Cathode Materials For Zinc-ion Batteries Research Articles

Using -NH and -OH rich organic cathodes to explore proton transport in aqueous zinc-ion batteries.

An organic cathode material for zinc-ion batteries shows a reliable proton transport mechanism. It uses a pyrazine ring as the energy storage unit and H+ as the shuttle ion, enabling high functionality utilization with rapid redox kinetics.

Exploring the unexpected electrochemical dynamics of lithium vanadyl phosphate electrodes in zinc battery systems

Our study explores the potential of β-LiVOPO4 as a high-energy and stable cathode material for zinc-ion batteries, achieving a high working voltage through comprehensive characterization techniques.

Manganese-based MOF interconnected carbon nanotubes as a high-performance cathode for rechargeable aqueous zinc-ion batteries

Aqueous zinc-ion batteries (ZIBs) have attracted extensive attention due to their low cost, environmental friendliness, and high volumetric specific capacity. However, the design of cathode materials with high performance for ZIBs is quite limited. In this paper, a kind of manganese-based metal-organic framework/carbon nanotubes (Mn-MOF/CNT) composite is prepared as the cathode material for ZIBs via a one-pot in situ solvothermal method. Particularly, the assembled Mn-MOF/CNT//Zn battery exhibits high specific capacity (260 mAh g−1 at 50 mA g−1) and excellent capacity retention (approximately 100 %) after 900 cycles at 1000 mA g−1. This significant electrochemical performance is attributed to the high porosity and the high conductivity of Mn-MOF/CNT, as well as the Mn2+ electrolyte additive. This work renders a new sight to design high-performance MOF-based cathode materials for aqueous ZIBs.

Constructing stable V2O5/V6O13 heterostructure interface with fast Zn2+ diffusion kinetics for ultralong lifespan zinc‐ion batteries

Given their plentiful reserves, impressive safety features, and economical pricing, aqueous zinc − ion batteries (ZIBs) have positioned themselves as strong competitors to lithium − ion batteries. Yet, the scarcity of available cathode materials poses a challenge to their continued development. In this study, a V2O5/V6O13 heterostructure has been synthesized using a one − pot hydrothermal approach and employed as the cathode material for ZIBs. As evidenced by both experimental and theoretical findings, V2O5/V6O13 heterostructure delivers a rapid electrons and ions diffusion kinetics promoted by the stable interface and strong electronic coupling with significant charge transfer between V2O5 and V6O13, as well as a stable interface achieved by adjusting V − O bond length. Consequently, the optimized V2O5/V6O13 heterostructure cathode of ZIBs demonstrates exceptional capacity (338 mAh g−1 at 0.1 A g−1), remarkable cycling stability (92.96 % retained after 1400 cycles at 1 A g−1). Through comprehensive theoretical calculations and ex situ characterization, the kinetic analysis and storage mechanism of Zn2+ are thoroughly investigated, providing a solid theoretical foundation for the advancement of novel V − based cathode materials aimed at enhancing the performance of ZIBs.

In-situ polymerization of polypyrrole on Prussian blue analogue for high capacity and flexible zinc-ion batteries

Prussian blue analogues (PBAs) have been considered as promising cathode materials for zinc-ion batteries. However, severe capacity decay issues hamper their deployment. Herein, Mn-ion-substituted zinc hexacyanoferrate (MZHCF) cathode materials were coated with polypyrrole (PPy) by in situ polymerization. The prepared MZHCF@PPy composites have exhibited significant ionic absorption affinity and great structural stability. Benefiting from the PPy coating, the ZIBs based on MZHCF@PPy cathodes and a conductive poly(acrylamide) (PAAM) hydrogel electrode exhibit enhanced capacities, which reach a maximum value of 190.1 mAh g−1 at 0.5 A g−1, three times higher than that of the device based on MZHCF electrodes. The flexible ZIBs not only present outstanding cyclic performance but also retain stable energy storage capability under various deformations. The presented method is a promising technology for the practical application of rechargeable ZIBs with high safety and flexibility.

