Inhibiting Demetalation of Fe─N─C via Mn Sites for Efficient Oxygen Reduction Reaction in Zinc-Air Batteries.

Demetalation caused by the electrochemical dissolution of metallic Fe atoms is a major challenge for the practical application of Fe─N─C catalysts. Herein, an efficient single metallic Mn active site is constructed to improve the strength of the Fe─N bond, inhibiting the demetalation effect of Fe─N─C. Mn acts as an electron donor inducing more delocalized electrons to reduce the oxidation state of Fe by increasing the electron density, thereby enhancing the Fe─N bond and inhibiting the electrochemical dissolution of Fe. The oxygen reduction reaction pathway for the dissociation of Fe─Mn dual sites can overcome the high energy barriers to direct O─O bond dissociation and modulate the electronic states of Fe─N4 sites. The resulting FeMn─N─C exhibits excellent ORR activity with a high half-wave potential of 0.92 V in alkaline electrolytes. FeMn─N─C as a cathode catalyst for Zn-air batteries has a cycle stability of 700 h at 25 °C and a long cycle stability of more than 210 h under extremely cold conditions at -40 °C. These findings contribute to the development of efficient and stable metal-nitrogen-carbon catalysts for various energy devices.

Potential Dominates Structural Recombination of Single Atom Mn Sites for Promoting Oxygen Reduction Reaction.

Single atom sites (SAS) often undergo structural recombination in oxygen reduction reaction (ORR), while the effect of valence state and reconstruction on active centers needs to be investigated thoroughly. Herein, the Mn-SAS catalyst with uniform and precise Mn-N4 configuration is rationally designed. We utilize operando synchrotron radiation to track the dynamic evolution of active centers during ORR. Under the applied potential, the structural evolution of Mn-N4 into Mn-N3 C and further into Mn-N2 C2 configurations is clarified. Simultaneously, the valence states of Mn are increased from +3.0 to +3.8 and then decreased to +3.2. When the potential is removed, the catalyst returned to its initial Mn+3.0 -N4 configuration. Such successive evolutions optimize the electronic and geometric structures of active centers as evidenced by theory calculations. The evolved Mn+3.8 -N3 C and Mn+3.2 -N2 C2 configurations respectively adjust the O2 adsorption and reduce the energy barrier of rate-determining step. Thus, it can achieve an onset potential of 0.99 V, superior stability over 10,000 cycles, and a high turnover frequency of 1.59 s-1 at 0.85 VRHE. Our present work provides new insights into the construction of well-defined SAS catalysts by regulating the valence states and configurations of active centers.

Iron Single Atoms-Assisted Cobalt Nitride Nanoparticles to Strengthen the Cycle Life of Rechargeable Zn-Air Battery.

The development of nonprecious metal catalysts with both oxygen reduction and evolution reactions (ORR/OER) is very important for Zn-air batteries (ZABs). Herein, a Co5.47 N particles and Fe single atoms co-doped hollow carbon nanofiber self-supporting membrane (H-CoFe@NCNF) is synthesized by a coaxial electrospinning strategy combined with pyrolysis. X-ray absorption fine spectroscopy analyses confirm the state of the cobalt nitride and Fe single atoms. As a result, H-CoFe@NCNF exhibits a superior bifunctional performance of Eonset  = 0.96 V for ORR, and Ej = 10 = 1.68 V for OER. Density functional theory calculations show that H-CoFe@NCNF has a moderate binding strength to oxygen due to the coexistence of nanoparticle and single atoms. Meanwhile, the Co site is more favorable to the OER, while the Fe site facilitates the ORR, and the proton and charge transfer between N and metal atoms further lower the reaction barriers. The liquid ZAB composed of H-CoFe@NCNF has a charge-discharge performance of ≈1100 h and a peak power density of 205 mW cm-2 . The quasi-solid-state ZAB assembled by the self-supporting membrane of H-CoFe@NCNF is proven to operate stably in any bending condition.

Copper Collector Generated Cu+/Cu2+ Redox Pair for Enhanced Efficiency and Lifetime of Zn-Ni/Air Hybrid Battery.

Although Zn-Ni/air hybrid batteries exhibit improved energy efficiency, power density, and stability compared with Zn-air batteries, they still cannot satisfy the high requirements of commercialization. Herein, the Cu+/Cu2+ redox pair generated from a copper collector has been introduced to construct the hybrid battery system by combining Zn-air and Zn-Cu/Zn-Ni, in which CuXO@NiFe-LDH and Co-N-C dodecahedrons are respectively adopted as oxygen evolution (OER) and oxygen reduction (ORR) electrodes. For fabricating CuXO@NiFe-LDH, the Cu foam collector is oxidized to in situ form 1D CuXO nanoneedle arrays, which could generate the Cu+/Cu2+ redox pair to enhance battery efficiency by providing an extra charging-discharging voltage plateau to reduce the charging voltage and increase the discharge voltage. Then, the 2D NiFe hydrotalcite nanosheets grow on the nanoneedle arrays to obtain 3D interdigital structures, facilitating the intimate contact of the ORR/OER electrode and electrolyte by providing a multichannel structure. Thus, the battery system could endow a high energy efficiency (79.6% at 10 mA cm-2), an outstanding energy density (940 Wh kg-1), and an ultralong lifetime (500 h). Significantly, it could stably operate under harsh environments, such as oxygen-free and any humidity. In situ X-ray diffraction (XRD) combined with ex situ X-ray photoelectron spectroscopy (XPS) analyses demonstrate the reversible process of Cu-O-Cu ↔ Cu-O and Ni-O ↔ Ni-O-O-H during the charging/discharging, which are responsible for the enhanced efficiency and lifetime of battery.

Reconstruction of Highly Dense Cu-N4 Active Sites in Electrocatalytic Oxygen Reduction Characterized by Operando Synchrotron Radiation.

The emerging star of single atomic site (SAS) catalyst has been regarded as the most promising Pt-substituted electrocatalyst for oxygen reduction reaction (ORR) in anion-exchange membrane fuel cells (AEMFCs). However, the metal loading in SAS directly affects the whole device performance. Herein, we report a dual nitrogen source coordinated strategy to realize high dense Cu-N4 SAS with a metal loading of 5.61 wt% supported on 3D N-doped carbon nanotubes/graphene structure wherein simultaneously performs superior ORR activity and stability in alkaline media. When applied in H2 /O2 AEMFC, it could reach an open-circuit voltage of 0.90 V and a peak power density of 324 mW cm-2 . Operando synchrotron radiation analyses identify the reconstruction from initial Cu-N4 to Cu-N4 /Cu-nanoclusters (NC) and the subsequent Cu-N3 /Cu-NC under working conditions, which gradually regulate the d-band center of central metal and balance the Gibbs free energy of *OOH and *O intermediates, benefiting to ORR activity.