Long-term Cycle Life Research Articles

Two-Dimensional Porphyrin-Based Covalent Organic Frameworks/g-C3N4 Composites as High-Performance Supercapacitor.

Covalent organic frameworks (COFs) with high porosity and redox-active properties have been advanced as electrode materials for energy storage systems, although poor electron conductivity and inaccessibility of active pore sites hinder their performance as electrode material for supercapacitor application. Thus, incorporation of a COF with various conductive materials can be an effective strategy to improve their electrochemical performances for supercapacitors. Herein, we report the synthesis of POR-COF@g-C3N4 composites by fabricating a porphyrin-based COF on g-C3N4 via in situ solvothermal conditions. A series of COF composites, known as POR-COF@g-C3N4-X, were prepared by incorporating different ratios of COF (X = 10%, 20%, 30%, and 40%) into g-C3N4 and investigated as electrode materials for supercapacitor performance. The optimized COF composite (POR-COF@g-C3N4-30) achieved a specific capacitance of 788 F g-1 at 4 A g-1, much higher compared to pristine COF. Further, the asymmetric device assembled using POR-COF@g-C3N4-30 demonstrated a high energy density of 24.4 Wh kg-1 at a power density of 1152 W kg-1 and a long-term cycling life of 74% capacity retention after 6000 cycles. Our work highlights the scope of COF-based composites as active electrode materials for highly efficient supercapacitor performance.

An Amphiphilic Molecule Induced Anion-Enrichment Interface for Next-Generation Lithium Metal Batteries.

The electrolyte engineering enables the fabrication of robust electrode/electrolyte interphase with excellent electrochemical stability for reliable lithium (Li) metal batteries (LMBs). Herein, an amphiphilic molecule nonafluoro-1-butanesulfonate (NFSA) is employed in electrolytes to realize anion-enrichment interfacial design. The functions of such an amphiphilic molecule in the electrolyte and anode/electrolyte interphases of LMBs are elucidated via theoretical and experimental analyses. The polar lithophilic segments (-SO3-) present a capability to solvate Li+, while the perfluoroalkyl chains (-CF2CF2CF2CF3) exhibit a solvent-phobic, which alters the Li+ solvation environment in the electrolyte and thus building a favorable interphase enriched with anion-derived inorganic compositions on Li electrode. As a result, the designed electrolyte enables stable operation of the Li||Cu cells for more than 200 cycles with a cumulative irreversible capacity loss of only 2.4 mAh cm-2, and the long-term cycle life of the Li||Li cells is extended to more than 1500h with a small overpotential (36.5mV). Moreover, prolonged cycle life of the full cell assembled with commercial LiFePO4 cathode (over 80% capacity retention after 500 cycles at 0.5 C) is achieved even under the limiting Li source (≈5 mAh cm-2), high cathode loading (≈12mg cm-2), and lean electrolyte (≈2.5µL mg-1).

Construction of Ordered and Fast Lithium Ion Channels in Gel Electrolytes for Li-SPAN Batteries.

As one of the most promising battery systems, the lithium sulfur battery is expected to be widely used in fields of high energy density demands. Owing to the unique solid-solid conversion mechanism, there is no shuttle effect for the Li-SPAN (sulfurized polyacrylonitrile) battery. However, the compatibility between Li anode and carbonate electrolyte has not been resolved, which prevents the SPAN from practical applications. Herein, an organic-inorganic gel carbonate electrolyte is proposed to stabilize interphases and structures of both the anode and cathode, where polyimide (PI) is used for electrolyte gelation, which can assist in the uniform distribution of inorganic components at the electrolyte interface. Furthermore, ZnS nanodots loaded on two-dimensional MoS2 flakes provide abundant Li-ion diffusion paths, improve the transfer kinetic of Li ions, and induce uniform nucleation and deposition of Li. This gel electrolyte ensures Li symmetric cells a long-term cycle life of more than 900 h under the condition of deep lithium plating/stripping at 5 mAh cm-1. Li∥Cu cells exhibit a prolonged lifespan of 800 h with a CE of 98.3%. Furthermore, the Li-SPAN battery shows stability of more than 850 cycles, with the capacity retention of 85.1%. This work provides an approach for high-energy Li-SPAN batteries with carbonate-based electrolytes.

Boosting the Structural Reversibility of Layered Oxide Cathode for Realizing Long-Term Cycle Life Through Electronic Structure Regulation.