Unveiling the X‐Ray Absorption Chemistry of H3.78V6O13 Cathode for Aqueous Zinc‐Ion Batteries

AbstractThe low cost and intrinsic safety of rechargeable aqueous zinc‐ion batteries (ZIBs) contribute to their significant potential in grid‐level energy storage systems. However, the limited cathode options still hinder the development of ZIBs, which always delivers poor rate capacities and cycling stability. Herein, Monoclinic phase H3.78V6O13 microspheres with a stable internal framework and intrinsic metallic properties as a high‐performance cathode for ZIBs are proposed and utilized. The reversible Zn2+insertion/de‐insertion mechanism in H3.78V6O13through ex situ X‐ray diffraction, X‐ray absorption near‐edge structure, and in situ Raman involves the enlargement/shrink of interplanar distance, the decrease/increase of the V valance, and the open/recombine of V─O/V─V bonds. Further, experiments and theoretical calculations elucidate the superior electrochemical performance and extraordinary reaction kinetics in H3.78V6O13. The as‐prepared H3.78V6O13 cathode delivers high specific capacity of 406 mAh g–1 at 0.1 A g–1, excellent structure stability with 100% manifested after 120 cycles at 0.5 A g–1, 72.9% retained after 15 000 cycles at 10 A g–1. This research offers distinctive perspectives on the development of high‐performance cathode materials for ZIBs and enhances the understanding of the electrochemical reaction mechanisms of vanadium oxides.

De/Protonation Associated Sustainable Conversion Reaction Applicable to High-Capacity Zinc Storage in Mildly Acidic Aqueous System

We introduce an unexpected finding of the de/protonation associated conversion reaction occurred in K2V3O8 as a promising cathode material for zinc-ion batteries. The structure undergoes a conversion reaction between amorphous V5+ 2O5 and V3+OOH upon cycling when a cut-off voltage up to 1.9 V is applied. A combination of operando X-ray diffraction, in situ Raman spectroscopy, X-ray photoelectron spectroscopy, time-of-flight secondary-ion mass spectroscopy, and operando pH measurement analyses reveal that the reaction of the proton (H+) is indispensable for progression of the conversion reaction. The conversion reaction results in a large reversible capacity of 362 mAh g−1 (~97 % of theoretical capacity) at 0.1 C (37 mA g−1) on discharge and an activity even at a rate of 7 C (187 mAh g−1), with the two-electron reaction by the V5+/3+ redox pair evidenced by operando X-ray absorption spectroscopy analysis. These findings underscore the importance of conversion reversibility associated with the proton reaction for a high cut-off voltage, contributing additional capacity to reach the theoretical capacity for cathode materials of zinc-ion batteries in mildly acidic aqueous systems.

Synthesis and properties of manganese-doped ZnO@2Mn1−xMxCO3 composite cathode material for zinc-ion batteries

Synthesis and properties of manganese-doped ZnO@2Mn1−xMxCO3 composite cathode material for zinc-ion batteries

Carbon reduction assist structured preparation stable three-dimensional V6O13 for durable aqueous zinc-ion batteries

Among various zinc-ion batteries (ZIBs) cathodes, vanadium-based oxides have received a great deal of research due to their high theoretical specific capacity. However, the severe problem of dissolution and sluggish kinetics of Zn2+ diffusion in vanadium-based oxides limit their further development as cathode materials for ZIBs. Herein, a novel monoclinic V6O13 nanoflowers (VONs) cathode is synthesized via an in-situ surface carbon reduction method from orthorhombic V2O5 at specific temperature. Benefiting from the intrinsic open tunnel-like structure and mixed states V4+/V5+ of V6O13, which are beneficial to facilitate the diffusion of Zn2+ and improve electronic conductivity of VONs. In addition, the dissolution of vanadium in VONs is suppressed remarkably. Based on the synergy of the advantages, the ZIBs with VONs electrode show excellent electrochemical performances, including high specific capacity (420 mAh g−1 at 0.2 A g−1) and rate capability, especially long-term cycling stability (above 88.9% capacity retention after 6000 cycles). Moreover, the kinetics and mechanism of the Zn2+ storage and diffusion in VONs have been investigated by combining experimental data with density functional theory (DFT) calculations. This in-situ preparation strategy provides a new approach to regulate the structure and phase of vanadium-based oxides to meet the requirements of high-performance ZIBs.

