Improving the Oxygen Evolution Reaction Kinetics in Zn-Air Battery by Iodide Oxidation Reaction.

Zinc-air batteries (ZABs) have garnered considerable attention as a highly promising contender in the field of energy storage and conversion. Nevertheless, their performance is considerably impeded by the proliferation of dendrites on the Zinc anode and the slow kinetics of the redox reaction on the air cathode. Herein, taking Ag30%@LaCoO3 (Ag30%@LCO) heterojunction catalyst as the cathode, it is demonstrated that adding KI additives to the alkaline electrolyte can not only enhance the oxygen electrocatalytic reaction but also inhibit the formation of zinc anode dendrites, thereby achieving a comprehensive improvement in the performance of ZABs. Under the action of the KI additive, the optimized Ag30%@LCO catalyst shows a decreased overpotential from 460 to 220 mV at j = 10 mA cm-2, while the assembled ZAB shows reduced charging potential (1.8 V), and long cycle stability (180 h). Furthermore, the morphology characterization results indicate a reduction in dendrites on the Zn anode. Both experimental and calculated results indicate that the presence of I- as a reaction modifier alters the trajectory of the conventional oxygen evolution reaction, resulting in a more thermodynamically favorable pathway. The introduction of KI additives as electrolytes provides a straightforward approach to developing comprehensively improved ZABs.

Tailoring Spin State of Perovskite Oxides by Fluorine Atom Doping for Efficient Oxygen Electrocatalysis.

Promoting the initially deficient but economical catalysts to high-performing competitors is important for developing superior catalysts. Unlike traditional nano-morphology construction methods, this work focuses on intrinsic catalytic activity enhancement via heteroatom doping strategies to induce lattice distortion and optimize spin-dependent orbital interaction to alter charge transfer between catalysts and reactants. Experimentally, a series of different concentrations of fluorine-doped lanthanum cobaltate (Fx -LaCoO3 ) exhibiting excellent electrocatalytic activity is synthesized, including a low overpotential of 390 mV at j = 10 mA cm-2 for OER and a large half-wave potential of 0.68 V for ORR. Meanwhile, the assembled rechargeable Zn-air batteries deliver an excellent performance with a large specific capacity of 811 mAh/gZn under 10 mA cm-2 and stability of charge/recharge (120 h). Theoretically, taking advantage of density functional theory calculations, it is found that the prominent OER/ORR performance arises from the spin state transition of Co3+ (Low spin state (LS, t2g 6 eg 0 ) → Intermediate spin state (IS, t2g 5 eg 1 ) and the mediated d-band center upshift by F atom incorporation. This work establishes a novel avenue for designing superior electrocatalysts in perovskite-based oxides by regulating spin states.

Measurement of harmful nanoparticle distribution among filters, smokers' respiratory systems, and surrounding air during cigarette smoking.

This study was undertaken to investigate the filtration effect of filter on nanoparticle and the deposition behavior of nanoparticle in the human respiratory system from the aspect of nanoparticle number during cigarette smoking. For that, two kinds of experiments were designed. One is machine experiment, a well-controlled simulated respiratory system was designed to measure the raw emission and filter effect. Another is human experiment, volunteers were asked to inhale smoke into the oral cavity only and lungs, respectively, to distinguish smoke path. Results revealed that effective inhaled nanoparticle amount of a Taishan and a Hongtaishan cigarette were 5.8E + 9 (#) and 9.4E + 7 (#), respectively. The filter's integrated reduction rate was 41.65% for nanoparticle. For Taishan cigarette, 35.4% and 41.7% of raw emitted nanoparticles were deposited in the oral cavity and lungs, respectively, the rest of 22.9% was exhaled to surrounding air. The corresponding values were 25.6%, 41.5% and 32.9%, respectively, for Hongtaishan. The current findings are expected to provide basic assessments of filter effect and harm to human and to be a warning for smokers.

Optimized Conductivity and Spin States in N-Doped LaCoO3 for Oxygen Electrocatalysis.

