Cathode Materials For Zinc-ion Batteries Research Articles

In Situ Electrochemical Transformation toward Structure Optimized VEG@MXene Cathode for Enhanced Zinc-Ion Storage.

Vanadium-based derivatives, featuring affordable cost and high theoretical capacity, have gathered widespread interest in the context of aqueous zinc-ion batteries (ZIBs). However, the further application of vanadium-based materials is hindered by the limited electrical conductivity and cycling lifespan. Herein, 1D chain-like structure vanadyl ethylene glycolate (VEG, (VO(CH2 O)2 )), growing on the Ti3 C2 Tx MXene nanosheets, is synthesized via a one-step oil-bath heating process as cathode materials for ZIBs. Benefiting from the hybrid structure with high conductivity and abundant reactive sites, the VEG@MXene cathode exhibits a remarkable specific capacity (360.3 mAh g-1 at 0.5 A g-1 ), and impressive capacity retention (up to 85.2% after 3000 cycles at 10 A g-1 ). Mechanism analysis reveals a gradual phase transition from the original VEG on MXene to the stable Zn3 V2 O7 (OH)2 ·2H2 O nanoflakes accompanied by continuous zinc ion intercalation/deintercalation, offering more pathways for zinc ion transport. This work suggests that engineering conductivity-enhanced vanadium-based materials is a rational approach for developing promising cathode materials of ZIBs.

High-Performance Aqueous Zinc-Ion Battery Based on an Al0.35 Mn2.52 O4 Cathode: A Design Strategy from Defect Engineering and Atomic Composition Tuning.

Rechargeable zinc-ion batteries (ZIBs), which adopt mild aqueous electrolytes with high power density and safety, have received significant interest. As the most widely used cathode material for ZIBs, manganese-based oxide has poor rate performance owing to its low electronic conductivity and slow ion diffusion kinetics. In this study, using the synergistic regulation strategy of defect engineering and atomic composition tuning, a mesoporous Al0.35 Mn2.52 O4 with an ultrahigh surface area (up to 82 m2 g-1 ) is fabricated through Al substitution in the Mn3 O4 , followed by an Al-selective leaching process. During the entire process, numerous defects are obtained in the spinel structure by removing ≈30% of the Al cations. Al substitution can improve the material conductivity, while cation defects can weaken the electrostatic effect and promote ion diffusion ability. Therefore, the Al0.35 Mn2.52 O4 cathode of ZIBs exhibits a high reversible capacity of 302 mAh g-1 at a current density of 100mA g-1 . Furthermore, the reversible capacity remains at 147 mAh g-1 after 1000 cycles at a current density of 1500mA g-1 . This synergistic regulation of atomic composition tuning and defect engineering provides a new perspective for improving the performance of electrode materials in ZIBs.

Synthesis and Performance Optimization of Manganese‐based Cathode Materials for Zinc‐Ion Batteries

AbstractOwing to the low cost, high specific capacity and high safety, zinc‐ion batteries (ZIBs) have great advantages in replacing lithium‐ion batteries to meet future demand for energy storage. Manganese‐based cathode materials, benefiting from the abundant reserves, non‐toxic, acceptable capacity and long cycle stability, have been widely developed and applied to develop high performance ZIBs. Unfortunately, poor conductivity, Mn2+ dissolution and unstable structure hinder it to achieve an ideal electrochemical performance. Thus, an overview of the cathodic performance optimization strategies and the synthesis is provided. Firstly, the synthesis methods and their influence on the morphology and structure are summarized. Secondly, various strategies of performance optimization, including structure design, compositing with conductive materials, pre‐intercalation, defect engineering and electrochemical activation, are categorized and analyzed in detail. Lastly, perspectives on the subsequent performance optimization are proposed. It is expected that this review will be beneficial to future scientific research on tailoring manganese‐based cathode materials for ZIBs.

Mn3O4 nanocrystalline@carbon nanotube-carbon nanotube for long-lifetime and excellent rate-capability zinc-ion storage

Rapid capacity decay and inferior rate capability are two main problems that affect the application of Mn3O4 in aqueous zinc-ion batteries (ZIBs). Herein, we synthesize ultrasmall Mn3O4 nanocrystalline on carbon nanotube-carbon nanotube through in-situ growth of ZIF-8 on carbon nanotube, etching by tannin acid, chemical reaction of carbon and KMnO4, and final calcination. It is found that Mn3O4 nanocrystalline tightly embraces the carbon matrix, with 8-10 nm in size, 59% of weight percentage, and 46.3 m2 g−1 of specific surface area. As cathode material for ZIBs, the composite exhibits outstanding electrochemical performance, superior to most of Mn-based composites. It can deliver discharge capacity of 234 mAh g−1 at 1 A g−1 after 400 cycles. At 5 A g−1, the discharge capacity may reach 49 mAh g−1, and recovery ability is still good. Electrochemical mechanism is further studied through various electrochemical kinetics analyses and ex-situ material characterizations. The excellent Zn storage performance mainly benefits from the synergistic effect of the high conductive carbon nanotube-carbon nanotube matrix, the unique composite structure and small size of Mn3O4 nanocrystalline. The work provides a new strategy to construct the long-lifetime and excellent rate-capability Mn-based cathodes for ZIBs.

