Zinc-air Research Articles

In situ-grown nitrogen-sulfur co-doped carbon nanotubes encapsulated with FeS particles as cathode materials for zinc-air batteries

Transition metal sulfides as ideal oxygen reduction reaction (ORR) catalysts have great potential to regulate multiple reaction pathways and understand their corresponding internal reaction mechanisms at cathode in zinc-air batteries (ZABS), effectively. This work adopted a facile one-pot synthesis method based on chemical vapor deposition (CVD), which utilizes the synergistic effect of zeolite imidazolium ester skeleton (ZIF-8) and polypyrrole (PPY) to grow nitrogen-sulfur co-doped carbon nanotubes (NS-CNT) in the shape of colonic with a relatively uniform size and encapsulated with FeS nanoparticles as the main active sites. The synthesized purpose catalyst noted as FeS-NS-CNT-900, in which that the FeS nanoparticles were tightly encapsulated in carbon nanotubes, and this special structure ensures that the FeS particles do not detach during the reaction, thus greatly enhancing their electrochemical activity and stability. As expected, the FeS-NS-CNT-900 catalyst exhibited a half-wave potential of 0.877 V which is higher than that of commercial platinum charcoal (0.847 V), at 0.1 mol KOH. More importantly, the formation of abundant FeS catalytic active sites, the optimal conditions for NS-CNT growth, and the covered mechanisms of the enhanced ORR reaction activity of FeS-NS-CNT-900 were thoroughly investigated. Additionally, whileFeS-NS-CNT-900 was used as an air cathode material for the assembly of a zinc-air battery, it exhibited a peak power density and specific capacity of 123 mW cm−2 and 785.81 mA h g−1, respectively, which were significantly better than that of platinum-carbon cathode (92.8 mW cm−2 and 740.4 mA h g−1). And surprisingly, the battery with FeS-NS-CNT-900 cathode exhibited (delivered/showed) a high cycle stability of 260 h at 5 mA cm−2. Conclusively, present work provides a feasible method for in situ growth of sulfur and nitrogen co-doped carbon nanotube encapsulated transition metal sulfide nanoparticle catalysts, which may pave a new avenue for the preparation of high ORR performance air cathode material for ZABS.

Dual‐Carbon Assisted Oxygen Vacancy Engineering for Optimizing Mn(III) Sites to Enhance Zn–air Battery Performances

AbstractOwing to kinetic‐sluggish nature of electrocatalytic oxygen transformation processes, it is pivotal to develop durable and efficient bifunctional air electrode catalysts for fabricating high‐performance Zn–air batteries (ZABs). In this work, oxygen vacancy (Ov) induced Mn(III) sites optimization is achieved via nano‐micro structure modulation. Protonated carbon nitride (p‐C3N4) is applied as a structure‐stiffening module to immobilize α‐MnO2 on N/P‐doped active carbon (NPAC) and induce Ov construction. X‐ray adsorption spectra (XAS) disclose the formation of Ov and Mn(III) sites in MCC, the unit coordination structure is well maintained with the aid of a dual‐carbon strategy. Mn(III) sites efficiently catalyze oxygen reduction/evolution reaction (ORR/OER), MCC shows high half‐wave potential (E1/2) of 0.88 V for ORR and low potential at 10 mA cm−2 (Ej = 10) of 1.64 V for OER. According to density functional theory (DFT) simulations analysis, the gorgeous bifunctional activity is owing to that optimized charge distribution facilitates the intermediates transformation. Aqueous ZABs based on MCC manifests high peak power density of 452 mW cm−2 and durable cycling stability of 1640 h. Quasi‐solid‐state ZABs based on MCC also show satisfactory performances (175 mW cm−2, 105 h). This work provides the route to develop efficient and durable electrocatalyst for constructing ZABs with long lifespan and high‐power‐density.

Heightening polyoxometalate encapsulation efficiency for biaxial strain-induced catalytic activity boosting

Controllable assembly of polyoxometalates (POMs) in confined nanochannels is crucial to understand the host-guest structures and tailor the emerging properties for applications. Here, we report the encapsulation of polyoxometalates inside single-walled carbon nanotubes (SWNTs) for target catalytic regulation. Theoretical modeling predicts the confined polyoxomolybdates are able to induce biaxial tensile strains of SWNTs for more stable interaction with iron phthalocyanine (FePc) and tailor the charge distribution and coordination environment of targetable FeN4 sites, leading to improved catalytic activity toward oxygen reduction reaction (ORR). The polyoxomolybdates are confined in the SWNTs via redox-driven encapsulation mechanism with a POM encapsulation efficiency of about 21 %. The constructed FePc/SWNT@POM molecule catalyst exhibits a high half-wave potential of 0.90 V, excellent stability and methanol tolerance in alkaline medium. The zinc-air battery also presents prominent charge-discharge ability and long-term durability over 400 h with a peak power density of 190.8 mW cm–2.

