Time-Resolved Structural Kinetics of an Organic Mixed Ionic–Electronic Conductor

The structure and packing of organic mixed ionic–electronic conductors have an especially significant effect on transport properties. In operating devices, this structure is not fixed but is responsive to changes in electrochemical potential, ion intercalation, and solvent swelling. Toward this end, the steady-state and transient structure of the model organic mixed conductor, poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), is characterized using multimodal time-resolved operando techniques. Steady-state operando X-ray scattering reveals a doping-induced lamellar expansion of 1.6 Å followed by 0.4 Å relaxation at high doping levels. Time-resolved operando X-ray scattering reveals asymmetric rates of lamellar structural change during doping and dedoping that do not directly depend on potential or charging transients. Time-resolved spectroscopy establishes a link between structural transients and the complex kinetics of electronic charge carrier subpopulations, in particular the polaron–bipolaron equilibrium. These findings provide insight into the factors limiting the response time of organic mixed-conductor-based devices, and present the first real-time observation of the structural changes during doping and dedoping of a conjugated polymer system via X-ray scattering.     

Recent Developments and Applications of Ionic Liquids in Gas Separation Membranes

Flue gas emissions and the harmful effects of these gases urge to separate and capture these unwanted gases. Ionic liquids due to negligible vapor pressure, thermal stability, and wide electrochemical stability have expanded its application in gas separations. A comprehensive overview of the recent developments and applications of ionic liquid membranes (ILMs) for gas separation is given. The three general classifications of ILMs, such as supported ionic liquid membranes (SILMs), ionic liquid polymeric membranes (ILPMs), and ionic liquid mixed‐matrix membranes (ILMMMs) along with their applications, for the separation of various mixed gases systems is discussed in detail. Furthermore, issues, challenges, computational study, and future perspectives for ILMs are also considered.     

Thermodiffusion‐Assisted Pyroelectrics—Enabling Rapid and Stable Heat and Radiation Sensing

Sensors for monitoring temperature, heat flux, and thermal radiation are essential for applications such as electronic skin. While pyroelectric and thermoelectric effects are suitable candidates as functional elements in such devices, both concepts show individual drawbacks in terms of zero equilibrium signals for pyroelectric materials and small or slow response of thermoelectric materials. Here, these drawbacks are overcome by introducing the concept of thermodiffusion‐assisted pyroelectrics, which combines and enhances the performance of pyroelectric and ionic thermoelectric materials. The presented integrated concept provides both rapid initial response upon heating and stable synergistically enhanced signals upon prolonged exposure to heat stimuli. Likewise, incorporation of plasmonic metasurfaces enables the concept to provide both rapid and stable signals for radiation‐induced heating. The performance of the concept and its working mechanism can be explained by ion–electron interactions at the interface between the pyroelectric and ionic thermoelectric materials.     

Pressureless all-solid-state sodium-ion battery consisting of sodium iron pyrophosphate glass-ceramic cathode and β″-alumina solid electrolyte composite

In recent years, the expansion of demand for lithium ion batteries has resulted in soaring prices of the constituent resources. From the viewpoint of safety, studies on all-solid-state batteries are actively being carried out. In this study, we succeeded in driving all-solid-state batteries derived from nontoxic oxide glasses at room temperature without requiring scarce resources such as lithium and cobalt. The main structure of the ceramic batteries with a simple structure in which Na₂FeP₂O₇ crystallized glass and β″-alumina solid solution are joined by pressureless cofiring at 550°C. During the crystallization of Na₂O-Fe₂O₃-P₂O₅ glass, fusion with the β″-alumina solid solution is achieved. Reversible charge and discharge of 80 mAh/g were achieved at room temperature. It is not necessary to apply pressure during cell preparation or the use of the batteries. Furthermore, the strong junction at the cathode and electrolyte interface does not peel off during charge and discharge over a long period of 623 cycles. Ex situ X-ray photoelectron spectroscopy revealed partial Fe⁴⁺ induction and a reversible charge and discharge reaction even after overcharging to 9 V. It was demonstrated that Na₂FeP₂O₇ is very stable against overcharging to 9 V.     