O3-type layered oxide cathode exhibits great application potential for practical sodium-ion batteries, due to its cost-effectiveness, abundant sodium and manganese resources, and high theoretical capacity. However, the irreversible phase transition, coupled with rapid capacity decay, which is primarily attributed to the Jahn-Teller effect of Mn3+, remains a significant bottleneck for commercial application. Additionally, the sluggish kinetics during the (de)sodiation process require urgent improvement. Herein, an electronic structure regulation strategy is proposed by low-valence Li/Cu co-substitution to address these issues. The roles of Li/Cu on the electronic structure, structural evolution, and electrochemical properties in the Na0.96Ni0.22Fe0.2Mn0.5Li0.04Cu0.04O2 (NFMLC) cathode are comprehensively explored through systematic in situ/ex situ characterization techniques and theoretical calculations. The results reveal that this strategy effectively activates more Ni2+/3+ and Fe3+/4+ redox reactions above 2.5V, while suppressing Mn3+/4+ redox activity below 2.5V, thereby achieving highly structural reversibility. Therefore, the NFMLC electrode displays excellent long-term cycling stability (81.5% capacity retention after 2000 cycles at 5 C), and significantly enhanced rate performance (from 45.5% to 80.4% under a ratio of 5 C to 0.5 C). This work provides a valuable perspective on the design of low-cost, long-life, and high-performance layered oxide cathodes for practical sodium-ion batteries.

Cationic and Anionic Dual Redox Activity of MoS2 for Electrochemical Potassium Storage.

MoS2 is regarded as one of the most promising potassium-ion battery (PIB) anodes. Despite the great progress to enhance its electrochemical performance, understanding of the electrochemical mechanism to store K-ions in MoS2 remains unclear. This work reports that the K storage process in MoS2 follows a complex reaction pathway involving the conversion reactions of Mo and S, showing both cationic redox activity of Mo and anionic redox activity of S. The presence of dual redox activity, characterized in-depth through synchrotron X-ray absorption, X-ray photoelectron, Raman, and UV-vis spectroscopies, reveals that the irreversible Mo oxidation during the depotassiation process directs the reaction pathway toward S oxidation, which leads to the occurrence of K-S electrochemistry in the (de)potassiation process. Moreover, the dual reaction pathway can be adjusted by controlling the discharge depth at different cycling stages of MoS2, realizing a long-term stable cycle life of MoS2 as a PIB anode.

Enhanced Long-Term Cycling Life of Ni-Rich NMC Cathodes in High-Voltage Lithium-Metal Batteries.

Li metal batteries (LMBs) have revived people's interest due to their high energy density. This work compares the cycling stability, structure stability, and thermal stability of Li||0.7Nb-NMC 9055 (0.7% Nb-modified LiNi0.9Co0.05Mn0.05O2) system in commercial carbonate electrolyte (1.0 M LiPF6 in EC/DMC) and designed carbonate electrolyte (1.0 M LiPF6-0.125 M LiNO3-0.025 M Mg(TFSI)2 in FEC-EMC). Li||0.7Nb-NMC 9055 battery with designed carbonate electrolyte exhibited superior capacity retention, 80% after ∼500 cycles. This can be explained by the improved mechanical integrity of the secondary particles and large reduced charge transfer resistance. Further, the real-time thermal monitoring of full cell via a high-precision, multimode calorimeter TAM IV Micro XL shows that the designed carbonate electrolyte with multisalt additive and FEC cosolvent has less heat release during the charging and discharge process, allowing these high-nickel (Ni) cathodes to reach closer to their full potential.

In Situ Inorganic/Organic Protective Layer on Carbon Paper as Advanced Current Collector for Robust Li Metal Anode.

Lithium (Li) metal is regarded as the most promising anode for next-generation batteries with high energy density. However, the uncontrolled dendrite growth and infinite volume expansion during cycling seriously hinder the application of Li metal batteries (LMBs). Herein, an inorganic/organic protective layer (labeled as BPH), composed of in situ formed inorganic constituents and PVDF-HFP, is designed on the 3D carbon paper (CP) surface by hot-dipping method. The BPH layer can effectively improve the mechanical strength and ionic conductivity of the SEI layer, which is beneficial to expedite the Li-ion transfer of the entire framework and achieve stable Li plating/stripping behavior. As a result, the modified 3D CP (BPH-CP) exhibits an ultrahigh average Coulombic efficiency (CE) of ≈99.7% over 400 cycles. Further, the Li||LiFePO4 (LFP) cell exhibits an extremely long-term cycle life of over 3000 cycles at 5 C. Importantly, the full cell with high mass loading LiFePO4 (20mgcm-2) or LiNi0.8Co0.1Mn0.1O2 (NCM, 16mgcm-2) cathode exhibits stable cycling for 100 or 150 cycles at 0.5 C with high-capacity retention of 86.5% or 82.0% even at extremely low N/P ratio of 0.88 or 0.94. believe that this work enlightens a simple and effective strategy for the application of high-energy-density and high-rate-C LMBs.