Rational Design of a Co/MnO-Embedded 2D Nitrogen-Doped Carbon/Carbon Nanotube Hybrid Catalyst for Efficient Oxygen Catalysis and High-Capacity Zn–Air Batteries

Rational Design of a Co/MnO-Embedded 2D Nitrogen-Doped Carbon/Carbon Nanotube Hybrid Catalyst for Efficient Oxygen Catalysis and High-Capacity Zn–Air Batteries

In situ green architecture of the 3D FeZn-N-C based electrocatalyst for efficient oxygen reduction.

We prepared a 3D FeZn-N-C based catalyst by green in situ growth of 1D Fe-N-C carbon nanotubes by introducing ferrocyanide ions on the surface of 2D exfoliated MOF-5. The 1D/2D FeZn-N-C based electrocatalyst is conducive to O2 diffusion and ionic/electron transfer, exhibiting an excellent ORR catalytic performance and a peak power density of 294 mW cm-2 for Zn-air batteries.

Accordion-like multilayered titanium nitride enables FeN4-O axial coordination of iron phthalocyanine as efficient catalysts for oxygen reduction reaction

The susceptibility of MXenes to oxidation leads to rapid chemical degradation and functional loss, and hence limits their diverse applications. In this study, we develop a scalable strategy to transform blocky, condensed titanium nitride (TiN) into accordion-like leafy titanium nitride (M-TiN), which exhibits enhanced chemical stability and an increased surface area. When functionalized with iron phthalocyanine (FePc), the resulting M-TiN/FePc composite displays a remarkable electrocatalytic activity towards the oxygen reduction reaction (ORR) due to the formation of FeN4-O axial coordination and a low-to-intermediate Fe spin state, as confirmed by spectroscopy and magnetic measurements. This leads to electron filling in the antibonding orbitals composed of Fe 3dz2 and O2 π* orbitals, significantly improving O2 activation and ORR activity. Significantly, with the M-TiN/FePc composite as the air cathode catalyst, a zinc-air battery achieves a superior power density of 270.31 mW cm−2 and enhanced cyclability compared to that with commercial Pt/C. Results from this study highlight the significance of morphological engineering of TiN in regulating the atomic configuration of adsorbed metal active centers and hence their catalytic activity, in particular, in harsh oxidative conditions.

Large-Scale Atomic Strain Defects on Palladium Surfaces for Enhanced Oxygen Reduction and Zinc-Air Batteries.

Designing nano-electrocatalysts rich in surface defects is critical to improve their catalytic performance. However, prevailing synthesis techniques rely heavily on complex procedures that compromise defect extensiveness and uniformity, casting a high demand for methods capable of synthesizing large-scale crystalline defects. An innovative design strategy is herein proposed that induces ample strain/dislocation defects during the growth of palladium (Pd), which is well-known as a good oxygen reduction reaction (ORR) catalyst. The controlled defect engineering on Pd core is achieved by the tensile stress exerted from an intentionally applied Fe3O4 skin layer during synthesis, which changes the surface free energy of Pd to stabilize the defect presence. With such large-scale crystalline defects, this Pd catalyst exhibits significantly higher ORR activity than commercial Pt/C, enabling its promising future in zinc-air battery catalysis. Additionally, the protective Fe3O4 skin covering the catalyst also enhances its catalytic stability. Theoretical calculations show that the superior catalytic property of such defect-engineered Pd is associated with the correspondingly modified adsorption energy of *O intermediates onto its surface, which further improves the reaction rate and thus boosts ORR kinetics. Findings here are expected to provide a paradigm for designing efficient and stable metal catalysts with plentiful large-scale strain defects.