The spin state of antibonding orbital (eg) occupancy in LaCoO3 is recognized as a descriptor for its oxygen electrocatalysis. However, the Co(III) cation in typical LaCoO3 (LCO) favors low spin state, which is mediocre for absorbing oxygen-containing groups involved in oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), thus hindering its further development in electrocatalysis. Herein, both experimental and theoretical results reveal the enhancement of bifunctional electrocatalytic activity in LaCoO3 by N doping. More specifically, electron energy loss spectroscopy and superconducting quantum interference devices magnetic analysis demonstrate that the Co(III) cation in N-doped LaCoO3 (LCON) achieves a moderate eg occupancy (≈1) compared with its low spin state in LaCO3. First-principle calculation results reveal that N dopants play a bifunctional role of tuning the spin-state transition of Co(III) cations and increasing the electrical conductivity of LCO. Thus, the optimized LCON exhibits an OER overpotential of 1.69 V at the current density of 50 mA/cm2 (1.94 V for pristine LCO) and yields an ORR limiting current density of 5.78 mA/cm2 (4.01 mA/cm2 for pristine LCO), which offers a new strategy to simultaneously modulate the magnetic and electronic structures of LCO to further enhance its electrocatalytic activity.

Hydrogen-etched CoS2 to produce a Co9S8@CoS2 heterostructure electrocatalyst for highly efficient oxygen evolution reaction.

There is a pressing requirement for developing high-efficiency non-noble metal electrocatalysts in oxygen evolution reactions (OER), where transition metal sulfides are considered to be promising electrocatalysts for the OER in alkaline medium. Herein, we report the outstanding OER performance of Co9S8@CoS2 heterojunctions synthesized by hydrogen etched CoS2, where the optimized heterojunction shows a low η 50 of 396 mV and a small Tafel slope of 181.61 mV dec-1. The excellent electrocatalytic performance of this heterostructure is attributed to the interface electronic effect. Importantly, the post-stage characterization results indicate that the Co9S8@CoS2 heterostructure exhibits a dynamic reconfiguration during the OER with the formation of CoOOH in situ, and thus exhibits a superior electrocatalytic performance.

High efficiency electrocatalyst of LaCr0.5Fe0.5O3 nanoparticles on oxygen-evolution reaction.

Due to the multistep proton-coupled electron transfer, it remains a huge challenge to accelerate the kinetics of oxygen evolution reaction (OER). Here, we demonstrate that perovskite-type LaCr0.5Fe0.5O3 nanoparticles can be used as highly active and stable OER electrocatalysts, where it shows a low overpotential of 390 mV at 10 mA/cm2, a small Tafel slope of 114.4 mV/dec and excellent stability with slight current decrease after 20 h, superior than that of their individual counterparts (LaFeO3 and LaCrO3). This finding confirms that the present hybrid material would be an effective means to electrocatalyst for catalyzing OER.

Dispersion behaviors of exhaust gases and nanoparticle of a passenger vehicle under simulated traffic light driving pattern.

In the present study, the flow structure and pollutants dispersions were investigated by experiment and simulation on a typical passenger vehicle under simulated traffic light driving pattern. Some important findings were achieved: 1) gaseous pollutants diffuse drastically during first 0.3-0.6 m distance depending on wind velocity, at 1.25 m/s wind speed which is the similar level of exhaust gas, the pollutant concentration rises suddenly at ~0.6 m because exhaust plume is twisted by bottom gas flow, and a low velocity zone is produced; 2) as wind speed increases, the vehicle-induced turbulence is more and more important on pollutant dispersion pattern than exhaust plume dynamics. For instance, at 1.25 m/s and 4.17 m/s wind speeds, pollutants decrease to zero at ~1.6 m behind tail pipe, but at 0 m/s condition, pollutant relative fraction is still at ~0.12 level even at very long distance; 3) solid particle has larger attenuation rate than gaseous pollutants, only after ~0.6 m the particle number (PN) and diameter are very close to background values. Solid particle can diffuse to farther distance in vehicle transverse direction, when a car passes through the pedestrians with a 3 m distance, pedestrians expose to 2.6-3 times higher PN relative to atmosphere with diameters of 28-33 nm, this is very hazardous for human health; 4) exhaust pollutants disperse difficultly when followed by a car with a commonly waiting distance. At free dispersion scenario only behind ~0.6 m, PN decreases to 5800 #/cm3 (background value), but in-cabin PN of the following car (behind 0.8 m) rises to 3.5 × 104 #/cm3 (even after 2-3 times decay through ventilation system). This study provides implications for future studies on transport planning.

