Oxygen Redox Research Articles

Unraveling the Anionic Redox Chemistry in Aqueous Zinc‐MnO2 Batteries

AbstractActivating anionic redox reaction (ARR) has attracted a great interest in Li/Na‐ion batteries owing to the fascinating extra‐capacity at high operating voltages. However, ARR has rarely been reported in aqueous zinc‐ion batteries (AZIBs) and its possibility in the popular MnO2‐based cathodes has not been explored. Herein, the novel manganese deficient MnO2 micro‐nano spheres with interlayer “Ca2+‐pillars” (CaMnO‐140) are prepared via a low‐temperature (140 °C) hydrothermal method, where the Mn vacancies can trigger ARR by creating non‐bonding O 2p states, the pre‐intercalated Ca2+ can reinforce the layered structure and suppress the lattice oxygen release by forming Ca−O configurations. The tailored CaMnO‐140 cathode demonstrates an unprecedentedly high rate capability (485.4 mAh g−1 at 0.1 A g−1 with 154.5 mAh g−1 at 10 A g−1) and a marvelous long‐term cycling durability (90.6 % capacity retention over 5000 cycles) in AZIBs. The reversible oxygen redox chemistry accompanied by CF3SO3− (from the electrolyte) uptake/release, and the manganese redox accompanied by H+/Zn2+ co‐insertion/extraction, are elucidated by advanced synchrotron characterizations and theoretical computations. Finally, pouch‐type CaMnO‐140//Zn batteries manifest bright application prospects with high energy, long life, wide‐temperature adaptability, and high operating safety. This study provides new perspectives for developing high‐energy cathodes for AZIBs by initiating anionic redox chemistry.

Promoting Surface Reconstruction in Spinel Oxides via Tetrahedral-Octahedral Phase Boundary Construction for Efficient Oxygen Evolution.

Understanding the origin of surface reconstruction is crucial for developing highly efficient lattice oxygen oxidation mechanism (LOM) based spinel oxides. Traditionally, the reconstruction has been achieved through electrochemical procedures, such as cyclic voltammetry (CV), linear sweep voltammetry (LSV). In this work, we found that the surface reconstruction in LOM-based CoFe0.25Al1.75O4 catalyst was an irreversible oxygen redox chemical reaction. And a lower oxygen vacancy formation energy (EO-V) could benefit the combination of the activated lattice oxygen atoms with adsorbed water molecular. Motivated by this finding, a strategy of phase boundary construction from Co tetrahedral to octahedral was employed to decrease EO-V in CoFe0.25Al1.75O4. The results showed that as the Co octahedral occupancy ratio rose to 64 %, a 3.5 nm-thick reconstructed layer formed on the catalyst surface with a 158 mV decrease in overpotential. Further experiments indicated that the coexistence of tetrahedral-octahedral (O-T) phase would result in lattice mismatch, promoting non-bonding oxygen states and lowering EO-V. Then more active lattice oxygen combined with H2O molecules to generate hydroxide ions (OH-), followed by soluble cation leaching, which enhanced the reconstruction process. This work provided new insights into the relationship between the intrinsic structure of pre-catalysts and surface reconstruction in LOM-based spinel electrocatalysts.

Unraveling the Anionic Redox Chemistry in Aqueous Zinc-MnO2 Batteries.