Construction of atom-scale Co/Fe/Ni M-N-C active sites within nitrogen-doped carbon spheres for high-performance bifunctional oxygen catalysts in rechargeable zinc-air batteries

Developing carbon-based catalysts with metal‑nitrogen‑carbon (M-N-C) active sites as efficient and low-cost bifunctional catalysts to replace precious metal catalysts for rechargeable zinc-air batteries devices has garnered significant attention. Herein, nitrogen-doped submicron carbon-based spherical bifunctional electrocatalysts (CNPD-CoFeNi) with abundant atom-scale Co/Fe/Ni M-N-C active sites and defects were synthesized. The introduction of massive amounts of Zn species increases the spatial distance of Co/Fe/Ni metal sites to prevent aggregation during pyrolysis, and the evaporation of Zn at high temperatures creates defects synergizing with M-N-C. Consequently, CNPD-CoFeNi possesses a stable carbon-based spherical structure, high electrical conductivity, rich nitrogen content, abundant atom-scale Co/Fe/Ni M-N-C active sites, and defects, displaying outstanding durability, oxygen reduction reaction (ORR) activity with a half-wave potential of 0.87 V, and satisfactory OER performance, surpassing or comparable with the state-of-art Pt/C and RuO2, respectively. Notably, liquid Zn-air batteries with CNPD-CoFeNi catalyst exhibit an exceptional high peak power density of 146.5 mW cm−2 and stable charge-discharge cycling over 270 h, outperforming Pt/C-RuO2 based devices. Additionally, the all-solid-state Zn-air battery also displays satisfactory practicability and stability. The synthesis strategy and its remarkable results provide valuable guidance and inspiration for the future advancement of precious metal substitutes in ORR/OER and rechargeable zinc-air batteries.

Co/CoOx–N–C bifunctional nanocatalyst derived from carbothermally optimized graphene networks with in-situ formed zeolitic imidazolate framework for high performance zinc-air batteries

Rechargeable zinc-air batteries are underpinned by high-performance and durable bifunctional oxygen electrocatalysts. Among the platinum-group metals (PGMs)-free catalysts, the redox-active cobalt-nitrogen-carbon (Co/CoOx–N–C) based materials are promising, however require further structural improvements. This work utilises extremely porous graphene networks (EGO) of hierarchical porosity to in-situ grow ZIF-67 nanocrystals extensively and homogeneously within the porous structure. A simple carbonization of nanoZIF-67@EGO not only generates finely dispersed redox capable Co/CoOx–N–C active sites with the help of residual oxygen functional groups of EGO, but also produces 2-3 dimensional hierarchical porous and conducting structure, readily facilitating high electrochemical surface area. This characteristic structure synergistically contributes to rapid charge and mass transfer rates along with high activity and stability for both ORR and OER. Here, it is worth mentioning that to produce equivalent catalyst material involving different graphitic or template supports requires prolonged and multi-step synthesis routes. The optimized catalyst delivers low potential difference of 0.86 V for bifucntional activity by offering superb ORR half-wave potential of 0.83 V vs RHE and limiting current density of 5.85 mA cm−2 in 0.1 M KOH electrolyte. Zinc-air battery exhibits peak power density of ∼175 mW cm−2 and specific capacity of ∼767 mAh g−1, along with durable cycling round trip efficiency of >63 % (correspond to low voltage gap of ∼0.74 V). These characteristics are better than numerous M–N–C based catalysts reported in the literature. This new strategy holds a great potential to boost the development of diverse MOFs and carbon-based electrocatalysts for a wide range of energy storage and conversion technologies.

Constructing Asymmetric Fe-Nb Diatomic Sites to Enhance ORR Activity and Durability.

Iron-nitrogen-carbon (Fe-N-C) materials have been identified as a promising class of platinum (Pt)-free catalysts for the oxygen reduction reaction (ORR). However, the dissolution and oxidation of Fe atoms severely restrict their long-term stability and performance. Modulating the active microstructure of Fe-N-C is a feasible strategy to enhance the ORR activity and stability. Compared with common 3d transition metals (Co, Ni, etc.), the 4d transition metal atom Nb has fewer d electrons and more unoccupied orbitals, which could potentially forge a more robust interaction with the Fe site to optimize the binding energy of the oxygen-containing intermediates while maintaining stability. Herein, an asymmetric Fe-Nb diatomic site catalyst (FeNb/c-SNC) was synthesized, which exhibited superior ORR performance and stability compared with those of Fe single-atom catalysts (SACs). The strong interaction within the Fe-Nb diatomic sites optimized the desorption energy of key intermediates (*OH), so that the adsorption energy of Fe-*OH approaches the apex of the volcano plot, thus exhibiting optimal ORR activity. More importantly, introducing Nb atoms could effectively strengthen the Fe-N bonding and suppress Fe demetalation, causing an outstanding stability. The zinc-air battery (ZAB) and hydroxide exchange membrane fuel cell (HEMFC) equipped with our FeNb/c-SNC could deliver high peak power densities of 314 mW cm-2 and 1.18 W cm-2, respectively. Notably, the stable operation time for ZAB and HEMFC increased by 9.1 and 5.8 times compared to Fe SACs, respectively. This research offers further insights into developing stable Fe-based atomic-level catalytic materials for the energy conversion process.

