High-performance Aqueous Zinc-ion Research Articles

Tunneling Proton Grotthuss Transfer Channels by Hydrophilic-Zincophobic Heterointerface Shielding for High-Performance Zn-MnO2 Batteries.

Hollandite-type manganese dioxide (α-MnO2) is recognized as a promising cathode material upon high-performance aqueous zinc-ion batteries (ZIBs) owing to the high theoretical capacities, high working potentials, unique Zn2+/H+ co-insertion chemistry, and environmental friendliness. However, its practical applications limited by Zn2+ accommodation, where the strong coulombic interaction and sluggish kinetics cause significant lattice deformation, fast capacity degradation, insufficient rate capability, and undesired interface degradation. It remains challenging to accurately modulate H+ intercalation while suppressing Zn2+ insertion for better lattice stability and electrochemical kinetics. Herein, proton Grotthuss transfer channels are first tunneled by shielding MnO2 with hydrophilic-zincophobic heterointerface, fulfilling the H+-dominating diffusion with the state-of-the-art ZIBs performance. Local atomic structure and theoretical simulation confirm that surface-engineered α-MnO2 affords to the synergy of Mn electron t2g-eg activation, oxygen vacancy enrichment, selective H+ Grotthuss transfer, and accelerated desolvation kinetics. Consequently, fortified α-MnO2 achieves prominent low current density cycle stability (≈100% capacity retention at 1C after 400 cycles), remarkable long-lifespan cycling performance (98% capacity retention at 20C after 12000 cycles), and ultrafast rate performance (up to 30C). The study exemplifies a new approach of heterointerface engineering for regulation of H+-dominating Grotthuss transfer and lattice stabilization in α-MnO2 toward reliable ZIBs.

Reversible Deposition/Dissolution of Double Hydroxides to Modulate Electrolyte pH Enabling High-Performance Aqueous Zinc-Ion Batteries.

Vanadium oxide has been extensively studied as a host of zinc ion intercalation but still suffers from low conductivity, dissolution, and byproduct accumulation during cycling. Here, we hydrothermally synthesize the VO2@MXene Ti3C2 (MV) composite and find that in the MV//3 M Zn(CF3SO3)2//Zn system, the double hydroxide Zn12(CF3SO3)9(OH)15·nH2O (ZCOH) uniformly covers VO2 during the charging process and dissolves reversibly during the discharge process. In situ X-ray diffraction of the MV combined with in situ pH measurements reveals that ZCOH acts as a pH buffer during cycling, which is beneficial to the cycling stability of batteries. And the theoretical calculation indicates that the decomposition energy required by ZCOH on the MV surface is lower than that on pure VO2, which is more conducive to ZCOH dissolution. The coin battery exhibits high-rate performance of 65.1% capacity retention at a current density of 15 A g-1 (compared to 0.6 A g-1) and a long cycling life of 20,000 cycles with a capacity retention of 80.7%. For a 22.4 mA h soft-packaged battery, its capacity remains at 72.1% after 2000 cycles. This work demonstrates the active role of ZCOH in the electrochemical process of VO2 and provides a new perspective for exploiting this mechanism to develop high-performance aqueous zinc-ion battery vanadium oxide cathode materials.

Crystalline MnCO3@Amorphous MnOx Composite as Cathode Material for High-Performance Aqueous Zinc-Ion Batteries.

Rechargeable aqueous zinc-ion batteries (RAZIBs) have received extensive attention because of their advantages of low cost, high safety, and nontoxicity. However, problems such as dissolution of the active cathode material, dendrites/passivation of the zinc anode, and slow reaction kinetics hindered their further applications. In this work, a crystalline/amorphous composite-type material composed of crystalline MnCO3 and amorphous MnOx was prepared and used as the cathode material for RAZIBs. The MnCO3@amorphous MnOx (MnCO3@A-MnOx) composite possesses the merits of both the pure crystalline phase of MnCO3 and the amorphous phase of MnOx, which can deliver better electrochemical performance than the corresponding single component in repeated cycles. In addition, crystalline MnCO3 undergoes a complex phase transition to the active MnO2 during the first charge process, providing the composite with a stable structure and additional electrochemical capacity. The electrochemical measurement results indicate that the MnCO3@A-MnOx electrode can display high reversible discharge capacity at 0.1 A g-1, excellent rate performance at 5.0 A g-1, and long cycling stability over 2000 cycles, showing great potential as a cathode material for high-performance RAZIBs.