The design of chemisorption and catalysis synergistic defender for efficient room temperature sodium-sulfur batteries

Room temperature sodium-sulfur (RT-Na/S) batteries are a promising candidate for large-scale energy storage systems owing to their low manufacturing cost and high energy density. However, the severe shuttle effects and sluggish reaction kinetics hinder their practical application. Here, a Fe3Se4 nanoparticle anchored three-dimensional nitrogen-doped porous carbon nanosheet was designed as a functional defender to inhibit the shuttle effect and achieve high sulfur utilization. The porous carbon nanosheet builds a fast platform for electron and ion transport and acts as a limiting barrier for polysulfide dissolution and shuttling. Additionally, Fe3Se4 nanoparticles are incorporated to enhance the chemical anchoring and catalytic activity of polysulfides. The ex-situ characterization revealed that the Fe sites can feed electrons to polysulfides, thus facilitating the conversion of long-chain polysulfides to Na2S, resulting in high sulfur availability (323 mAh/g at 2 A/g) and long-term cycle life (72 % capacity retention at 1 A/g for 500 cycles).

Li-Ion Batteries with a Binder-Free Cathode of Carbon Nanotubes-LiFePO4-Al Foam

With the increasing demand for Li resources worldwide, the easy recycling of Li-ion batteries materials becomes essential. We report a binder-free cathode consisting of carbon nanotubes (CNTs) and LiFePO4 (LFP) nanoparticles embedded in a 3D Al network. The electrode stability depends on the CNT ratio, where 3% CNT-wrapping LFPs provide a stable structure free of detachment from Al foam, as observed on Al foil. The binder-free cathode sheet exhibited excellent performance for high-rate discharge and long-term cycle life. Materials on the cathode can be easily detached with ultrasonic treatment when immersed in organic solvent, which is advantageous for a green and high-efficiency strategy of recycling all valuable materials compared to the binder-used electrode.

Regulating the inner Helmholtz plane with an electrophilic cation additive enabled stacked stratiform growth for highly reversible Zn anodes

Achieving consecutive flattening and dendrite-free deposition for the zinc anodes is essential to avoid internal short circuits or premature failure in the Zn-ion hybrid supercapacitor (ZHSC), which largely depends on the crystal growth during the electrocrystallization process. Herein, the tetrapropyl ammonium bromide additive was employed to reconstruct the inner Helmholtz plane (IHP) structure for manipulating the Zn deposition behavior and stabilizing the interfacial electrochemistry. Joint experimental and theoretical results show that electrophilic quaternary ammonium cations (TPA+) provoke the linkage effect after the specifical adsorption at IHP of the Zn electrode, which includes the molecular/ion distribution regulation, electrostatic shielding effect, crystallographic optimization, and solid electrolyte interphase (SEI) layer formation. The adsorbed TPA+ cations at IHP expel SO42− anions, bringing a reconfiguration of the ion/molecule distribution, which leads to a relatively uniform Zn2+ions distribution at electrode/electrolyte interface and a sluggish electroreduction reaction kinetics. Meanwhile, the electrostatic shielding effect regulates the crystallographic energetic preference of Zn deposits and induces the stratiform Zn growth and dominant Zn (002) texture. Concomitantly, the partial interfacial adsorbed TPA+ cations were electrochemically reduced to form the inorganic-organic hybrid SEI layer to further enhance the corrosion resistance and stability of the Zn electrode. Consequently, TPA+ cations mediated electrolyte enables Zn||Zn cells to exhibit a reversible plating/stripping performance for more than 2800 h. Additionally, a long-term cycling life can be obtained in the Zn||activated carbon ZHSC with this electrolyte. The electrolyte mediation strategy to realize the complementary interface effect and crystalline optimization provides promising feasibility on highly reversible Zn anodes.