Synergistic effect of Fe-Ru alloy and Fe-N-C sites on oxygen reduction reaction

In the pursuit of optimizing Fe-N-C catalysts for the oxygen reduction reaction (ORR), the incorporation of alloy nanoparticles has emerged as a prominent strategy. In this work, we effectively synthesized the FeRu-NC catalyst by anchoring Fe-Ru alloy nanoparticles and FeN4 single atom sites onto carbon nanotubes. The FeRu-NC catalyst exhibits significantly enhanced ORR activity and long-term stability, with a high half-wave potential of 0.89 V (vs. RHE) in alkaline conditions, and the half-wave potential remains nearly unchanged after 5000 cycles. The zinc-air battery (ZAB) assembled with FeRu-NC demonstrates a power density of 169.1 mW cm−2, surpassing that of commercial Pt/C. Density functional theory (DFT) calculations reveal that the synergistic interaction between the Fe–Ru alloy and FeN4 single atoms alters the electronic structure and facilitates charge transfer at the FeN4 sites, thereby modulating the adsorption and desorption of ORR intermediates. This enhancement in catalytic activity for the ORR process underscores the potential of this approach for refining M-N-C catalysts, providing novel insights into their optimization strategies.

Poly(Vinyl Alcohol)/Poly(Acrylic Acid) Gel Polymer Electrolyte Modified with Multi-Walled Carbon Nanotubes and SiO2 Nanospheres to Increase Rechargeability of Zn-Air Batteries.

Zn-air batteries (ZABs) are a promising technology; however, their commercialization is limited by challenges, including those occurring in the electrolyte, and thus, gel polymer electrolytes (GPEs) and hydrogels have emerged as substitutes for traditional aqueous electrolytes. In this work, PVA/PAA membranes were synthesized by the solvent casting method and soaked in 6 M KOH to act as GPEs. The thickness of the membrane was modified (50, 100, and 150 μm), and after determining the best thickness, the membrane was modified with synthesized SiO2 nanospheres and multi-walled carbon nanotubes (CNTs). SEM micrographs revealed that the CNTs displayed lengths of tens of micrometers, having a narrow diameter (95 ± 7 nm). In addition, SEM revealed that the SiO2 nanospheres had homogeneous shapes with sizes of 110 ± 10 nm. Physicochemical experiments revealed that SiO2 incorporation at 5 wt.% increased the water uptake of the PVA/PAA membrane from 465% to 525% and the ionic conductivity to 170 mS cm-1. The further addition of 0.5 wt.% CNTs did not impact the water uptake but it promoted a porous structure, increasing the power density and the stability, showing three-times-higher rechargeability than the ZAB operated with the PVA/PAA GPE.

Construction of Fe/Co-N4 Single-Atom Sites for the Oxygen Reduction Reaction in Zinc-Air Batteries.

Insight into the modulation effect of oxygen reduction reaction (ORR) active centers is of profound significance but remains a great challenge. Here, we designed Co, Fe dual-metal single-atom sites (CoFe-DSAs/NC) uniformly anchored on nitrogen-doped multiwalled carbon nanotubes for boosting ORR performance through regulating the 4d electronic orbitals of the Co-N4 active site. Mechanism studies revealed that for the first time the neighboring Fe-N4 atomic sites were able to regulate the d-band center of Co-N4 single-atom active centers while maintaining the balance of adsorption-desorption affinity for O2 and oxygen-containing species on Co-N4, thereby resulting in a superior ORR performance with a positive half-wave potential (0.90 V vs RHE). The assembled zinc-air battery based on CoFe-DSAs/NC exhibited an increased open-circuit voltage (1.48 V) and an elevated specific capacity (782.33 mAh·g-1). The work provides a new clue for reasonably designing high-performance ORR catalysts through adjusting the d-band center of active sites.

Diatomic Iron with a Pseudo-Phthalocyanine Coordination Environment for Highly Efficient Oxygen Reduction over 150,000 Cycles.