Activating anionic redox reaction (ARR) has attracted a great interest in Li/Na-ion batteries owing to the fascinating extra-capacity at high operating voltages. However, ARR has rarely been reported in aqueous zinc-ion batteries (AZIBs) and its possibility in the popular MnO2-based cathodes has not been explored. Herein, the novel manganese deficient MnO2 micro-nano spheres with interlayer "Ca2+-pillars" (CaMnO-140) are prepared via a low-temperature (140 °C) hydrothermal method, where the Mn vacancies can trigger ARR by creating non-bonding O 2p states, the pre-intercalated Ca2+ can reinforce the layered structure and suppress the lattice oxygen release by forming Ca-O configurations. The tailored CaMnO-140 cathode demonstrates an unprecedentedly high rate capability (485.4 mAh g-1 at 0.1 A g-1 with 154.5 mAh g-1 at 10 A g-1) and a marvelous long-term cycling durability (90.6 % capacity retention over 5000 cycles) in AZIBs. The reversible oxygen redox chemistry accompanied by CF3SO3 - (from the electrolyte) uptake/release, and the manganese redox accompanied by H+/Zn2+ co-insertion/extraction, are elucidated by advanced synchrotron characterizations and theoretical computations. Finally, pouch-type CaMnO-140//Zn batteries manifest bright application prospects with high energy, long life, wide-temperature adaptability, and high operating safety. This study provides new perspectives for developing high-energy cathodes for AZIBs by initiating anionic redox chemistry.

Enhancing the Reaction Kinetics and Stability of Co-Free Li-Rich Cathode Materials via a Multifunctional Strategy.

Co-free Li-rich layered oxides (CFLLOs) with anionic redox activity are among the most promising cathode materials for high-energy-density and low-cost lithium-ion batteries (LIBs). However, irreversible oxygen release often causes severe structural deterioration, electrolyte decomposition, and the formation of unstable cathode-electrolyte interface (CEI) film with high impedance. Additionally, the elimination of cobalt elements further deteriorates the reaction kinetics, leading to reduced capacity and poor rate performance. Here, a multifunctional strategy is proposed, incorporating Li2MnO3 phase content regulation, micro-nano structure design, and heteroatom substitution. The increased content of Li2MnO3 phase enhances the capacity through oxygen redox. The smaller nanoscale primary particles induce greater tensile strain and introduce more grain boundaries, thereby improving the reaction kinetics and reactivity, while the larger micron-sized secondary particles help to reduce interfacial side reactions. Furthermore, Na⁺ doping modulates the local coordination environment of oxygen, stabilizing both the anion framework and the crystal structure. As a result, the designed cathode exhibits enhanced rate performance, delivering a capacity of 158 mAh g⁻¹ at 5.0 C and improved cyclic stability, with a high capacity retention of 99% after 400 cycles at 1.0 C. This multifunctional strategy holds great promise for advancing the practical application of CFLLOs in next-generation LIBs.

Importing Atomic Rare‐Earth Sites to Activate Lattice Oxygen of Spinel Oxides for Electrocatalytic Oxygen Evolution

Spinel oxides have emerged as highly active catalysts for the oxygen evolution reaction (OER). However, due to covalency competition, the OER process on spinel oxides often follows an arduous adsorbate evolution mechanism (AEM) pathway. Herein, we propose a novel rare‐earth sites substitution strategy to tune the lattice oxygen redox of spinel oxides and bypass the AEM scaling relationship limitation. Taking NiCo2O4 as a model, the incorporation of Ce into the octahedral site induces the formation of Ce‐O‐M (M: Ni, Co) bridge, which triggers charge redistribution in NiCo2O4. The developed Ce‐NiCo2O4 exhibits remarkable OER activity with a low overpotential, satisfactory electrochemical stability, and good practicability in anion‐exchange membrane water electrolyzer. Theoretical analyses reveal that OER on Ce‐NiCo2O4 surface follows a more favorable lattice oxygen mechanism (LOM) pathway and non‐concerted proton‐electron transfers compared to pure NiCo2O4, as further verified by pH‐dependent behavior and in situ Raman analysis. 18O‐labeled electrochemical mass spectrometry directly demonstrates that oxygen originates from the lattice oxygen of Ce‐NiCo2O4 during OER. It is discovered that electron delocalization of Ce 4f states triggers charge redistribution in NiCo2O4 through the Ce‐O‐M bridge, favoring antibonding state occupation of Ni‐O bonding in [Ce‐O‐Ni] site, thereby activating lattice oxygen redox of NiCo2O4 in OER.