Constructing hierarchical CuS hollow spheres as efficient anode for aqueous zinc-ion batteries

In recent years, aqueous zinc-ion batteries (ZIBs) have emerged as a prominent research topic due to their inherent safety attributes, relatively low cost, and comparatively higher energy density. However, the challenges associated with the zinc metal anode in the form of dendrite formation, hydrogen evolution, and severe side reactions have proven to be particularly vexing. Thus, it is imperative to investigate novel intercalation-type anode materials for ZIBs that exhibit exceptional structural properties and appropriate redox potentials based on conversion mechanisms. In this work, through adding polyvinylpyrrolidone (PVP) surfactant to precursors and tailoring reaction time, hierarchical CuS hollow spheres are successfully constructed by a facile one-step hydrothermal process. When applied as an anode in ZIBs, the hollow hierarchical CuS with large surface area can effectively reduce the transport distance of electrons and Zn2+ and alleviate volume expansion during the insertion/extraction of Zn2+. The hierarchical CuS hollow spheres prepared over 8 h (CuS-8) exhibit a specific capacity of 126 mAh/g and long-term cycle life (1500 cycles) at a current density of 3 A/g. In addition, CuS-8//MnO2@CNTs full-cell shows a capacity retention of 117 mAh/g after 300 cycles at 1 A/g current density, which proves the advantage of hierarchical CuS hollow spheres in serving as an efficient and durable anode material for ZIBs.

Double-skeleton interpenetrating network-structured alkaline solid-state electrolyte enables flexible zinc-air batteries with enhanced power density and long-term cycle life

The alkaline solid-state electrolytes have received widespread attention for their good safety and electrochemical stability. However, they still suffer from low conductivity and poor mechanical properties. Herein, we report the synthesis of double-network featured hydroxide-conductive membranes fabricated by polyvinyl alcohol (PVA) and chitosan (CS) as the double-skeletons. Then, we implanted quaternary ammonium salt guar hydroxypropyltrimonium chloride (GG) as the OH− conductor for high-performance electrochemical devices. By virtue of the unique stripe-like structure shared from the double skeleton with a high degree of compatibility and stronger hydrogen bond interactions, the polyvinyl alcohol/chitosan-guar hydroxypropyltrimonium chloride (PCG) solid-state electrolytes achieved optimal thermal stability (> 300 °C), mechanical property (∼ 34.15 MPa), dimensional stability (at any bending angle), and high ionic conductivity (13 mS cm−1) and ion mobility number (tion ∼ 0.90) compared with chitosan-guar hydroxypropyltrimonium chloride (CG) and polyvinyl alcohol-guar hydroxypropyltrimonium chloride (PG) electrolyte membrane. As a proof-of-concept application, the “sandwich”-type zinc-air battery (ZAB) assembled using PCG membrane as the electrolyte realized a high open-circuit voltage (1.39 V) and an excellent power density (128 mW cm−2). Notably, in addition to its long-term cycle life (30 h, 2 mA cm−2) and stable discharge plateau (12 h, 5 mA cm−2), it could even enable a flexible ZAB (F-ZAB) to readily power light-emitting diodes (LED) at any bending angle. These merits afford the PCG membrane a promising electrolyte for improving the performance of solid-state batteries.

A novel bimetallic-polyanion Na4Fe2.82Ni0.18(PO4)2P2O7 cathode with superior rate performance and long cycle-life for sodium-ion batteries

Na4Fe3(PO4)2P2O7, with the advantages of strong structural stability, suitable voltage window, low cost and green pollution-free, is considered as a highly researchable cathode material for sodium-ion batteries. However, the low conductivity of Na4Fe3(PO4)2P2O7 and the inevitable electrochemical inertia from maricite-NaFePO4 impurity during the preparation process lead to the low reversible capacity and poor cycling stability. In this work, a new bimetallic-polyanion cathode material Na4Fe2.82Ni0.18(PO4)2P2O7 capped with an in-situ nitrogen-doped carbon layer is proposed. Ni-substituting inhibits the generation of electrochemical inert maricite-NaFePO4 impurity and enhances the Na+ ion conductivity. Meanwhile, a lower volume-change during the charging/discharging process can be achieved in Na4Fe2.82Ni0.18(PO4)2P2O7 electrode compared with conventional Na4Fe3(PO4)2P2O7 electrode. With the synergistic effect of in-situ N-doping and Ni-substituting, an ultra-high initial discharge capacity (128.4 mAh g−1 at 0.2C), superior rate performance (62.5 mAh g−1 at 50C) and significant long-term cycle life (capacity retention rate of about 83 % after 3000 cycles at 10C) can be achieved in the optimal Na4Fe2.82Ni0.18(PO4)2P2O7@C-N (Ni6-NFPP@C-N) cathode. This study suggests a practical strategy to produce Na4Fe3(PO4)2P2O7-based electrode material with no impurities and superior electrochemical properties for sodium-ion batteries.

