In situ self-assembly of molybdenum carbide and iron carbide heterostructures on N-doped carbon for an efficient oxygen reduction reaction.

Identifying highly stable, cost-effective, platinum-free, and efficient electrocatalysts for the oxygen reduction reaction (ORR) remains a formidable challenge. The ORR is important for advancing fuel cell and zinc-air battery (ZAB) technologies towards cost-efficiency and environmental sustainability. This work presents the utilization of economically viable materials through a straightforward synthesis process, exhibiting the development of efficient Mo2C/Fe3C-NC catalysts ingeniously derived from phosphomolybdic acid (PMA) and iron phthalocyanine (FePc). The results demonstrate that the optimized Mo2C/Fe3C-NC3 catalysts exhibit remarkable electrochemical performance, evidenced by an impressive onset potential of ∼1.0 V versus RHE, a half-wave potential of 0.89 V, and a superior current density of about 6.2 mA cm-2. As for their performance in ZABs, the optimized catalysts reach a peak power density of 142 mW cm-2 at a current density of 200 mA cm-2. This synergy, coupled with the uniform distribution of Mo2C and Fe3C nanoparticles, greatly enhances the active catalytic sites and promotes electrolyte diffusion. Our approach diverges from traditional methods by employing an in situ self-assembled heterostructure of Mo2C/Fe3C on nitrogen-doped carbon tubes, avoiding the conventional high-temperature hydrogen gas reduction process. Beyond serving as feasible alternatives to commercially available Pt/C catalysts, these materials hold promise for large-scale production owing to their affordability and the simplicity of the synthesis technique. Such a breakthrough paves the way towards the realization of sustainable energy technologies and lays the groundwork for further exploration into amplifying the scalability and efficiency of ORR catalysts.

Stabilizing a zinc anode via a tunable covalent organic framework-based solid electrolyte interphase.

Zinc (Zn) is an excellent material for use as an anode for rechargeable batteries in water-based electrolytes. Nevertheless, the high activity of water leads to Zn corrosion and hydrogen evolution, along with the formation of dendrites on the Zn surface during repeated charge-discharge (CD) cycles. To protect the Zn anode and limit parasitic side reactions, an artificial solid electrolyte interphase (ASEI) protective layer is an effective strategy. Herein, an ASEI made of a covalent organic framework (COFs: HqTp and BpTp) was fabricated on the surface of a Zn anode via Schiff base reactions of aldehyde and amine linkers. It is seen that COFs can regulate the Zn-ion flux, resulting in dendritic-free Zn. COFs can also mitigate the formation of an irreversible passive layer and the hydrogen evolution reaction (HER). Zn plating/stripping tests using a symmetrical cell suggest that HqTpCOF@Zn shows superior stability and greater coulombic efficiency (CE) compared to bare Zn. The full cell having COFs@Zn also displays much improved cyclability. As a result, the COF proves to be a promising ASEI material to enhance the stability of the Zn anode in aqueous media.

Compressed composite carbon felt as a negative electrode for a zinc-iron flow battery.

Flow batteries possess several attractive features including long cycle life, flexible design, ease of scaling up, and high safety. They are considered an excellent choice for large-scale energy storage. Carbon felt (CF) electrodes are commonly used as porous electrodes in flow batteries. In vanadium flow batteries, both active materials and discharge products are in a liquid phase, thus leaving no trace on the electrode surface. However, zinc-based flow batteries involve zinc deposition/dissolution, structure and configuration of the electrode significantly determine stability and performance of the battery. Herein, fabrication of a compressed composite using CF with polyvinylidene fluoride (PVDF) is investigated in a Zn-Fe flow battery (ZFB). Graphene (G) is successfully introduced in order to improve its electrochemical activity towards zinc reactions on the negative side of the ZFB. A compressed composite CF electrode offers more uniform electric field and lower nucleation overpotential (NOP) of zinc than a pristine CF, resulting in higher zinc plating/stripping efficiency. Batteries with modified electrodes are seen to provide lower overpotential. Particularly, the G-PVDF-CF electrode demonstrates maximum discharge capacity of 39.6 mAh cm-2 with coulombic efficiency and energy efficiency over 96% and 61%, respectively. Finally, results lead to increased efficiency and cycling stability for flow batteries.