Atomically dispersed Fe-N-C catalysts emerged as promising alternatives to commercial Pt/C for the oxygen reduction reaction. However, the majority of Fe-N-C catalysts showed unsatisfactory activity and durability due to their inferior O-O bond-breaking capability and rapid Fe demetallization. Herein, we create a pseudo-phthalocyanine environment coordinated diatomic iron (Fe2-pPc) catalyst by grafting the core domain of iron phthalocyanine (Fe-Nα-Cα-Nβ) onto defective carbon. In situ characterizations and theoretical calculation confirm that Fe2-pPc follows the fast-kinetic dissociative pathway, whereby Fe2-pPc triggers bridge-mode oxygen adsorption and catalyzes direct O-O radical cleavage. Compared to traditional Fe-N-C and FePc-based catalysts exhibiting superoxo-like oxygen adsorption and an *OOH-involved pathway, Fe2-pPc delivers a superior half-wave potential of 0.92 V. Furthermore, the ultrastrong Nα-Cα bonds in the pPc environment endow the diatomic iron active center with high tolerance for reaction-induced geometric stress, leading to significantly promoted resistance to demetallization. Upon an unprecedented harsh accelerated degradation test of 150,000 cycles, Fe2-pPc experiences negligible Fe loss and an extremely small activity decay of 17 mV, being the most robust candidate among previously reported Fe-N-C catalysts. Zinc-air batteries employing Fe2-pPc exhibit a power density of 255 mW cm-2 and excellent operation stability beyond 440 h. This work brings new insights into the design of atomically precise metallic catalysts.

Carbon Nanofibers Encapsulated CoNiFe Bifunctional Electrocatalysts for Durable Zn-Air Batteries at Room and −40 °C Ultralow Temperatures

Carbon Nanofibers Encapsulated CoNiFe Bifunctional Electrocatalysts for Durable Zn-Air Batteries at Room and −40 °C Ultralow Temperatures

Surface Engineering of N‐Doped Carbon Derived from Polyaniline for Primary Zinc‐Air Batteries

AbstractZinc‐air batteries (ZABs) with metal‐free cathodes are considered environmentally friendly and cost‐effective. However, more active and durable catalysts are required for this purpose. Herein, polyaniline (PANI)‐derived carbon materials were obtained to boost the oxygen reduction reaction (ORR) and, consequently, the performance of a primary ZAB. The developed porous N‐doped carbon (NDC) materials were engineered by varying the polymerization time and calcination temperature (500–900 °C). SEM micrographs and BET surface areas showed that the polymerization of aniline under cold conditions (5 °C) at 6, 8, or 24 h did not have a significant effect on the morphology or surface area. The fibrous structure of PANI was engineered by temperature, resulting in a progressive increase in the surface area until a three‐dimensional porous structure was achieved at 900 °C with the highest area of 601.9 m2 g−1. The surface doping of nitrogen species shifted from PANI‐rich N species to enriched graphitic N from 12.69 % (500 °C) to 24.26 % at 900 °C. The NDC 900 °C presented a voltage of 1.4 V and power density of 56 mW cm−2 (only 7 mW cm−2 lower than that of Pt/C). The results demonstrate that this material is an excellent candidate for high‐performance primary ZABs.

Surface-Engineered Ni2P: An Efficient Oxygen Electrocatalyst for Zinc-Air Battery.

The surface engineering of electrocatalysts is one of the promising strategies to increase the intrinsic activity of electrocatalysts. It generates anion/cation vacancy defects and increases the electrochemically active surface area. We describethe surface engineering of Ni2P to favorably tune the bifunctional oxygen electrocatalytic activity and the development of a rechargeable zinc-air battery (ZAB). Ni2P encapsulated with N and P-dual doped carbon (Ni2P@NPC) is synthesized using a single-source precursor complex tris-(2,2'-bipyridine)nickel(II) bis(hexafluorophosphate). The surface engineering of the as-synthesized Ni2P@NPC is achieved by the controlled acid treatment at room temperature. The surface engineering removes carbon debris and opens the pores, exfoliates the encapsulating carbon layer, increases the P-vacancy in the crystal lattice, and boosts the electrochemically active surface area. Thesurface-engineered catalyst exhibits enhanced bifunctional activity towards oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The electrocatalytically active sites of engineered catalysts are highly accessible for facilitated electron transfer kinetics. P-vacancy favors the facile formation of defect-rich OER active metal oxyhydroxide species. The rechargeable ZAB based on the engineered catalyst delivers a specific capacity of 770.25 mA h gZn-1, energy density of 692 Wh kgZn-1, and excellent charge-discharge cycling performance with negligible voltaic efficiency loss (0.6 %) after 100 h.

