Stable Zinc Electrode Reaction Enabled by Combined Cationic and Anionic Electrolyte Additives for Non-Flow Aqueous Zn─Br2 Batteries.

Aqueous zinc-bromine batteries hold immense promise for large-scale energy storage systems due to their inherent safety and high energy density. However, achieving a reliable zinc metal electrode reaction is challenging because zinc metal in the aqueous electrolyte inevitably leads to dendrite growth and related side reactions, resulting in rapid capacity fading. Here, it is reported that combined cationic and anionic additives in the electrolytes using CeCl3 can simultaneously address the multiple chronic issues of the zinc metal electrode. Trivalent Ce3+ forms an electrostatic shielding layer to prevent Zn2+ from concentrating at zinc metal protrusions, while the high electron-donating nature of Cl- mitigates H2O decomposition on the zinc metal surface by reducing the interaction between Zn2+ and H2O. These combined cationic and anionic effects significantly enhance the reversibility of the zinc metal reaction, allowing the non-flow aqueous Zn─Br2 full-cell to reliably cycle with exceptionally high capacity (>400 mAh after 5000 cycles) even in a large-scale battery configuration of 15 × 15 cm2.

A Gram Scale Soft-Template Synthesis of Heteroatom Doped Nanoporous Hollow Carbon Spheres for Oxygen Reduction Reaction.

Heteroatom-doped nanoporous carbon materials with unique hierarchical structures have been shown to be promising supports and catalysts for energy conversion; however, hard-template methods are limited by their inflexibility and time-consuming process. Soft-template methods have been suggested as an alternative, but they are limited by their picky requirements for stable reactions and the few known precursors for small-batch synthesis. In this study, a gram-scale soft-template-based silica-assisted method was investigated for producing nitrogen-doped hollow nanoporous carbon spheres (N-HNCS). Nitrogen doping is accomplished during preparation with enhanced electrocatalytic activity without complicating the methodology. To investigate the effect of the unique structural characteristics of N-HNCS (specific surface area: 1250 m2 g-1; pore volume: 1.2 cm3 g-1), cobalt was introduced as an active center for the oxygen reduction reaction. Finely tuned reaction conditions resulted in well-dispersed cobalt particles with minimal agglomeration. This sheds light on the advancement of new experimental procedures for developing more active and promising non-noble catalysts in large and stable batches.

Controllable Triboelectric Series Using Gradient Positive and Negative Charge-Confinement Layer with Different Particle Sizes of Mesoporous Carbon Materials.

As a method to maximize the energy efficiency of triboelectric nanogenerators (TENGs), high-voltage charge injection (HVCI) on the surface is a simple and effective method for increasing surface charge densities. In this study, positive and negative triboelectric series are controlled using a 3-layer gradient charge-confinement wherein the particle sizes of the mesoporous carbon spheres (mCSs) are sequentially arranged depending on the external surface area of the mCSs. In the gradient charge-confinement layers of this study, the mCS with different sizes perform charge transport from the surface to a deep position during HVCI while mitigating the charge loss through charge confinement to induce the high space charge densities. Through this process, the output voltage-which is initially 15.2 V-is measured to be 600 V after HVCI, thus representing an increase of about 40 times. Further, to amplify the low output current, which is a disadvantage of triboelectric energy, two types of electrical energy-triboelectric and electromagnetic energy-are produced in single mechanical motion. As a result, the output current produced by the cylindrical TENG and electromagnetic generator is recorded as being 1300 times higher, increasing from 12.8 µA to 17.5 mA.

Pore Modification and Phosphorus Doping Effect on Phosphoric Acid-Activated Fe-N-C for Alkaline Oxygen Reduction Reaction.

The price and scarcity of platinum has driven up the demand for non-precious metal catalysts such as Fe-N-C. In this study, the effects of phosphoric acid (PA) activation and phosphorus doping were investigated using Fe-N-C catalysts prepared using SBA-15 as a sacrificial template. The physical and structural changes caused by the addition of PA were analyzed by nitrogen adsorption/desorption and X-ray diffraction. Analysis of the electronic states of Fe, N, and P were conducted by X-ray photoelectron spectroscopy. The amount and size of micropores varied depending on the PA content, with changes in pore structure observed using 0.066 g of PA. The electronic states of Fe and N did not change significantly after treatment with PA, and P was mainly found in states bonded to oxygen or carbon. When 0.135 g of PA was introduced per 1 g of silica, a catalytic activity which was increased slightly by 10 mV at -3 mA/cm2 was observed. A change in Fe-N-C stability was also observed through the introduction of PA.

Impact of N-Substituent and pKa of Azole Rings on Fuel Cell Performance and Phosphoric Acid Loss.

The influence of N-substituent and pKa of azole rings has been investigated for the performance of high-temperature polymer electrolyte membrane fuel cells (HT-PEMFCs). Imidazole, benzimidazole, and triazole groups were functionalized on the side chains of poly(phenylene oxide), respectively. Each azole group is categorized by their N-substituent into two types: unsubstituted and methyl-substituted azoles. The membranes with methyl-substituted azoles showed higher phosphoric acid (PA) doping levels with an average increase of 20% compared to those with unsubstituted azoles in the full-doped states. However, unsubstituted azoles more effectively improved the proton conductivity and the membrane with unsubstituted imidazole (IMPPO-H) showed a high anhydrous proton conductivity of 153 mS/cm at 150 °C. In contrast, the membranes with methyl-substituted azoles showed a higher PA retention with an average increase of 81% compared to those with unsubstituted azoles. The higher PA retention of methyl-substituted azoles also led to the higher fuel cell performance with the maximum increase of 95% in the power density. It was also revealed that higher pKa of azoles enhanced the PA retention and the fuel cell performance. Based on the experimental results of PA retention and density functional theory calculations, the PA loss mechanism was also proposed.

