Metal anode instability, including dendrite growth, metal corrosion, and hetero-ions interference, occurring at the electrolyte/electrode interface of aqueous batteries, are among the most critical issues hindering their widespread use in energy storage. Herein, a universal strategy is proposed to overcome the anode instability issues by rationally designing alloyed materials, using Zn-M alloys as model systems (M = Mn and other transition metals). An in-situ optical visualization coupled with finite element analysis is utilized to mimic actual electrochemical environments analogous to the actual aqueous batteries and analyze the complex electrochemical behaviors. The Zn-Mn alloy anodes achieved stability over thousands of cycles even under harsh electrochemical conditions, including testing in seawater-based aqueous electrolytes and using a high current density of 80 mA cm−2. The proposed design strategy and the in-situ visualization protocol for the observation of dendrite growth set up a new milestone in developing durable electrodes for aqueous batteries and beyond.
has been widely regarded as one of the most promising energy conversion and storage technologies to meet the growing energy demands of largescale application for electric vehicles and other electricity-related devices. [1] The two prominent reactions involved in ZABs are oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), both of which determine the practical performance of ZABs. Thus, the use of highly efficient and stable electrocatalysts as air electrodes is of paramount significance for facilitating the sluggish ORR and OER, thereby attaining high power and long operating lifetime performance for ZABs. Typically, platinum group metals (PGM) are most favorable ORR and OER catalysts displaying the absolute superiority of catalytic activity. However, the high cost, poor stability/durability, and low poison resistance of PGM have been the primary barriers that hamper widespread commercialization of ZABs. [1b,2] With decades of intensive effort in developing the cost-effective catalysts that possess remarkable catalytic performance, a new generation of PGM-free electrocatalystsThe oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) in zinc-air batteries (ZABs) require highly efficient, cost-effective, and stable electrocatalysts as alternatives to high cost and low poison resistant platinum group metals (PGM) catalysts. Although nitrogen-doped carbon nanotube (NCNT) arrays are now capable of catalyzing ORR efficiently, their hydrophobic surface and base-growth mode are found to limit the catalytic performance in the practical ZABs. Here, the concept of an apically dominant mechanism in improving the catalytic performance of NCNT by precisely encapsulating CoNi nanoparticles (NPs) within the apical domain of NCNT on the Ni foam (denoted as CoNi@NCNT/NF) is demonstrated. The CoNi@NCNT/NF exhibits a more excellent catalytic performance toward both ORR and OER than that of traditional NCNT derived from the base-growth method. The ZAB coin cell using CoNi@NCNT/NF as an air electrode shows a peak power density of 127 mW cm −2 with an energy density of 845 Wh kg Zn −1 and rechargeability over 90 h, which outperforms the performance of PGM catalysts. Density functional theory calculations reveal that the ORR catalytic performance of the CoNi@NCNT/NF is mainly attributed to the synergetic contributions from NCNT and the apical active sites on NCNT near to CoNi NPs.
A novel strategy is designed to stabilize atomic Pt catalysts in alloyed platinum cobalt nanosheets with trapped interstitial fluorine (SA-PtCoF) for zinc-air batteries.
We present a facile way to fabricate phosphorus and aluminum codoped nickel oxide-based nanosheets by using layered double hydroxide (AlNi-LDH) as precursors, which showed an overall water-splitting performance in alkaline solution. The codoping of phosphorus and aluminum into nickel oxide nanosheets leads to an optimum balance among surface chemical state, electrochemically active surface area, and density of active sites. As a result, it can afford a current density of 100 mA cm–2 at the overpotential of 310 mV for oxygen evolution reaction (OER) and a current density of 10 mA cm–2 at the overpotential of 138 mV for hydrogen evolution reaction (HER) in 1 M KOH. When it was used as a bifunctional catalyst in a two-electrode water-splitting device, a potential of 1.56 V was achieved at the current density of 10 mA cm–2.
Alkaline hydrogen evolution reaction (A-HER) holds great promise for clean hydrogen fuel generation but its practical utilization is severely hindered by the sluggish kinetics for water dissociation in alkaline solutions....