A Novel Ni-doped ZnMn2O4/Mn2O3 nanocomposite synthesized by pulsed potential as superior zinc ion battery cathode material

The research and development of suitable cathode materials for Zn2+ storage is crucial to meet the large-scale energy storage application of zinc-ion batteries (ZIBs). However, manganese-based oxide cathodes, the most-studied category of cathode materials, suffer from capacity decline and weak electrical conductivity. Herein, Ni-doped ZnMn2O4/Mn2O3 nanocomposite has been synthesized using pulsed potential electrodeposition technique and then applied as cathode material for ZIBs. The Ni2+ doping effectively boosts the electrical conductivity and electrochemical performance of electrodes. Furthermore, simultaneous production of ZnMn2O4 /Mn2O3 nanocomposite as a two-phase compound and incorporation of Ni2+ in crystal structure leads to an improvement in reversibility and cyclability of Ni-doped ZnMn2O4/Mn2O3 nanocomposite. Moreover, the Ni-doped ZnMn2O4/Mn2O3 nanocomposite presents a specific capacity of 235.10 mAh g−1 (0.2 A g−1), higher than Undoped nanocomposite (215 mAh g−1). Besides, the Ni-doped ZnMn2O4/Mn2O3 nanocomposite shows superior electrochemical performance, with a reversible capacity of 114.67 mAh g−1 and capacity retention of 91.32%, obtained after 3000 cycles at 2 A g−1, while the Undoped -ZnMn2O4/Mn2O3 nanocomposite possesses the capacity of 61.85 mAh g−1 with 64.54% capacity retention at the same condition. The obtained results suggest that the synergistic effect of doping and two-phase compound synthesis provide new features for the practical application of ZIBs.

Exploring Cathode Materials for Zn-Ion Batteries: A First-Principles Investigation

Aqueous zinc-ion batteries (ZIBs) are a promising technique for large-scale energy storage, however, the large ionic potential of Zn2+ ions leads to slow diffusion kinetics of Zn2+ ions in cathode hosts. To address this issue, we predicted two vanadium-based compounds for potential applications as cathode materials for ZIBs through the evolutionary algorithm. The dynamic, mechanical, and thermodynamic stabilities of the newly discovered ZnVO3 polymorphs were confirmed by ab initio calculations. CI-NEB results show impressively low Zn2+-ion migration barriers of 0.44 and 0.40 eV for the predicted P2/c and P21/c polymorphs, respectively. Furthermore, the P21/c-structured ZnVO3 exhibits a small band gap of 1.62 eV, a high voltage plateau of 1.16 V, and a trivial volume change upon charging, which may suggest excellent rate performance and a long cycle life when functioning as a cathode material for ZIBs. The work may provide fundamental guidance for the design and development of electrode materials featuring intrinsic fast Zn2+ ion transportation.

The Promotion of Research Progress of Zinc Manganate Cathode Materials for Zinc-Ion Batteries by Characterization and Analysis Technology.

Zinc-ion batteries (ZIBs) have recently attracted great interest and are regarded as a promising energy storage device due to their low cost, environmental friendliness, and superior safety. However, the development of suitable Zn-ion intercalation cathode materials remains a great challenge, resulting in unsatisfactory ZIBs that cannot meet commercial demands. Considering that spinel-type LiMn2O4 has been shown to be a successful Li intercalation host, spinel-like ZnMn2O4 (ZMO) is expected to be a good candidate for ZIBs cathodes. This paper first introduces the zinc storage mechanism of ZMO and then reviews the promotion of research progress in improving the interlayer spacing, structural stability, and diffusivity of ZMO, including the introduction of different intercalated ions, introduction of defects, and design of different morphologies and in combination with other materials. The development status and future research directions of ZMO-based ZIBs characterization and analysis techniques are summarized.