Importing Atomic Rare-Earth Sites to Activate Lattice Oxygen of Spinel Oxides for Electrocatalytic Oxygen Evolution.

Spinel oxides have emerged as highly active catalysts for the oxygen evolution reaction (OER). However, due to covalency competition, the OER process on spinel oxides often follows an arduous adsorbate evolution mechanism (AEM) pathway. Herein, we propose a novel rare-earth sites substitution strategy to tune the lattice oxygen redox of spinel oxides and bypass the AEM scaling relationship limitation. Taking NiCo2O4 as a model, the incorporation of Ce into the octahedral site induces the formation of Ce-O-M (M: Ni, Co) bridge, which triggers charge redistribution in NiCo2O4. The developed Ce-NiCo2O4 exhibits remarkable OER activity with a low overpotential, satisfactory electrochemical stability, and good practicability in anion-exchange membrane water electrolyzer. Theoretical analyses reveal that OER on Ce-NiCo2O4 surface follows a more favorable lattice oxygen mechanism (LOM) pathway and non-concerted proton-electron transfers compared to pure NiCo2O4, as further verified by pH-dependent behavior and in situ Raman analysis.18O-labeled electrochemical mass spectrometry directly demonstrates that oxygen originates from the lattice oxygen of Ce-NiCo2O4 during OER. It is discovered that electron delocalization of Ce 4f states triggers charge redistribution in NiCo2O4 through the Ce-O-M bridge, favoring antibonding state occupation of Ni-O bonding in [Ce-O-Ni] site, thereby activating lattice oxygen redox of NiCo2O4 in OER.

Stabilizing the Layer-Structured Oxide Cathode by Modulating the Oxygen Redox Activity for Sodium Ion Batteries.

The layer-structured oxide cathode for sodium-ion batteries has attracted a widespread attention due to the unique redox properties and the anionic redox activity providing additional capacity. Nevertheless, such excessive oxygen redox reactions will lead to irreversible oxygen release, resulting in a rapid deterioration of the cycling stability. Herein, sulfur ion is successfully introduced to the O3-NaNi0.3Mn0.5Cu0.1Ti0.05W0.05O2 material through high-temperature quenching, thereby developing a novel Na2S-modified O3/P2-NaNi0.3Mn0.5Cu0.1Ti0.05W0.05O2 composite with extended cycling life. The S2- is analyzed for the ability to enhance the reversibility of oxidation-reduction reactions under high voltage and suppress the loss of lattice oxygen during cycling. The stable S─O covalent bonds are found to inhibit the oxygen generation and release within the structure. Benefiting from these improvements, the Na₂S-modified O3/P2-NaNi0.3Mn0.5Cu0.1Ti0.05W0.05O2 exhibited a high reversible capacity of 173.1mA h g-1 over a wide voltage range of 1.5-4.3V under test conditions at 0.1 C and 81.5% capacity retention after 120 cycles at 1 C. The Na₂S-modified O3/P2-NaNi0.3Mn0.5Cu0.1Ti0.05W0.05O2 demonstrates the excellent rate capability with the reversible capacities of 173.1,137.0,114.7,96.7, and 80.1mA h g-1 at 0.1, 0.2, 0.5, 1, and 2 C.

Efficient biodecolorization of direct black 22 Azo Dye by Aspergillus tamarii Kita UCP1279 isolated from caatinga soil