Synthesis of binder-free hydrated vanadium oxide-polyaniline electrodes via in situ polymerization for high-performance aqueous zinc-ion batteries

Hydrated vanadium oxide, a kind of layered electrode material with high theoretical specific capacity, has great potential for developing high-performance, low-cost, and eco-friendly aqueous zinc-ion batteries. However, its characteristics of poor electronic conductivity, vanadium dissolution, and unstable structure lead to poor electrochemical performance, such as low specific capacity, poor rate performance and short cycle life. Combining PANI with layered hydrated vanadium oxide is expected to overcome the shortcomings and achieve high zinc storage performance. In this work, binder-free hydrated vanadium oxide-polyaniline inorganic–organic hybrid compounds deposited on carbon cloth (VOH-PANI/CC) are developed by combination of layer-by-layer and in-situ polymerization process. Benefiting from synergistic effect between polyaniline and hydrated vanadium pentoxide, the hybrid electrode (VOH-PANI/CC) delivers high capacities of 290 mA h/g at 0.5 A/g and 165 mA h/g at 4 A/g. In contrast, the specific capacities of VOH/CC are only 185 and 70 mA h/g at 0.5 and 4 A/g, respectively. This in-situ polymerization of aniline via layer-by-layer strategy on hydrated vanadium oxide provides a novel synthesis scheme for the use of vanadium oxide as cathode material for aqueous zinc-ion batteries.

Cations-Pillared and Polyaniline-Encapsulated Vanadate Cathode for High-Performance Aqueous Zinc-Ion Batteries.

Layered vanadium-based oxides have emerged as highly promising candidates for aqueous zinc-ion batteries (AZIBs) due to their open-framework layer structure and high theoretical capacity among the diverse cathode materials investigated. However, the susceptibility to structural collapse during charge-discharge cycling severely hampers their advancement. Herein, we propose an effective strategy to enhance the cycling stability of vanadium oxides. Initially, the structural integrity of the host material is significantly reinforced by incorporating bi-cations Na+ and NH4+ as "pillars" between the V2O5 layers (NaNVO). Subsequently, surface coating with polyaniline (PA) is employed to further improve the conductivity of the active material. As anticipated, the assembled Zn//NaNVO@PA cell exhibits a remarkable discharge capacity of 492 mAh g-1 at 0.1 A g-1 and exceptional capacity retention up to 89.2% after 1000 cycles at a current density of 5 A g-1. Moreover, a series of in-situ and ex-situ characterization techniques were utilized to investigate both Zn ions insertion/extraction storage mechanism and the contribution of polyaniline protonation process towards enhancing capacity.

Co-insertion of K+ and Ca2+ in vanadium oxide as high-performance aqueous zinc-ion battery cathode material

Inserting metal ions into vanadium oxides can effectively improve their electrochemical properties, and the insertion of different single metal ions into vanadium-based compounds can enhance their electrochemical performance in different ways. Moreover, the insertion of multiple metal ions into vanadium-based compounds may provide a synergistic effect. Therefore, in this work a K0.02Ca0.18V2O5·0.7H2O (KCaVOH) cathode material was obtained by co-inserting the monovalent metal ion K+ and the divalent metal ion Ca2+ into vanadium oxide through a one-step hydrothermal method. The insertion of K+ enhances the structural stability of the cathode material, while the insertion of Ca2+ increases the layer spacing between the V-O layers and improves the specific capacity of the cathode material. The co-insertion of K+ and Ca2+ effectively enhances the electrochemical performance of V2O5·1.6H2O, and the KCaVOH cathode provides a high specific capacity of 410 mAh·g−1 at 0.3 A·g−1. Moreover, the capacity still reaches 265 mAh·g−1 after 1800 cycles at 5 A·g−1. This method provides a strategy for significantly enhancing the electrochemical performance of vanadium-based cathode materials.

Induced Anionic Functional Group Orientation-Assisted Stable Electrode-Electrolyte Interphases for Highly Reversible Zinc Anodes.