A systematic corrosion failure analysis of Li-ion powered hearing aids from various markets

Hearing aids (HA) are low-power electronic devices used worldwide. The ongoing trend in the HA industry has been to move towards Li-ion battery technology replacing conventional zinc-air batteries. The corrosion reliability of HA devices is a critical issue, due to their exposure to harsh user environments including body fluid contact, high humidity, and temperature. The combined effect of higher operating voltage (4.3 V) and design miniaturisation poses new risks for corrosion reliability. To fully understand the environmental reliability issues of the Li-ion powered HA, it is crucial to investigate field performance by conducting root cause failure analysis on the field-returned failed devices. This study investigated two different HA models (open vs. glued model). The analysis used a systematic FMEA-based approach to identify and understand failure modes, mechanisms, and potential causes using various analysis techniques (e.g., LOM, SEM&EDS, and ICP-OES). Furthermore, statistical analysis was conducted based on the repair data created by the global service centre to reveal the failure percentage, and time to failure of different components. Passive components, solder connections, and galvanic charging contact showed the highest failure percentages. The most common causes of corrosion failures were high levels of chloride ions, high humidity, flux residues, and insufficient coating protection.

The Asymmetrical Fe-O-Se Bonds in Fe2O(SeO3)2 Boosting Bifunctional Oxygen Electrocatalytic Performance for Zinc-Air Battery.

HereFe2O(SeO3)2/Fe3C@NC catalysts with high performance werefabricated for zinc-air batteries (ZABs). The experimental results confirmed that the existence of Fe-O-Se bonds in Fe2O(SeO3)2 crystal phase, and the Fe-O-Se bonds could obviously enhance ORR and OER catalytic performance of Fe2O(SeO3)2/Fe3C@NC. Density functional theoretical calculations (DFT) confirmed that the Fe2O(SeO3)2 in Fe2O(SeO3)2/Fe3C@NC had a higher d-band center of Fe atom and a lower p-orbital coupling degree with its own lattice O atom than Fe2O3, which leads to Fe site of Fe2O(SeO3)2 being more likely to adsorb external oxygen intermediates. The Fe-O-Se bonds in Fe2O(SeO3)2 results in the modification of coordination environment of Fe atoms and optimizes the adsorption energy of Fe site for oxygen intermediates. Compared with Fe2O3/Fe3C@NC, the Fe2O(SeO3)2/Fe3C@NC showed obvious enhancements of ORR/OER catalytic activities with a half-wave potential of 0.91 V for ORR in 0.1 M KOH electrolyte and a low overpotential of 345 mV for OER at 10 mA cm-2 in a 1.0 M KOH electrolyte. The peak power density and specific capacity of Fe2O(SeO3)2/Fe3C@NC-based ZABs are higher than those of Pt/C+RuO2-ZABs. The above results demonstrate that the asymmetrical Fe-O-Se bonds in Fe2O(SeO3)2 plays a key role in improving the bifunctional catalytic activities of ORR/OER for ZABs.

Decorated and reconstructed perovskite-oxide electrodes for oxygen electrocatalysis and Zn-air batteries

Although decorated nanoparticles offer a great potential to generate extra active sites, their preparation usually requires time- and energy-consuming approaches. We report the remarkable activity and durability augmentation for the oxygen evolution reaction (OER) via effective and facile on-site electrochemical manipulation, using LaNiO3 as a model catalyst. When compared to the pristine LaNiO3, the electrochemically manipulated LaNiO3 cycled in Fe3+-containing 0.1 M KOH (i.e., E-LNO+Fe) exhibits an almost three-fold improvement in current density at 1.65 V. It is experimentally and theoretically shown that the electrochemical manipulation leads to the creation of defective LaNiO3−δ and NiO on the surfaces, which accelerate phase transformation to (oxy)hydroxides and hence the OER. Furthermore, a Zn–air battery assembled with E-LNO+Fe has demonstrated superior activity by presenting 171 mW cm−2. Thus, our work demonstrates that substantial performance increases may be achieved by decorating and reconstructing perovskite-oxide electrodes via on-site electrochemical modification.