Nitrogen-doped carbon/V2O3 nanorod composites as cathode material for high-performance aqueous Zn-ion battery

At present, the main challenge facing the aqueous zinc ion batteries (ZIBs) system is to find a kind of cathode material with high stability and large capacity. In this study, the precursor of metal-organic framework (MOF) was synthesized by hydrothermal method. Then, the carbon composite vanadyl oxide (N/C@V2O3) was synthesized by vacuum heat treatment and used as cathode material for ZIBs. The electrode material underwent an in situ phase change process during the first charge, where the corundum structure of N/C@V2O3 was oxidized and transformed into layered basic zinc vanadate (N/C@Zn2(OH)3(VO3)). The layered structure helps to achieve fast and stable storage and transport of zinc ions. Resulting in stable electrochemical performance, high specific capacity up to 285 mAh g−1 (1 A g−1), and ultra-long cycle stability (capacity retention of 98% at 10 A g−1 after 4500 cycles). In situ phase transition takes place inside the battery, which is a simple method to improve the theoretical capacity limit of materials, and has positive significance for realizing large magnification and long cycle ZIBs cathode materials.

Triggering High Capacity and Superior Reversibility of Manganese Oxides Cathode via Magnesium Modulation for Zn//MnO2 Batteries.

Aqueous zinc-ion batteries (ZIBs) have attracted extensive attention in recent years because of its high volumetric energy density, the abundance of zinc resources, and safety. However, ZIBs still suffer from poor reversibility and sluggish kinetics derived from the unstable cathodic structure and the strong electrostatic interactions between bivalent Zn2+ and cathodes. Herein, magnesium doping into layered manganese dioxide (Mg-MnO2 ) via a simple hydrothermal method as cathode materials for ZIBs is proposed. The interconnected nanoflakes of Mg-MnO2 possess a larger specific surface area compared to pristine δ-MnO2 , providing more electroactive sites and boosting the capacity of batteries. The ion diffusion coefficients of Mg-MnO2 can be enhanced due to the improved electrical conductivity by doped cations and oxygen vacancies in MnO2 lattices. The assembled Zn//Mg-MnO2 battery delivers a high specific capacity of 370mAhg-1 at a current density of 0.6Ag-1 . Furthermore, the reaction mechanism confirms that Zn2+ insertion occurred after a few cycles of activation reactions. Most important, the reversible redox reaction between Zn2+ and MnOOH is found after several charge-discharge processes, promoting capacity and stability. It believes that this systematic research enlightens the design of high-performance of ZIBs and facilitates the practical application of Zn//MnO2 batteries.

Oxygen vacancies and heterointerface co-boosted Zn2+ (De)intercalation kinetics in VO2 for ultra-efficient aqueous zinc-ion batteries

In this study, we demonstrated the co-modification of oxygen vacancies and heterojunctions in VO2(B) (VO–VO2/MXene) as a cathode material for zinc-ion batteries (ZIBs). VO2 nanobelts are uniformly distributed on MXene nanosheets, which providing complete electron transport channels during the insertion or de-insertion of Zn2+. The formation of oxygen vacancies provides additional active sites and enhances the conductivity of VO2. Density functional theory calculations reveal that the oxygen vacancies effectively facilitate reversible intercalation/deintercalation process, which results in rapid intra-crystal zinc ion diffusion. The combination of VO–VO2 with MXene introduces an interfacial electric field, ultimately leading to synergistic enhancement in electrochemical activity. The VO–VO2/MXene composite exhibits the highest specific capacity (287 mAh g−1) at 10 A g−1 and excellent cycling lifespan (253 mAh g−1 after 3000 cycles) for ZIBs. This work provides a reliable strategy for the co-modification of metal oxide electrodes with oxygen vacancies and heterostructures.

Hexagonal Carbon Nanoplates Decorated with Layer-Engineered MoS2: High-Performance Cathode Materials for Zinc-Ion Batteries.