Dendrite growth and other side-reaction problems of zinc anodes in aqueous zinc-ion batteries heavily affect their cycling lifespan and Coulombic efficiency, which can be effectively alleviated by the application of polymer-based functional protection layer on the anode. However, the utilization rate of functional groups is difficult to improve without destroying the polymer chain. Here, a simple and well-established strategy is proposed by controlling the orientation of functional groups (─SO3H) to assist the optimization of zinc anodes. Depending on the electrostatic effect, the surface-enriched ─SO3H groups increase the ionic conductivity and homogenize the Zn2+ flux while inhibiting anionic permeation. This approach avoids the destruction of the polymer backbone by over-sulfonation and amplifies the effect of functional groups. Therefore, the modified sulfonated polyether ether ketone (H-SPEEK) coating-optimized zinc anode is capable of longtime stable zinc plating/stripping, and moreover an enhanced cycling steadiness under high current densities is also detected in a series of Zn batteries with different cathode materials, which achieved by the inclusion of H-SPEEK coating without causing any harmful effects on the electrolyte and cathode. This work provides an easy and efficient approach to further optimize the plating/stripping of cations on metal electrodes, and sheds lights on the scale-up of high-performance aqueous zinc-ion battery technology.

Cation-driven self-assembly of core–shell covalent organic frameworks@Ti3CN MXene nanospheres for high-performance aqueous zinc-ion hybrid supercapacitors

Rechargeable aqueous Zn-ion hybrid supercapacitors (ZISCs) with the superiorities of high theoretical capacity, low redox potential and aqueous electrolytes with superior ionic conductivity (∼1 S cm−1) are promising energy storage systems. However, a primary concern persists due to the absence of cathode materials with both high energy densities and satisfactory cycling stability for robust ZISCs. In this study, we design a spherical core–shell covalent organic frameworks@Ti3CN MXene (CM-P) cathode via a cation-driven electrostatic self-assembly strategy. The CM-P with the constructed heterostructures shows both well-organized pore channels and excellent intrinsic conductivity, facilitating fast accessibility to intrinsic redox-active sites (such as C = O and N), and promoting effective ion diffusion characterized by low energy barriers. Consequently, the CM-P cathodes demonstrate excellent electrochemical performance, featuring an ultrahigh specific capacity of 260 mAh/g at 0.1 A, a high-rate capability with 68 % retention at 1 A/g, and long-term cycling stability. First-principle calculations elucidate that the enhanced charge-storage mechanism relies on the heterostructures of CM-P, accelerating ion adsorption/diffusion and electron transfer. Furthermore, the assembled CM-P//Zn ZISCs devices show a high energy density of 217.1 Wh kg−1 along with power density of 22.3 kW kg−1. This work provides an innovative approach to design COFs-based heterostructures for advanced ZISCs.

Enhancing the electrochemical activation kinetics of V2O3 for high-performance aqueous zinc-ion battery cathode materials

The discharge capacity and lifespan of zinc ion batteries currently remain impractical due to limitations in the cathode. Low-valence vanadium oxides are promising cathode material precursors that can be electrochemically converted into highly active hydrated amorphous oxides. However, the activation process itself suffers from structural instability or high local strain, due to the low electronic conductivity and the limited ion diffusion kinetics. To tackle this issue, herein, we synthesize porous carbon-coated nitrogen-doped V2O3 (p-NVO@C) microparticles utilizing a nitrogen-containing vanadium-based metal–organic framework (MOF) as the precursor. The uniform N doping and carbon coating improve the electronic conductivity of the active material particles. The carbon coating also traps the active material to reduce its dissolution loss; the high porosity of the p-NVO@C alleviates the stress from Zn2+-intercalation-induced expansion and shortens the ion transport paths. Moreover, first-principles calculations indicate that the doped N atoms in vanadium oxides generate a locally enhanced electric field, which accelerates the diffusion of Zn2+. Given the above advantages, the p-NVO@C particles demonstrate an outstanding specific capacity of 501 mAh/g at a current density of 0.2 A/g and a remarkable rate performance after the initial activation. The capacity retention rate remains as high as 95.7 % after 2000 cycles at a current density of 10 A/g. Ex-situ characterizations confirm the robust structural stability during phase transition cycles. This work provides an excellent solution to developing cathode materials for high-performance aqueous zinc ion batteries.