Fe-based species anchored on N-doped carbon nanotubes as a bifunctional electrocatalyst for acidic/neutral/alkaline Zn-air batteries.

Exploring efficient and durable bifunctional catalysts in pH-universal media is critical for versatile fuel cells. Herein, Fe-based species anchored on N-doped carbon nanotubes (Fe/Fe3C@N-C) are used for bifunctional oxygen electrocatalysts. The composite electrocatalyst exhibits low potential gaps (ΔE, ΔE = Ej =10 - E 1/2) in a pH-universal environment. The estimated values are about 0.70, 1.07,and 1.10 V in alkaline, neutral, and acidic medias. A neutral Zn-air battery (ZAB) is constructed using an Fe/Fe3C@N-C composite as the air electrode, which exhibits a favorable performance in energy storage with an open-circuit potential (OCP) of 1.42 V and a high power density of 80 mW cm-2. The ZAB also has superior cycling stability with only a 0.5% decay after 1200 charge-discharge cycles at 2 mA cm-2. While the assembled ZAB in acidic media indicates an OCP of 1.40 V, a power density of 23 mW cm-2, and 612 discharge-charge cycles. The ZAB is rechargeable and has a cycling lifespan of 120 h. This work provides potential applications of Fe/Fe3C@N-C as air electrodes for advanced pH-universal media based on ZABs for future energy storage devices.

Bifunctional Oxygen Electrocatalyst of Mesoporous Ni/NiO Nanosheets for Flexible Rechargeable Zn-Air Batteries.

One approach to accelerate the stagnant kinetics of both the oxygen reduction and evolution reactions (ORR/OER) is to develop a rationally designed multiphase nanocomposite, where the functions arising from each of the constituent phases, their interfaces, and the overall structure are properly controlled. Herein, we successfully synthesized an oxygen electrocatalyst consisting of Ni nanoparticles purposely interpenetrated into mesoporous NiO nanosheets (porous Ni/NiO). Benefiting from the contributions of the Ni and NiO phases, the well-established pore channels for charge transport at the interface between the phases, and the enhanced conductivity due to oxygen-deficiency at the pore edges, the porous Ni/NiO nanosheets show a potential of 1.49 V (10 mA cm-2) for the OER and a half-wave potential of 0.76 V for the ORR, outperforming their noble metal counterparts. More significantly, a Zn-air battery employing the porous Ni/NiO nanosheets exhibits an initial charging-discharging voltage gap of 0.83 V (2 mA cm-2), specific capacity of 853 mAh g Zn -1 at 20 mA cm-2, and long-time cycling stability (120 h). In addition, the porous Ni/NiO-based solid-like Zn-air battery shows excellent electrochemical performance and flexibility, illustrating its great potential as a next-generation rechargeable power source for flexible electronics.

Bifunctional catalysts of CoNi nanoparticle-embedded nitrogen-doped carbon nanotubes for rechargeable Zn-air batteries.

It is essentially important to improve the performance of Zn-air batteries by studying bifunctional catalysts for oxygen evolution reactions (OER) and oxygen reduction reactions (ORR) with low-cost, high-efficiency and high-stability properties. Here, CoNi nanoparticles embedded in the bamboo-like N-doped carbon tubes (Co x Ni y @NC) were synthesized, where the optimized catalyst of Co2Ni1@NC exhibits superior bifunctional electrocatalytic activity, showing a low overpotential of 300 mV under the current density of 10 mA cm-2 for OER and a large limiting current density of 3.76 mA cm-2 under 0.40 V for ORR in an alkaline solution. In addition, the Co2Ni1@NC also shows excellent electrocatalytic activity in acidic and neutral solutions. Importantly, primary Zn-air batteries based on Co2Ni1@NC affords an excellent specific capacity of 834 mAh/gZn with a discharge potential of 1.25 V at 5 mA cm-2. A rechargeable Zn-air battery assembled with Co2Ni1@NC shows excellent cycling stability, where the first discharge and charge voltages reach 1.21 and 2.00 V under 1 mA cm-2, respectively. This finding provides a simple synthesis approach, which allows one to construct bifunctional catalysts based on metal@NC for future energy conversion and storage devices.