Producing Fatty Acid Methyl Esters from Free Fatty Acids with Ionic Liquids as Catalyst

Three Brønsted acidic imidazole dicationic ionic liquids (ILs) with different length of alkyl chains, [C_n(Mim)₂][HSO₄]₂ (n = 3, 6, 12), were prepared and used as catalyst for the esterification reaction of free fatty acids and methanol. Taking oleic acid as model acid, the catalytic performances of the synthesized ILs for the esterification were evaluated. The main physicochemical properties of the ILs, thermal stability, acidity, solubility in common solvents, and causticity on Austenitic stainless steel 316, were examined. [C₃(Mim)₂][HSO₄]₂ demonstrated the highest catalytic activity and enabled to assess the preliminary optimum esterification condition of oleic acid and methanol. Under optimized reaction conditions, the yield of oleic acid methyl ester was up to 95 %. The ILs have great potential as catalysts for producing fatty acid methyl esters from long‐chain free fatty acids.     

Humidity-Induced Simultaneous Visible and Fluorescence Photonic Patterns Enabled by Integration of Covalent Bonds and Ionic Crosslinks

Stimuli-responsive photonic crystals (PCs) have been extensively studied due to their potential in fabrication of anti-counterfeiting devices and information storage. In this work, using Ca²⁺ ionic crosslinker, a cholesteric liquid crystalline network (CLCN) based PC able to simultaneously present visible and fluorescence pattern by moisture treatment is designed and prepared. The circularly polarized light from helical structure of CLCN makes the reflected pattern distinguishable under different circular polarizer, implying the unique advantage of this novel coating as anti-counterfeiting devices. More importantly, due to the thermochromic property of the liquid crystal monomers, permanent pattern is achievable by chemically crosslinking specific region at different temperature. By integrating chemically crosslinking and physically ionic crosslinking, a permanent pattern and a dynamic humidity responsive pattern can be incorporated in a single device, indicating the great potential of this novel photonic coating in information storage.     

Simulation studies on a rotating ring disk electrode: Effects of ionic migration with kinetic complication-disk results

In continuation to my previous work (Guha S. AIChE J. 2013;59(4):1390-1399), in this work, effects of ionic migration are evaluated for disk region of a rotating ring disk electrode system by numerically solving complex differential equations, developed for mass transfer along with kinetic complication in presence of ionic migration under limiting current condition. The system for simulation is 0.01 M Fe₂(SO₄)₃ solution with H₂SO₄ as supporting electrolyte. Simulation cases are presence and absence of ionic migration with kinetic complication (oxidation of Fe²⁺ to Fe³⁺ under O₂ pressure). Results show that concentration boundary layer thickness of reactant Fe³⁺ reduces appreciably and steady-state disk current reduces substantially in presence of migration. Simulated steady-state disk current in absence of migration case agrees well with published data. Results indicate higher Fe²⁺ concentration in presence of migration and thereby higher rate of oxidation of Fe²⁺ to Fe³⁺ at all rate constant values.     

Novel composite membrane based on zirconium phosphate-ionic liquids for high temperature PEM fuel cells

Composite membranes composed of zirconium phosphate (ZrP) and imidazolium-based ionic liquids (IL), supported on polytetrafluoroethylene (PTFE) were prepared and evaluated for their application in proton exchange membrane fuel cells (PEM) operating at 200 °C. The experimental results reported here demonstrate that the synthesized membrane has a high proton conductivity of 0.07 S cm^?1, i.e, 70% of that reported for Nafion. Furthermore, the composite membranes possess a very high proton conductivity of 0.06 S cm^?1 when processed at 200 °C under completely anhydrous conditions. Scanning electron microscopy (SEM) images indicate the formation of very small particles, with diameters in the range of 100–300 nm, within the confined pores of PTFE. Thermogravimetric analysis (TGA) reveals a maximum of 20% weight loss up to 500 °C for the synthesized membrane. The increase in proton conductivity is attributed to the creation of multiple proton conducting paths within the membrane matrix. The IL component is acting as a proton bridge. Therefore, these membranes have potential for use in PEM fuel cells operating at temperatures around 200 °C.