Enhancement of zinc-ion storage capability by synergistic effects on dual-ion adsorption in hierarchical porous carbon for high-performance aqueous zinc-ion hybrid capacitors

Aqueous zinc-ion capacitors (AZICs) are considered potential energy storage devices thanks to their ultrahigh power density, high safety, and extended cycling life. Carbon-based materials widely used as cathodes in AZICs face challenges, such as inappropriate pore sizes, poor electrolyte–electrode wettability, and insufficient vacancy defects and active sites. These limitations hinder efficient energy storage capacity and long-term stability. To address these issues, the B and F co-doped hierarchical porous carbon cathode materials (BFPC) are constructed through a facile annealing treatment process. The BFPC-2//Zn device exhibited high capacities of 222.4 and 118.3 mAh g−1 at current densities of 0.2 and 10 A g−1, respectively. Notably, the BFPC-2//Zn device demonstrated long-term cycling stability with a high capacity retention of 96.9 % after 20,000 cycles at 10 A g−1. Additionally, the assembled BFPC-2 based AZICs displayed a maximum energy density of 175.8 Wh kg−1 and an ultrahigh power density of 17.3 kW kg−1. Mechanism studies revealed that the exceptional energy storage ability and charge-transfer process of the BFPC cathode are attributed to the synergistic effect of B and F heteroatoms and the coupling effect between vacancy defects and pore size. This work presents a novel design strategy by incorporating B and F active sites into hierarchical porous carbon materials, providing enhanced energy storage capabilities for practical application in AZICs.

Steric-hindrance Effect Tuned Ion Solvation Enabling High Performance Aqueous Zinc Ion Batteries.

Despite many additives have been reported for aqueous zinc ion batteries, steric-hindrance effect of additives and its correlation with Zn2+ solvation structure have been rarely reported. Herein, large-sized sucrose biomolecule is selected as a paradigm additive, and steric-hindrance electrolytes (STEs) are developed to investigate the steric-hindrance effect for solvation structure regulation. Sucrose molecules do not participate in Zn2+ solvation shell, but significantly homogenize the distribution of solvated Zn2+ and enlarge Zn2+ solvation shell with weakened Zn2+-H2O interaction due to the steric-hindrance effect. More importantly, STEs afford the water-shielding electric double layer and in situ construct the organic and inorganic hybrid solid electrolyte interface, which effectively boost Zn anode reversibility. Remarkably, Zn//NVO battery presents high capacity of 3.9 mAh ⋅ cm-2 with long cycling stability for over 650 cycles at lean electrolyte of 4.5 μL ⋅ mg-1 and low N/P ratio of 1.5, and the stable operation at wide temperature (-20 °C~+40 °C).

A new In Situ Oxidized 2D Layered MnBi2Te4 Cathode for High-Performance Aqueous Zinc-Ion Battery.

Recently, aqueous zinc ion batteries (AZIBs) with the superior theoretical capacity, high safety, low prices, and environmental protection, have emerged as a contender for advanced energy storage. However, challenges related to cathode materials, such as dissolution, instability, and structural collapse, have hindered the progress of AZIBs. Here, a novel AZIB is constructed using an oxidized 2D layered MnBi2Te4 cathode for the first time. The oxidized MnBi2Te4 cathode with large interlayer spacing and low energy barrier for zinc ion diffusion at 240°C, exhibited impressive characteristics, including a high reversibility capacity of 393.1mAhg-1 (0.4Ag-1), outstanding rate performance, and long cycle stability. Moreover, the corresponding aqueous button cell also exhibits excellent electrochemical performance. To demonstrate the application in practice in the realm of flexible wearable electronics, a quasi-solid-state micro ZIB (MZIB) is constructed and shows excellent flexibility and high-temperature stability (the capacity does not significantly degrade when the temperature reaches 100°C and the bending angle exceeds 150°). This research offers effective tactics for creating high-performance cathode materials for AZIBs.

Unveiling Phenoxazine's Unique Reversible Two-Electron Transfer Process and Stable Redox Intermediates for High-Performance Aqueous Zinc-ion Batteries.