Heterogeneous Electrocatalyst of Palladium-Cobalt-Phosphorus on Carbon Support for Oxygen Reduction Reaction in High Temperature Proton Exchange Membrane Fuel Cells.

Palladium-cobalt-phosphorus (PdCoP) catalysts supported on carbon (Ketjen Black) were investigated as a cathode catalyst for oxygen reduction reaction (ORR) in high temperature proton exchange membrane fuel cells (HT-PEMFCs). The PdCoP catalyst was synthesized via a modified polyol process in teflon-sealed reactor by microwave-heating. From X-ray diffraction and transmission electron microscopic analysis, the PdCoP catalyst exhibits a face-centered cubic structure, similar to palladium (Pd), which is attributed to form a good solid solution of Co atoms and P atoms in the Pd lattice. The PdCoP nanoparticles with average diameter of 2.3 nm were uniformly distributed on the carbon support. The electrochemical surface area (ECSA) and ORR activity of PdP, PdCo and PdCoP catalysts were measured using a rotating disk electrode technique with cyclic voltammetry and the linear sweep method. The PdCoP catalysts showed the highest performances for ECSA and ORR, which might be attributed both to formation of small nanoparticle by phosphorus atom and to change in lattice constant of Pd by cobalt atom. Furthermore, The HT-PEMFCs single cell performance employing PdCoP catalyst exhibited an enhanced cell performance compared to a single cell using the PdP and PdCo catalysts. This result indicates the importance of electric and geometric control of Pd alloy nanoparticles that can improve the catalytic activity. This synergistic combination of Co and P with Pd could provide the direction of development of non-Pt catalyst for fuel cell system.

Discovery of abnormal lithium-storage sites in molybdenum dioxide electrodes.

Developing electrode materials with high-energy densities is important for the development of lithium-ion batteries. Here, we demonstrate a mesoporous molybdenum dioxide material with abnormal lithium-storage sites, which exhibits a discharge capacity of 1,814 mAh g(-1) for the first cycle, more than twice its theoretical value, and maintains its initial capacity after 50 cycles. Contrary to previous reports, we find that a mechanism for the high and reversible lithium-storage capacity of the mesoporous molybdenum dioxide electrode is not based on a conversion reaction. Insight into the electrochemical results, obtained by in situ X-ray absorption, scanning transmission electron microscopy analysis combined with electron energy loss spectroscopy and computational modelling indicates that the nanoscale pore engineering of this transition metal oxide enables an unexpected electrochemical mass storage reaction mechanism, and may provide a strategy for the design of cation storage materials for battery systems.

Communication: Enhanced oxygen reduction reaction and its underlying mechanism in Pd-Ir-Co trimetallic alloys.

Based on a combined density functional theory and experimental study, we present that the electrochemical activity of Pd3Co alloy catalysts toward oxygen reduction reaction (ORR) can be enhanced by adding a small amount of Ir. While Ir tends to favorably exist in the subsurface layers, the underlying Ir atoms are found to cause a substantial modification in the surface electronic structure. As a consequence, we find that the activation barriers of O/OH hydrogenation reactions are noticeably lowered, which would be mainly responsible for the enhanced ORR activity. Furthermore, our study suggests that the presence of Ir in the near-surface region can suppress Co out-diffusion from the Pd3Co substrate, thereby improving the durability of Pd-Ir-Co catalysts. We also discuss the relative roles played by Ir and Co in enhancing the ORR activity relative to monometallic Pd catalysts.

Combinatorial high-throughput screening for highly active Pd-Ir-Ce based ternary catalysts in electrochemical oxygen reduction reaction.

A combinatorial library having 66 different ternary compositions of Pd-Ir-Ce was prepared via the impregnation method to find the optimum ternary composition with the highest performance toward oxygen reduction reaction (ORR) in acid media. Its performance in ORR activity of the combinatorial array was evaluated through two different combinatorial high-throughput screening methods to gain validity: (1) multielectrode half-cell method and (2) optical screening method. From the combinatorial results, the spot at 79:12:9 for Pd-Ir-Ce (at. %) in the array showed the highest ORR activity. The electrochemical characterizations of the single catalyst demonstrates that the optimized Pd79Ir12Ce9/C catalyst shows 1.5 times the ORR activity compared to that of Pd/C catalyst at 0.85 V (vs. RHE). In the Pd-Ir-Ce based catalysts, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) results reveal that Ir and Ce are present in the form of IrO2 and CeO2, respectively, and the electron configuration of Pd is effectively modified through the decoration with IrO2 and CeO2. From the results, we suggest that the electro-modification of Pd through strong metal-metal oxide interaction with IrO2-CeO2 was a reason for the enhanced ORR activity.

Palladium-nickel alloys loaded on tungsten carbide as platinum-free anode electrocatalysts for polymer electrolyte membrane fuel cells.

The strong interaction between PdNi alloys and WC makes PdNi/WC a novel Pt-free electrocatalyst for the anode hydrogen oxidation reaction of polymer electrolyte membrane fuel cells with activity and stability comparable to those of the conventional Pt/C catalysts.

Rational design of ordered mesoporous carbon with controlled bimodal porosity via dual silica templating route.

Combining both nano-replication and nano-imprinting techniques using dual silica templates provides a simple way to synthesize ordered mesoporous carbons with bimodal pore size distributions ( approximately 1.5 nm and approximately 3.5 nm).