, and integrin-mediated adhesion was dispensable. Therefore, surface nanotopography may play a prominent role in generating migratory patterns for T cells. Because the majority of cells in periphery migrate along the topography of extracellular matrices with much lower motility than T cells, nanotopography-guided migration of T cells would be an important strategy to efficiently perform cell-mediated immune responses by increasing chances of encountering other cells within a given amount of time.

Two Gel States of a PEO-PPO-PEO Triblock Copolymer Formed by Different Mechanisms

We are very grateful to the financial support from the National Research Laboratory Fund (Grant M1- 0104-00-0191) by the Ministry of Science and Technology of Korea, the Brain Korea 21 Program endorsed by the Ministry of Education of Korea, and the Seoul National University Nanoelectronics Institute. Experiments performed at Pohang Light Source (PLS) were supported by MOST.

Phase behavior of a PEO-PPO-PEO triblock copolymer in aqueous solutions: Two gelation mechanisms

Phase behavior of a PEO-PPO-PEO (Pluronic P103) triblock copolymer in water is investigated using small-angle neutron scattering (SANS), small-angle X-ray scattering (SAXS), dynamic light scattering (DLS) and rheology. Pluronic P103 shows apparent two gel states in different temperature regions. The first sol-to-gel transition at a lower temperature (i.e., the hard gel I state) turns out to be the hexagonal microphase as evidenced by the combined SANS and SAXS and the frequency dependence of bothG′ andG′ in rheology. In contrast to the hard gel I, the second sol-to-gel transition (i.e., the hard gel II state) at a higher temperature represents the block copolymer micelles in somewhat disordered state rather than the ordered state seen in the hard gel I. Moreover, turbidity change depending only on the temperature with four distinct regions is observed and the large aggregates with size larger than 5,000 nm are detected with DLS in the turbid solution region. Based upon the present study, two different gelation mechanisms for aqueous PEO-PPO-PEO triblock copolymer solutions are proposed.