Chemical Transformation Induced Core-Shell Ni2P@Fe2P Heterostructures toward Efficient Electrocatalytic Oxygen Evolution.

The oxygen evolution reaction (OER) is a crucial reaction in water splitting, metal-air batteries, and other electrochemical conversion technologies. Rationally designed catalysts with rich active sites and high intrinsic activity have been considered as a hopeful strategy to address the sluggish kinetics for OER. However, constructing such active sites in non-noble catalysts still faces grand challenges. To this end, we fabricate a Ni2P@Fe2P core-shell structure with outperforming performance toward OER via chemical transformation of rationally designed Ni-MOF hybrid nanosheets. Specifically, the Ni-MOF nanosheets and their supported Fe-based nanomaterials were in situ transformed into porous Ni2P@Fe2P core-shell nanosheets composed of Ni2P and Fe2P nanodomains in homogenous dispersion via a phosphorization process. When employed as the OER electrocatalyst, the Ni2P@Fe2P core-shell nanosheets exhibits excellent OER performance, with a low overpotential of 238/247 mV to drive 50/100 mA cm-2, a small Tafel slope of 32.91 mV dec-1, as well as outstanding durability, which could be mainly ascribed to the strong electronic interaction between Ni2P and Fe2P nanodomains stabilizing more Ni and Fe atoms with higher valence. These high-valence metal sites promote the generation of high-active Ni/FeOOH to enhance OER activity.

Construction of Core-Shell CoMoO4@γ-FeOOH Nanosheets for Efficient Oxygen Evolution Reaction.

The oxygen evolution reaction (OER) occurs at the anode in numerous electrochemical reactions and plays an important role due to the nature of proton-coupled electron transfer. However, the high voltage requirement and low stability of the OER dramatically limits the total energy converting efficiency. Recently, electrocatalysts based on multi-metal oxyhydroxides have been reported as excellent substitutes for commercial noble metal catalysts due to their outstanding OER activities. However, normal synthesis routes lead to either the encapsulation of excessively active sites or aggregation during the electrolysis. To this end, we design a novel core-shell structure integrating CoMoO4 as support frameworks covered with two-dimensional γ-FeOOH nanosheets on the surface. By involving CoMoO4, the electrochemically active surface area is significantly enhanced. Additionally, Co atoms immerge into the γ-FeOOH nanosheet, tuning its electronic structure and providing additional active sites. More importantly, the catalysts exhibit excellent OER catalytic performance, reducing overpotentials to merely 243.1 mV a versus 10 mA cm-2. The current strategy contributes to advancing the frontiers of new types of OER electrocatalysts by applying a proper support as a multi-functional platform.

Carboxymethyl cellulose-based polyelectrolyte as cationic exchange membrane for zinc-iodine batteries.

The aim of this research is an evaluation of polyelectrolytes. In the application of zinc-iodine batteries (ZIBs), polyelectrolytes have high stability, good cationic exchange properties and high ionic conductivity. Polyelectrolytes are also cost-effective. Important component of ZIBs are cation exchange membranes (CEMs). CEMs prevent the crossover of iodine and polyiodide from zinc (Zn) electrodes. However, available CEMs are costly and have limited ionic conductivity at room temperature. CEMs are low-cost, have high stability and good cationic exchange properties. Herein, polyelectrolyte membranes prepared from carboxymethyl cellulose (CMC) and polyvinyl alcohol (PVA) are examined. It is seen that an increase in the ratio of PVA leads to enhanced ionic conductivity as well as increased iodine and polyiodide crossover. ZIBs using polyelectrolytes having 75:25 wt.% CMC/PVA and 50:50 wt.% CMC/PVA show decent performance and cycling stability. Due to their low-cost and other salient features, CMC/PVA polyelectrolytes prove they have the capacity for use as cation exchange separators in ZIBs.