Directional Polarization of a Ferroelectric Intermediate Layer Inspires a Built-In Field in Si Anodes to Regulate Li+ Transport Behaviors in Particles and Electrolyte.

The silicon (Si) anode is prone to forming a high electric field gradient and concentration gradient on the electrode surface under high-rate conditions, which may destroy the surface structure and decrease cycling stability. In this study, a ferroelectric (BaTiO3) interlayer and field polarization treatment are introduced to set up a built-in field, which optimizes the transport mechanisms of Li+ in solid and liquid phases and thus enhances the rate performance and cycling stability of Si anodes. Also, a fast discharging and slow charging phenomenon is observed in a half-cell with a high reversible capacity of 1500.8mAhg-1 when controlling the polarization direction of the interlayer, which means a fast charging and slow discharging property in a full battery and thus is valuable for potential applications in commercial batteries. Simulation results demonstrated that the built-in field plays a key role in regulating the Li+ concentration distribution in the electrolyte and the Li+ diffusion behavior inside particles, leading to more uniform Li+ diffusion from local high-concentration sites to surrounding regions. The assembled lithium-ion battery with a BaTiO3 interlayer exhibited superior electrochemical performance and long-term cycling life (915.6mAhg-1 after 300 cycles at a high current density of 4.2Ag-1). The significance of this research lies in exploring a new approach to improve the performance of lithium-ion batteries and providing new ideas and pathways for addressing the challenges faced by Si-based anodes.

In situ nitrogen-doped into MnO2/carbon derived from manganese (II) – triazole framework to achieve superior zinc ions storage

The widespread application of MnO2 as cathodes for aqueous zinc ions batteries (AZIBs) suffers from challenging issues of inferior ion storage capability, poor intrinsic electronic conduction and undesirable Mn dissolution. Herein, we demonstrate that the nitrogen can be successfully in situ doped into both the MnO2 and carbon lattice to form N-doped MnO2/C (NMC) by pyrolyzing the Mn based metal-triazole (Mn-MET) framework. The generation of oxygen vacancies in MnO2 and the presence of N-doped carbon in the composite not only increase the electronic conductivity to accelerate charges transfer in MnO2, but also relieve the Mn dissolution to stabilize the MnO2 structure. As a result, the NMC cathode based AZIB is able to display high discharge capacity of 339.3 mAh g−1, much higher than the bare Mn2O3 cathode (147.8 mAh g−1). The excellent long-term cycling life with a capacity retention of 82.8 % can be also achieved after 1000 cycles under 3 A g−1. The energy storage mechanism of the NMC cathode related to the reversible H+ and Zn2+ interaction/extraction are systematically investigated through multiple ex situ characterizations. Thus, these inspiring results in our work are expected to stimulate the exploitation of MOFs derived cathode materials for high-performance AZIBs.

A dual-functional rare earth halide additive for high-performance aqueous zinc ion batteries

Aqueous zinc ion batteries have received much attention due to their high theoretical capacity, inherent safety, and low cost. However, the growth of zinc dendrites and side reactions hinder its practical application. In this study, a rare-earth metal salt, europium chloride (EuCl3), is used as a new electrolyte additive to regulate the uniform deposition of zinc and inhibit the interfacial side reactions. The EuCl3 additive benefits for preferentially Zn2+ deposition along the (002) crystal plane, as well as suppress the hydrogen evolution reaction (HER) at electrode-electrolyte interface. As a result, the capacity retention of the Zn//NaV3O8 full cell assembled with the modified electrolyte much better than that without additives, showing a long-term cycling life and high coulombic efficiency at a current density of 10 A g−1. This new dual-functional rare earth halide additive strategy provides great potential for the development of practical aqueous zinc ion batteries and other battery systems.

Temperature-Dependent Electrochemical Performance of Ta-Substituted SrCoO3 Perovskite for Supercapacitors.