The low specific capacity determined by the limited electron transfer of p-type cathode materials is the main obstruction to their application towards high-performance aqueous zinc-ion batteries (ZIBs). To overcome this challenge, boosting multi-electron transfer is essential for improving the charge storage capacity. Here, as a typical heteroaromatic p-type material, we unveil the unique reversible two-electron redox properties of phenoxazine in the aqueous electrolytes for the first time. The second oxidation process is stabilized in the aqueous electrolytes, a notable contrast to its less reversibility in the non-aqueous electrolytes. A comprehensive investigation of the redox chemistry mechanism demonstrates remarkably stable redox intermediates, including a stable cation radical PNO⋅+ characterized by effective electron delocalization and a closed-shell state dication PNO2+. Meanwhile, the heightened aromaticity contributes to superior structural stability during the redox process, distinguishing it from phenazine, which features a non-equivalent hybridized sp2-N motif. Leveraging these synergistic advantages, the PNO electrodes deliver a high capacity of 215 mAh g-1 compared to other p-type materials, and impressive long cycling stability with 100 % capacity retention over 3500 cycles. This work marks a crucial step forward in advanced organic electrodes based on multi-electron transfer phenoxazine moieties for high-performance aqueous ZIBs.

Heterojunction tunnelled vanadium-based cathode materials for high-performance aqueous zinc ion batteries

Rechargeable aqueous zinc ion batteries (ZIBs) have emerged as a promising alternative to lithium-ion batteries due to their inherent safety, abundant availability, environmental friendliness and cost-effectiveness. However, the cathodes in ZIBs encounter challenges such as structural instability, low capacity, and sluggish kinetics. In this study, we constructed BiVO4@VO2 (BVO@VO) heterojunction cathode material with bismuth vanadate and vanadium dioxide phases for ZIBs, which demonstrate significant advancements in both aqueous and quasi-solid-state ZIBs. Benefitting from the heterojunction structure, the materials present a high capacity of 262 mAh g−1 at 0.1 A g−1, superb cyclic stability with 96% capacity retention after 1000 cycles at 2 A g−1, and outstanding rate property with a specific capacity of 218 mAh g−1 even at a high rate of 5.0 A g−1. Furthermore, the flexible quasi-solid-state ZIBs incorporating the BVO@VO cathode demonstrate prolonged cyclic life performance with a remarkable specific capacity of 234 mAh g−1 over 100 cycles at a current density of 0.1 A g−1. This study potentially paves the way for the utilization of heterointerface-enhanced zinc ion diffusion for vanadium-based materials in ZIBs, thereby providing a new approach for the design and investigation of high-performance zinc-ion systems.

Coupling effect of vacancy defects and multi-adsorption sites in porous carbon cathode for high-performance aqueous zinc-ion hybrid capacitors

Aqueous zinc-ion hybrid capacitors (AZICs) are considered to be an auspicious electrochemical energy storage device due to their superior cycling stability and high power density, but the inadequate electrolyte ions storage active sites and inconsistent pore sizes of porous carbon materials result in poor energy storage performance. Thus, unveiling the interplay between the heteroatom dopant, carbon vacancy defects, and pore sizes in carbon cathode is essential for promoting the Zn2+ and SO42− ions storage capability. In this work, N, S co-doped multi-adsorption sites porous carbon materials with abundant vacancy defects (HC-0.2) are successfully prepared by a facile direct activating/annealing method, which exhibit strong interaction adsorption ability and boost ion and electron transfer. In terms of zinc storage performance, the HC-0.2 cathode exhibits a high capacity of 245.8mAh/g at 0.2A/g and a long cycling stability with 82.3 % capacity retention over 10,000 cycles at 10A/g. Moreover, the HC-0.2//Zn device has a supreme energy density of 164.1Wh/kg and an ultrahigh power density of 30.1 kW/kg. Meanwhile, through theoretical calculations, the N, S multi-adsorption sites, a suitable pore size, and vacancy defects of the HC-0.2 cathode are crucial for improving the Zn2+ and SO42− ions storage capability. This work can provide a comprehensive understanding of the coupling effect of the multi-adsorption sites and vacancy defects of N, S co-doped porous carbon materials on energy storage capability.

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.