Correction: Abbasi, A. et al. Poly(2,6-dimethyl-1,4-phenylene oxide)-Based Hydroxide Exchange Separator Membranes for Zinc-Air Battery. Int. J. Mol. Sci. 2019, 20, 3678.

The authors would like to make the following corrections to their paper published in the International Journal of Molecular Science [...].

Poly(2,6-Dimethyl-1,4-Phenylene Oxide)-Based Hydroxide Exchange Separator Membranes for Zinc-Air Battery.

Rechargeable zinc-air batteries are deemed as the most feasible alternative to replace lithium-ion batteries in various applications. Among battery components, separators play a crucial role in the commercial realization of rechargeable zinc-air batteries, especially from the viewpoint of preventing zincate (Zn(OH)42-) ion crossover from the zinc anode to the air cathode. In this study, a new hydroxide exchange membrane for zinc-air batteries was synthesized using poly (2,6-dimethyl-1,4-phenylene oxide) (PPO) as the base polymer. PPO was quaternized using three tertiary amines, including trimethylamine (TMA), 1-methylpyrolidine (MPY), and 1-methylimidazole (MIM), and casted into separator films. The successful synthesis process was confirmed by proton nuclear magnetic resonance and Fourier-transform infrared spectroscopy, while their thermal stability was examined using thermogravimetric analysis. Besides, their water/electrolyte absorption capacity and dimensional change, induced by the electrolyte uptake, were studied. Ionic conductivity of PPO-TMA, PPO-MPY, and PPO-MIM was determined using electrochemical impedance spectroscopy to be 0.17, 0.16, and 0.003 mS/cm, respectively. Zincate crossover evaluation tests revealed very low zincate diffusion coefficient of 1.13 × 10-8, and 0.28 × 10-8 cm2/min for PPO-TMA, and PPO-MPY, respectively. Moreover, galvanostatic discharge performance of the primary batteries assembled using PPO-TMA and PPO-MPY as initial battery tests showed a high specific discharge capacity and specific power of ~800 mAh/gZn and 1000 mWh/gZn, respectively. Low zincate crossover and high discharge capacity of these separator membranes makes them potential materials to be used in zinc-air batteries.

δ-MnO2 nanoflower/graphite cathode for rechargeable aqueous zinc ion batteries.

Manganese oxide (MnO2) is one of the most promising intercalation cathode materials for zinc ion batteries (ZIBs). Specifically, a layered type delta manganese dioxide (δ-MnO2) allows reversible insertion/extraction of Zn2+ ions and exhibits high storage capacity of Zn2+ ions. However, a poor conductivity of δ-MnO2, as well as other crystallographic forms, limits its potential applications. This study focuses on δ-MnO2 with nanoflower structure supported on graphite flake, namely MNG, for use as an intercalation host material of rechargeable aqueous ZIBs. Pristine δ-MnO2 nanoflowers and MNG were synthesized and examined using X-ray diffraction, electron spectroscopy, and electrochemical techniques. Also, performances of the batteries with the pristine δ-MnO2 nanoflowers and MNG cathodes were studied in CR2032 coin cells. MNG exhibits a fast insertion/extraction of Zn2+ ions with diffusion scheme and pseudocapacitive behavior. The battery using MNG cathode exhibited a high initial discharge capacity of 235 mAh/g at 200 mA/g specific current density compared to 130 mAh/g which is displayed by the pristine δ-MnO2 cathode at the same specific current density. MNG demonstrated superior electrical conductivity compared to the pristine δ-MnO2. The results obtained pave the way for improving the electrical conductivity of MnO2 by using graphite flake support. The graphite flake support significantly improved performances of ZIBs and made them attractive for use in a wide variety of energy applications.