Hexagonal carbon nanoplates bearing MoS2 (HCN@MoS2) were synthesized using two-dimensional (2D) microporous organic polymers as templating materials. The layer number of MoS2 in HCN@MoS2 and the 2D morphology of composites were critical factors to achieve high-performance cathode materials for aqueous zinc-ion batteries. The best cathode performance was obtained with HCN@MoS2 bearing 2-3 layered MoS2 (HCN@MoS2-2), showing excellent discharge capacities of 602 mAh/g (@50 mA/g), 498 mAh/g (@0.1 A/g), and 328 mAh/g (@1 A/g). The promising electrochemical performance of HCN@MoS2-2 is attributable to the facilitated insertion of zinc ions into 2-3 layered MoS2 due to the reduced lattice energy and the efficient electrochemical utilization of composite materials.

Amorphous carbon and carbon nanotubes synergistically reinforced with MnO2 as a cathode material for zinc-ion batteries

Amorphous carbon and carbon nanotubes synergistically reinforced with MnO2 as a cathode material for zinc-ion batteries

Supramolecular Engineering of Cathode Materials for Aqueous Zinc-ion Energy Storage Devices: Novel Benzothiadiazole Functionalized Two-Dimensional Olefin-Linked COFs.

Two-dimensional covalent organic frameworks (COFs) have emerged as promising materials for energy storage applications exhibiting enhanced electrochemical performance. While most of the reported organic cathode materials for zinc-ion batteries use carbonyl groups as electrochemically-active sites, their high hydrophilicity in aqueous electrolytes represents a critical drawback. Herein, we report a novel and structurally robust olefin-linked COF-TMT-BT synthesized via the aldol condensation between 2,4,6-trimethyl-1,3,5-triazine (TMT) and 4,4'-(benzothiadiazole-4,7-diyl)dibenzaldehyde (BT), where benzothiadiazole units are explored as novel electrochemically-active groups. Our COF-TMT-BT exhibits an outstanding Zn2+storage capability, delivering a state-of-the-art capacity of 283.5 mAh g-1at 0.1 A g-1. Computational and experimental analyses reveal that the charge-storage mechanism in COF-TMT-BT electrodes is based on the supramolecularly engineered and reversible Zn2+coordination by the benzothiadiazole units.

In Situ Electrochemically Oxidative Activation Inducing Ultrahigh Rate Capability of Vanadium Oxynitride/Carbon Cathode for Zinc-Ion Batteries.

As a promising candidate for large-scale energy storage, aqueous zinc-ion batteries (ZIBs) still lack cathode materials with large capacity and high rate capability. Herein, a spherical carbon-confined nanovanadium oxynitride with a polycrystalline feature (VNxOy/C) was synthesized by the solvothermal reaction and following nitridation treatment. As a cathode material for ZIBs, it is interesting that the electrochemical performance of the VNxOy/C cathode is greatly improved after the first charging process viain situ electrochemically oxidative activation. The oxidized VNxOy/C delivers a greatly enhanced reversible capacity of 556 mAh g-1 at 0.2 A g-1 compared to the first discharge capacity of 130 mAh g-1 and a high capacity of 168 mAh g-1 even at 80 A g-1. The ex situ characterizations verify that the insertion/extraction of Zn2+ does not affect the crystal structure of oxidized VNxOy/C to promise a stable cycle life (retain 420 mAh g-1 after 1000 cycles at 10 A g-1). The experimental analysis further elucidates that charging voltage and H2O in the electrolyte are curial factors to activate VNxOy/C in that the oxygen replaces the partial nitrogen and creates abundant vacancies, inducing a conversion from VNxOy/C to VNx-mOy+2m/C and then resulting in considerably strengthened rate performance and improved Zn2+ storage capability. The study broadens the horizons of fast ion transport and is exceptionally desirable to expedite the application of high-rate ZIBs.

Intercalation-induced amorphous hydrated vanadium oxide for boosted aqueous Zn2+ storage.

An amorphous hydrated vanadium oxide induced by Zn2+ intercalation in Mg-ion inserted V2O5·nH2O (MgVOH) is developed as a high-performance cathode for ZIBs. In particular, zinc pyrovanadate as the product of the second phase transition is found to suppress the dissolution issue of the vanadium species for the cathode to facilitate long lifespan.