Developing new electrode materials with good temperature-dependent electrochemical performance has become a great issue for the deployment of hybrid supercapacitors with wide temperature tolerance. In this work, a series of Ta-substituted SrCo1-x Tax O3-δ (x=0.05, 0.10, 0.15, 0.20) perovskites have been studied as positive electrodes for hybrid supercapacitors in terms of their structures, elemental valence states and electrochemical performances. Incorporating Ta into SrCoO3-δ perovskite not only stabilizes the crystallite structure but also notably improves electrochemical activities. The SrCo0.95 Ta0.05 O3-δ @CC delivers the highest specific capacity (Qsp ) of 227.91 C g-1 at 1 A g-1 , which is attributed to the highest oxygen vacancy content and the fastest oxygen diffusion kinetics. The hybrid supercapacitor SrCo0.95 Ta0.05 O3-δ @CC//AC@CC exhibits a high energy density of 22.82 Wh kg-1 @775.09 W kg-1 and a stable long-term cycle life (5000 cycles) with 90.7 % capacity retention. As temperature increases from 25 to 85 °C, the capacitance properties are improved at elevated temperatures for both electrode and device due to the increased electrolyte conductivity. The outstanding electrochemical results present that SrCo1-x Tax O3-δ perovskite holds good prospects for hybrid supercapacitors with wide temperature tolerance.

A surface-modified Na3V2(PO4)2F3 cathode with high rate capability and cycling stability for sodium ion batteries.

High voltage, high rate, and cycling-stable cathodes are urgently needed for development of commercially viable sodium ion batteries (SIBs). Herein, we report a facial ball-milling to synthesize a carbon-coated Na3V2(PO4)2F3 composite (C-NVPF). Benefiting from the highly conductive carbon layer, the C-NVPF material exhibits a high reversible capacity (110.6 mA h g-1 at 0.1C), long-term cycle life (54% of capacity retention up to 2000 cycles at 5C), and excellent rate performance (35.1 mA h g-1 at 30C). The present results suggest promising applications of the C-NVPF material as a high-performance cathode for sodium ion batteries.

Heterointerface regulation of covalent organic framework-anchored graphene via a solvent-free strategy for high-performance supercapacitor and hybrid capacitive deionization electrodes.

Covalent organic frameworks (COFs) with customizable geometry and redox centers are an ideal candidate for supercapacitors and hybrid capacitive deionization (HCDI). However, their poor intrinsic conductivity and micropore-dominated pore structures severely impair their electrochemical performance, and the synthesis process using organic solvents brings serious environmental and cost issues. Herein, a 2D redox-active pyrazine-based COF (BAHC-COF) was anchored on the surface of graphene in a solvent-free strategy for heterointerface regulation. The as-prepared BAHC-COF/graphene (BAHCGO) nanohybrid materials possess high-speed charge transport offered by the graphene carrier and accelerated electrolyte ion migration within the BAHC-COF, allowing ions to effectively occupy ion storage sites inside BAHC. As a result, the BAHCGO//activated carbon asymmetric supercapacitor achieves a high energy output of 61.2 W h kg-1 and a satisfactory long-term cycling life. More importantly, BAHCGO-based HCDI possesses a high salt adsorption capacity (SAC) of 67.5 mg g-1 and excellent long-term desalination/regeneration stability. This work accelerates the application of COF-based materials in the fields of energy storage and water treatment.

Realizing long-term cycling stability of O3-type layered oxide cathodes for sodium-ion batteries.

O3-type layered oxide cathodes are promising for practical sodium-ion batteries (SIBs) owing to their high theoretical capacity, facile synthesis, and sufficient Na+ storage. However, they face challenges such as rapid capacity loss and poor cycling stability, mainly attributed to irreversible phase transitions. To address these challenges, a novel cathode material, Li/Sn co-substituted O3-Na0.95Li0.07Sn0.01Ni0.22Fe0.2Mn0.5O2 (LSNFM), has been designed by regulating the electronic structure, in which Li+ activates more redox reactions of Ni2+/3+ and Fe3+/4+ above 2.5 V and suppresses the redox reactivity of Mn3+/4+ below 2.5 V, while Sn4+ can prevent the charge delocalization in the transition metal layer, contributing to structural stability. Due to this synergistic effect, the as-prepared LSNFM electrode with high structural reversibility displays a 27.2% capacity increase contributed by the high-voltage transition metal ion redox activity and exhibits excellent long-term cycling stability, an 84.0% capacity retention after 500 cycles at 1 C and an 84.7% capacity retention after 2000 cycles at 5 C. The fundamental mechanism is fully investigated using systematic in situ/ex situ characterization techniques and density functional theory computations. This work provides a paradigm for designing long-term cycle life cathode materials by synergistically regulating the electronic structure in practical SIBs.