Understanding the synergism of bimetallic transition metal (TM)-based catalysts for oxygen evolution reaction (OER) is very difficult because it is complicated to identify the surface active sites in a bimetal system. Herein, we rationally designed Cu oxide (CuO x ) nanoarray film (NF) as an example to investigate the synergism and doping effects of iron group metals on OER. This is an advantage because CuO x is electrocatalytically inert and oxidatively stable, which is much better than carbon-based platforms. Especially, cobalt (Co) shows a much stronger synergism as compared with nickel (Ni) and iron (Fe). By introducing Co into the inert CuO x NFs, the Co active sites can be correlated to the OER activity by rationally regulating the morphology of CuO x NFs. In addition, the phase transformation from Cu2O to CuO occurs during the OER testing, further boosting the OER activity of Co-doped CuO x NF due to the hybridization change of Co active site. As a result, the Co-doped CuO x NF with 0.30 at. % Co (denoted as Co0.30CuO x ) shows a remarkable OER activity (an overpotential of 0.29 V at 10 mA cm–2) in basic solution, superior to those of the state-of-the-art OER catalysts. Both experimental and computational studies indicate that the introduction of Co-dopant in CuO x changes the rate-limiting step from M-OHads → M-Oads to M-Oads → M-OOHads and decreases the theoretical onset potential by 0.31 V. The optimal concentration of Co-dopant in CuO x nanocrystals renders the favorable surface properties for the electron transfer, the adsorption, and desorption of OER-relevant intermediates. Moreover, the small size of CuO x nanocrystals contributes to the large electrochemically active surface area, which enables the sufficient Co active sites to the electrolyte.
The Zn‐air battery (ZAB) is attracting increasing attention due to its high safety and preeminent performance. However, the practical application of ZAB relies heavily on developing durable support materials to replace conventional carbon supports which have unrecoverable corrosion issues, severely jeopardizing ZAB performance. Herein, a novel porous FeCo glassy alloy is developed as a bifunctional catalytic support for ZAB. The conducting skeleton of the porous glassy alloy is used to stabilize oxygen reduction cocatalysts, and more importantly, the FeCo serves as the primary phase for oxygen evolution. To demonstrate the concept of catalytic glassy alloy support, ultrasmall Pd nanoparticles are anchored, as oxygen reduction active sites, on the porous FeCo (noted as Pd/FeCo) for ZAB. The Pd/FeCo exhibits a significantly improved electrocatalytic activity for oxygen reduction (a half‐wave potential of 0.85 V) and oxygen evolution (a potential of 1.55 V to reach 10 mA cm−2) in the alkaline media. When used in the ZAB, the Pd/FeCo delivers an output power density of 117 mW cm−2 and outstanding cycling stability for over 200 h (400 cycles), surpassing the conventional carbon‐supported Pt/C+IrO2 catalysts. Such an integrated design that combines highly active components with a porous architecture provides a new strategy to develop novel nanostructured electrocatalysts.
The design and synthesis of low-cost and efficient bifunctional electrocatalysts for water splitting are critical and challenging. Hereby, a bimetallic phosphide embedded in a N and P co-doped porous carbon (FeCoP2@NPPC) material was synthesized by using sustainable biomass-derived N- and P-containing carbohydrates and non-noble metal salts as precursors. The obtained material exhibits good catalytic activities in hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and overall water splitting. The bimetallic alloy phosphide (FeCoP2) is the active site for electrocatalysis. Theoretical calculation indicates that the sub-layer Fe atoms and top-layer Co atoms in FeCoP2 exhibit a synergistic effect for enhanced electrocatalytic performance. The carbon matrix around the FeCoP2 can prevent the corrosion during the catalytic reactions. The hierarchically porous structure of the FeCoP2@NPPC material can promote the transfer of electrons and electrolyte, and increase the contact area of the active sites and electrolytes. N- and P-containing functionalities improve the wetting and conductivity properties of the porous carbon. Due to the synergistic effects, FeCoP2@NPPC requires a low overpotential of 114 and 150 mV at the current density of 10 mA cm–2 for HER in 0.5 M H2SO4 and 1.0 M KOH, and an overpotential of 236 mV for OER in 1.0 M KOH solution, which are much lower than those of FeP@NPPC and CoP@NPPC. Based on the density functional theory calculation, FeCoP2 yields the smallest Gibbs free energy change of rate-determining step among the samples, which leads to better electrochemical performances. In addition, when FeCoP2@NPPC was used as a bifunctional catalyst in water splitting, the electrolyzer needed a low voltage of 1.60 V to deliver the current density of 10 mA cm–2. Furthermore, this work provides a strategy for preparing sustainable, stable, and highly active electrocatalysts for water splitting.
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