The textile industry is a major consumer of water, generating large volumes of wastewater contaminated with harmful substances, particularly azo dyes, which contain aromatic rings, amines, and sulfonic groups that contribute to their environmental toxicity. The use of microbial agents for wastewater treatment offers a cost-effective and sustainable solution, minimizing sludge production. Fungi from the Caatinga biome have demonstrated potential for bioremediation, especially under extreme environmental conditions. This study explores the ability of Aspergillus tamarii Kita to decolorize the azo dye Direct Black 22 (DB22) under varying conditions, including the use of both active and inactive fungal biomass, in static and agitated systems (120 rpm), at a controlled temperature of 30°C. Dye concentrations of 50, 125, and 250 mg/L were evaluated over time intervals of 75, 180, and 180 minutes, respectively. The influence of dissolved oxygen concentration and redox potential on the decolorization process was also investigated to identify optimal treatment conditions. Decolorization efficiency was quantified via spectrophotometric analysis. Results revealed decolorization rates of 100%, 97%, and 63% for the respective dye concentrations, with active biomass in agitated conditions achieving the highest removal rates. The study further demonstrated that dissolved oxygen levels and redox potential are critical factors in enhancing dye decolorization. These findings underscore the bioremediation potential of Aspergillus tamarii Kita in treating textile dye effluents, offering a promising approach to sustainable industrial wastewater management.

Bulk/Interfacial Structure Design of Li-Rich Mn-Based Cathodes for All-Solid-State Lithium Batteries.

Li-rich Mn-based cathode materials (LRMO) are promising for enhancing energy density of all-solid-state batteries (ASSBs). Nonetheless, the development of efficient Li+/e- pathways is hindered by the poor electrical conductivity of LRMO cathodes and their incompatible interfaces with solid electrolytes (SEs). Herein, we propose a strategy of in-situ bulk/interfacial structure design to construct fast and stable Li+/e- pathways by introducing Li2WO4, which reduces the energy barrier for Li+ migration and enhances the stability of the surface oxygen structure. The reversibility of oxygen redox was improved, and the voltage decay of the LRMO cathode was addressed significantly. As a result, the bulk structure of the LRMO cathodes and the high-voltage solid-solid interfacial stability are improved. Therefore, the ASSBs achieve a high areal capacity (∼3.15 mAh/cm2) and outstanding cycle stability of ≥1200 cycles with 84.1% capacity retention at 1 C at 25 °C. This study offers new insights into LRMO cathode design strategies for ASSBs, focusing on ultrastable high-voltage interfaces and high-loading composite electrodes.

Near-surface reconstruction strategy stabilizing high-voltage redox reactions in single crystal Li-rich Mn-based oxides

Li-rich Mn-based oxides (LRMO) greatly increase its output energy density due to its additional oxygen redox activity. However, the inherent oxygen loss and irreversible phase transition induce low initial coulombic efficiency and serious voltage decay, further seriously impeding its industrial application. Herein, a near-surface in-situ reconstruction strategy has been proposed, which constructs the oxygen vacancies and spinel phase coating on the surface of single-crystal Li-rich Mn-based oxide (SC-LRMO) concurrently to improve Li+ storage performance via the oxalic acid induction method. Intensive exploration based on structure characterizations demonstrates that such a near-surface in-situ reconstruction strategy not only accelerates the transmission of Li+, but also stabilizes high-voltage redox reactions by trapping the escaping On− within the newly formed spinel phase coating. Impressively, the modified sample exhibit 91.1% capacity retention ratio after 300 cycles, superior to the SC-LRMO (74.5% capacity retention ratio after 300 cycles). Additionally, even at a high cut-off voltage of 5 V, the acid etched sample exhibits significantly enhanced cycling stability, delivering 200 mAh g−1 with a 94% capacity retention ratio after 300 cycles. This surface self-reconstruction strategy provides profound insights into regulating the surface structure of LRMO for high-energy-density lithium-ion batteries.