Heat activated VO2 (R) cathodes for high-performance aqueous zinc ion batteries

We introduce a novel approach for design and production of vanadium dioxide (VO2) cathodes activated by heat, specifically tailored for use in aqueous zinc-ion batteries (ZIBs). Our cathodes exhibit distinctive metal-insulator transition (MIT) characterized by the shift between monoclinic (M) and tetragonal rutile (R) phases. The employment of an aqueous electrolyte in ZIBs enables successful operation of VO2 cathodes, showcasing phase transition and enhanced electrochemical performance above a readily attainable temperature of approximately 68 °C. The MIT feature enhances the charge transfer properties at electrode-electrolyte interfaces, resulting in notable improvements in specific capacity and energy densities. Fabricated VO2(M) cathodes underwent heat-triggered transformation to VO2(R), resulting in a remarkable increase (400 %) in capacity. At 0.1 A g−1, VO2(R) cathodes show specific capacity of 354.6 mAh g−1, yielding an impressive energy density of 461.0 Wh kg−1 for aqueous ZIBs. This exceptional performance can be attributed to abrupt change in electrical conductivity upon thermal activation of MIT. This work underscores pivotal role of thermally activated MIT in finely tuning electrochemical performance of energy storage systems, prospecting a promising avenue for further advancements.

Electrochemical Activation in Vanadium Oxide with Rich Oxygen Vacancies for High-Performance Aqueous Zinc-Ion Batteries

Electrochemical Activation in Vanadium Oxide with Rich Oxygen Vacancies for High-Performance Aqueous Zinc-Ion Batteries

In-situ growth of hydrophobic zinc succinate interphase with high ionic conductivity toward stable zinc anodes

Aqueous zinc-ion batteries (ZIBs) are a promising solution for energy storage due to their affordability, high performance, environmental friendliness, and excellent safety features. However, zinc metal anodes are prone to capacity degradation and short circuits due to side reactions and dendrite growth during cycling. To address this issue, a dual-function artificial solid electrolyte interphase (SEI) made of zinc succinate complex (ZnSA) is in-situ constructed on zinc anodes by a simple and cost-effective soaking approach. This interphase is hydrophobic and highly ionic conductive (4.5 mS cm−1). It has a low electronic conductivity (1.6 mS cm−1) and a large Zn2+ transfer number (0.63). The hydrophobic SEI progressively represses water-induced side reactions, lowers zinc nucleation overpotential, accelerates zinc ion diffusion, and regulates homogeneous zinc deposition. As a result, the ZnSA@Zn symmetric cell achieves an impressive lifespan of 4450 h at 1 mA cm−2 for 0.5 mAh cm−2, which is significantly better than the bare zinc cell and superior to many recently reported zinc anodes. Furthermore, the V2O5//ZnSA@Zn batteries exhibit outstanding rate performance and remarkable long-term operation stability for 2000 cycles at 1 A/g. This innovative and cost-effective strategy opens up new possibilities for developing high-performance aqueous zinc-ion batteries.

Uncovering Se, P co-doping effect in MnO2 toward high-performance aqueous zinc-ion batteries

MnO2, a promising cathode material for aqueous zinc ion batteries (AZIBs), is vigorously developed. The development of MnO2 as the electrode for AZIBs is inevitably limited by low conductivity and slow reaction kinetics. Herein, Se, P co-doping MnO2 (Se, P-MnO2) nanorods are proposed as high-performance cathodes for AZIBs. Benefitting from the synthetic effect, the stability and reaction kinetics of Se, P-MnO2 cathode are significantly improved. The capacity of Se, P-MnO2 cathode is up to 295 mAh g−1 at 0.5 A g-1, surpassing that of MnO2 (126 mAh g−1), Se-MnO2 (216 mAh g−1) and P-MnO2 (250 mAh g−1). And Se, P-MnO2 cathode also displays stability with the capacity of 232 mAh g−1 at 1 A g-1 after 1000 cycles, and outstanding rate performance (122.4 mAh g−1 at 5.0 A g-1). Besides, the theoretical calculation verifies that doping Se and P with low electronegativity to replace O with high electronegativity can tune the inherent electronic structure of MnO2, equilibrate H+/Zn2+ adsorption–desorption, and impair the electrostatic interaction between MnO2 and H+/Zn2+, thus accelerating the reaction kinetics and endowing tremendous redox ability. This study indicates that Se and P co-doping is a successful tactic to upgrade the electrochemical performance of MnO2 cathode, which provides innovative viewpoints on the advance of suitable cathode materials for AZIBs, as well as fresh ideas for the logical design of electrode materials in alternative battery systems.