Achievable dual-strategy to stabilize Li-rich layered oxide interface by a one-step wet chemical reaction towards long oxygen redox reversibility

Oxygen release and electrolyte decomposition under high voltage endlessly exacerbate interfacial ramifications and structural degradation of high energy-density Li-rich layered oxide (LLO), leading to voltage and capacity fading. Herein, the dual-strategy of CrxB complex coating and local gradient doping is simultaneously achieved on LLO surface by a one-step wet chemical reaction at room temperature. Density functional theory (DFT) calculations prove that stable B–O and Cr–O bonds through the local gradient doping can significantly reduce the high-energy O 2p states of interfacial lattice O, which is also effective for the near-surface lattice O, thus greatly stabilizing the LLO surface. Besides, differential electrochemical mass spectrometry (DEMS) indicates that the CrxB complex coating can adequately inhibit oxygen release and prevents the migration or dissolution of transition metal ions, including allowing speedy Li+ migration. The voltage and capacity fading of the modified cathode (LLO-CrB) are adequately suppressed, which are benefited from the uniformly dense cathode electrolyte interface (CEI) composed of balanced organic/inorganic composition. Therefore, the specific capacity of LLO-CrB after 200 cycles at 1C is 209.3 mA h g–1 (with a retention rate of 95.1%). This dual-strategy through a one-step wet chemical reaction is expected to be applied in the design and development of other anionic redox cathode materials.

Mechano‐Electrochemical Behavior of Nanostructured Li‐ and Mn‐Rich Layered Oxides with Superior Capacity Retention and Voltage Decay for Sulfide‐Based All‐Solid‐State Batteries

AbstractLi‐ and Mn‐rich layered oxides (LMROs) are recognized as promising cathode materials for lithium‐ion batteries (LIBs) due to their high specific capacity and cost efficiency. However, LMROs encounter challenges such as manganese dissolution in electrolytes and the release of oxygen gas from irreversible oxygen redox reactions, leading to structural degradation and voltage decay that reduce energy density. Consequently, recent research has shifted toward employing LMROs in all‐solid‐state batteries (ASSBs), where Mn dissolution is negligible. Herein, nanostructured LMROs demonstrate superior electrochemical compatibility with sulfide‐based solid electrolytes in ASSBs compared to conventional LIBs. Nanostructured LMRO exhibits outstanding capacity retention (97.1% after 1300 cycles at 30 °C) with significantly suppressed voltage decay. Furthermore, the initial electrochemical activation of Li2MnO3 domains within LMRO is explored in terms of the mechano‐electrochemical interactions in the composite cathode. At elevated temperatures, interfacial degradation accelerates due to the chemical oxidation of Li6PS5Cl solid electrolytes, driven by oxygen released from LMRO. To address this, LMRO surfaces are modified with thioglycolic acid through esterification, suppressing interfacial degradation of Li6PS5Cl and ensuring stable capacity retention over 500 cycles at 60 °C. These findings underscore the potential of LMRO materials as promising cathode options for ASSBs, surpassing those used in LIBs.

Topological Protection of Oxygen Redox in Li-Rich Cathodes.

Lithium-rich layered oxides (LRLOs) are regarded as promising candidates for next-generation cathode materials because of their high energy density derived from anionic redox activity. Recent years have seen increasing efforts in promoting the cyclability of LRLO cathodes, at the core of which is the suppression of irreversible internal structural evolution during cycling. The present article aims to provide an informative perspective on the materials design strategies related to the issue of oxygen release. Emphasis is placed on the underlying chemistry of oxygen redox in LRLOs and the strategies based on material topology that can mitigate oxygen migration to the cathode surface. We speculate that these insights could guide researchers in developing high-capacity cathodes with intrinsically high reversibility of oxygen redox.

Stabilizing oxygen redox reaction in phase-transition-free P2-type Co/Ni-free cathode via Cu doping for sodium-ion batteries

Stabilizing oxygen redox reaction in phase-transition-free P2-type Co/Ni-free cathode via Cu doping for sodium-ion batteries

Fulvic acid impact on constructed wetland–microbial electrolysis cell system performance: Metagenomic insights

This study explores the roles of fulvic acid (FA) in both a conventionally constructed wetland (CCW) and a newly constructed wetland–microbial electrolysis cell (ECW). The results showed that FA increased the average removal efficiency of chemical oxygen demand, total phosphorus, total nitrogen, and ammonia nitrogen in ECW by 8.6, 46.2, 33.0, and 27.9 %, respectively, compared to CCW, and reduced the global warming potential by > 60 %. FA promoted the proliferation of electroactive bacteria (e.g., Chlorobaculum and Candidatus Tenderia) and FA-degrading bacteria (e.g., Anaerolineaceae and Gammaproteobacteria) and reduced methanogens (e.g., Methanothrix) via type-changing. The study’s findings suggest that FA influences pollutant removal and microbiome dynamics by altering dissolved oxygen levels and redox potential. In summary, FA and ECW enhanced the efficiency of constructed wetlands by facilitating electron transfer and consumption, and supporting microbial growth and metabolism.

Effect of sites of doped Mg on the stability of lattice oxygen in lithium-rich manganese-based cathode materials

Elemental doping is considered as an effective method for altering the localized electronic structure of lattice oxygen in lithium-rich manganese-based oxides (LRMO) and enhancing their structural stability. However, the effect of doping heteroatoms at different sites on the oxygen redox is not clear. In this work, Mg is introduced into transition metals (TM) and lithium (Li) sites of LRMO at co-precipitation stage and lithiation stage to prepare LRMO-TM and LRMO-Li, respectively. The experimental results and density-functional theory calculations demonstrate that the oxygen release is reduced from 4.1653 nmol mg−1 of pristine to 3.3886 nmol mg−1 of LRMO-Li, and 2.7688 nmol mg−1 of LRMO-TM. The reduction of oxygen release of LRMO-Li is related to the formation of strong Mg-O interactions. Different from that, the lower oxygen release of LRMO-TM is mainly due to the reduction of electron holes in the O 2p state caused by the weaker Mn-O covalency, which effectively restricts the over-oxidization of oxygen. The capacity retention of LRMO-TM is 85.18 % at 0.2C after 200 cycles, which is higher than that of LRMO (78.63 %) and LRMO-Li (82.28 %). This work reveals the mechanism of enhancing lattice oxygen stability caused by Mg doping at different sites.

Spin Manipulation of Heterogeneous Molecular Electrocatalysts by an Integrated Magnetic Field for Efficient Oxygen Redox Reactions.

Understanding the spin-dependent activity of nitrogen-coordinated single metal atom (M-N-C) electrocatalysts for oxygen reduction and evolution reactions (ORR and OER) remains challenging due to the lack of structure-defined catalysts and effective spin manipulation tools. Herein, both challenges using a magnetic field integrated heterogeneous molecular electrocatalyst prepared by anchoring cobalt phthalocyanine (CoPc) deposited carbon black on polymer-protected magnet nanoparticles, are addressed. The built-in magnetic field can shift the Co center from low- to high-spin (HS) state without atomic structure modification, affording one-order higher turnover frequency, a 50% increased H2O2 selectivity for ORR, and a ≈4000% magnetocurrent enhancement for OER. This catalyst can significantly minimize magnet usage, enabling safe and continuous production of a pure H2O2 solution for 100 h from a 100 cm2 electrolyzer. The new strategy demonstrated here also applies to other metal phthalocyanine-based catalysts, offering a universal platform for studying spin-related electrochemical processes.

Promoting Surface Reconstruction in Spinel Oxides via Tetrahedral‐Octahedral Phase Boundary Construction for Efficient Oxygen Evolution

AbstractUnderstanding the origin of surface reconstruction is crucial for developing highly efficient lattice oxygen oxidation mechanism (LOM) based spinel oxides. Traditionally, the reconstruction has been achieved through electrochemical procedures, such as cyclic voltammetry (CV), linear sweep voltammetry (LSV). In this work, we found that the surface reconstruction in LOM‐based CoFe0.25Al1.75O4 catalyst was an irreversible oxygen redox chemical reaction. And a lower oxygen vacancy formation energy (EO‐V) could benefit the combination of the activated lattice oxygen atoms with adsorbed water molecular. Motivated by this finding, a strategy of phase boundary construction from Co tetrahedral to octahedral was employed to decrease EO‐V in CoFe0.25Al1.75O4. The results showed that as the Co octahedral occupancy ratio rose to 64 %, a 3.5 nm‐thick reconstructed layer formed on the catalyst surface with a 158 mV decrease in overpotential. Further experiments indicated that the coexistence of tetrahedral‐octahedral (O−T) phase would result in lattice mismatch, promoting non‐bonding oxygen states and lowering EO‐V. Then more active lattice oxygen combined with H2O molecules to generate hydroxide ions (OH−), followed by soluble cation leaching, which enhanced the reconstruction process. This work provided new insights into the relationship between the intrinsic structure of pre‐catalysts and surface reconstruction in LOM‐based spinel electrocatalysts.

Achieving Stable Cycling Performance in a P2-Type Layered Oxide Cathode through a Synergic Li/Zn Doping for Sodium-Ion Batteries.

It has been suggested that sodium layered transition metal oxides could potentially serve as excellent cathodes for sodium-ion batteries (SIBs) because of their appropriate operating potentials and high capacities. However, the growing reliance on energy requirements has necessitated a higher energy density of SIBs. It has been demonstrated that activating oxygen-related activities for SIBs is a viable method to improve energy density. Herein, we suggest applying the synergy of Li and Zn codoping to activate the anionic redox reactions (ARRs) and improve their reversibility in Na0.75Ni0.3Mn0.7O2. The dual ion doping alleviates the phase transition and inhibits the Na+/vacancy arrangements, consequently improving the rate capacity and cyclic stability. The Na0.75Li0.15Ni0.1Zn0.05Mn0.7O2 delivers a discharge capacity of 134 mA h g-1 and no significant capacity loss at 100 mA g-1 between 2 and 4.5 V after 200 cycles. More importantly, the density functional theory (DFT) calculation proves that the codoping strategy triggers more ARRs compared to single-element doping, thereby providing enhanced capacity. The codoping induced oxygen redox strategies will create a new path for rational design of cathodes to enhance the energy density for SIBs.

Effects of multi-element composition regulation on the structure and electrochemistry of P2-type layered cathode materials

P2-type Mn-based oxides are promising cathode materials for sodium-ion batteries due to their low cost and high capacity virtue. However, the irreversible phase transition and unstable anion redox at high operating voltages (∼4.2 V) will cause structural distortions, leading to slow sodium-ion diffusion kinetics and severe capacity degradation. Herein, a multi-elemental composition regulation strategy is proposed to enhance the structural stability of P2-type cathode by optimizing the structure and modulating the irreversible oxygen redox during high-voltage cycling. A series of multi-element cathodes Na0.67(Fe1/4Co1/4Ni1/4Ti1/4)1-xMnxO2 (x = 0.4,0.5,0.6,0.7,0.8,0.9) are designed and the effects of component modulation on their structure and electrochemical behavior are systematically investigated. Especially, the optimized Na0.67Fe0.05Co0.05Ni0.05Ti0.05Mn0.8O2 cathode maintains P2 phase during the initial charging/discharging between 1.5 V and 4.5 V, inhibits irreversible oxygen redox, and exhibits small lattice expansion. Impressively, the above optimized cathode exhibits superior cycling stability with capacity retention of nearly 90 % and reversible capacity of 130.1 mAhg−1 after 100 cycles at 1C rate. Furthermore, the optimized cathode also displays an excellent rate capability (capacity of 108.2 mAh g−1 at 5 C rate) due to the enhanced Na+ diffusion kinetics. This work provides new insight into developing high-stable Mn-based oxide cathodes operating at high voltage for sodium-ion batteries.