High-performance reversible aqueous Zinc-Ion battery based on Zn2+ pre-intercalation alpha-manganese dioxide nanowires/carbon nanotubes

Rechargeable aqueous zinc ion batteries (ZIBs) have attracted more and more attention due to the advantages of high safety, low cost, and environmental friendly in recent years. However, the lack of high-performance cathode materials and uncertain reaction mechanisms hinder the large-scale application of ZIBs. Herein, a 1D structure interlaced by ZnxMnO2 nanowires and carbon nanotubes is synthesized as cathode material for ZIB. The ZnxMnO2/CNTs cathode exhibits excellent specific capacity of 400 mAh g−1 at 100 mA g−1 and outstanding long-cycle stability (with a capacity retention of 93% after 100 cycles at 1000 mA g−1), which indicates the Zn2+ pre-intercalation and composite carbon nanotubes can effectively change the storage space of the tunnel structure and increase the electron transmission rate. In addition, the energy storage mechanism of the highly reversible co-insertion of H+ and Zn2+ is further elaborated. This work has enlightenment and promotion for the future research of ZIBs cathode materials. Moreover, the simple preparation method, low cost and excellent performance of ZnxMnO2/CNTs cathode material provide a new way for the practical application of ZIBs.

Electrospun V2O5 nanofibers as high-capacity cathode materials for zinc-ion batteries

Vanadium pentoxide (V2O5) has attracted significant attention in recent years as a cathode material for aqueous zinc-ion batteries (AZIBs). Its unique layered structure allows for reversible intercalation of various multivalent ions, including Zn2+.This paper proposes a sol–gel electrospinning method for preparation of vanadium pentoxide nanofibers, followed by thermal treatment in air. The composition and structure of the obtained powders were verified by X-ray diffraction, energy-dispersive X-ray elemental analysis, and X-ray photoelectron spectroscopy, while the morphology of the samples was investigated by scanning electron microscopy. The electrochemical properties and performance of the electrode materials based on V2O5 nanofibers were studied using cyclic voltammetry, galvanostatic charge–discharge, and electrochemical impedance spectroscopy methods. V2O5 electrodes demonstrate high specific capacity (357 mA h g−1 at 0.05Ag−1) and good long-term cyclic stability.

Iron-Based NASICON-Type Na4 Fe3 (PO4 )2 (P2 O7 ) Cathode for Zinc-Ion Battery: Zn2+ /Na+ Co-Intercalation Enabling High Capacity.

The development of high-performance cathode materials for aqueous zinc-ion batteries (ZIBs) based on nontoxic and earth-abundant elements remains a great challenge. This study introduces the iron-based NASICON-type material Na4 Fe3 (PO4 )2 (P2 O7) with carbon layer (NFPP@C) as a cathode material for ZIBs. When Zn2+ /Na+ dual ion electrolyte is employed, NFPP@C shows a high capacity of 114.4 mAh g-1 with two voltage plateaus, excellent rate capability (95 mAh g-1 at 2 A g-1 ), and long-term cycling stability (66.4 mAh g-1 after 1800 cycles at 1 A g-1 ). The outstanding electrochemical performance is ascribed to the synergistic use of NFPP@C and dual ion electrolyte. The NASICON-structure and carbon layer of NFPP@C enable fast ion and electron transport, whereas Na+ in the electrolyte reduces the concentration gradient between the electrode and electrolyte, and thus inhibits excessive extraction of Na+ from NFPP, maintaining structural stability. Moreover, Zn2+ /Na+ co-intercalation in NFPP@C brings two potential platforms and enhanced capacity.

Carbonyl-based polyimide immobilization on carbon nanotubes for aqueous zinc-ion batteries

The aqueous-based zinc-ion batteries (ZIBs) with higher safety and performance have gained great attention from scientists. Nevertheless, previous electrode materials mainly rely on inorganic metal oxides, and their structure is prone to collapse during charge and discharge, thus resulting in poor cycle stability, which severely limits the development of ZIBs. Here, a novel conjugated polyimide based conjugated microporous polymer (CMP) and multi-walled carbon nanotubes (CNT) hybrid has been gained and used as cathode material for ZIBs. The aromatic carbonyl group as active site can reversibly receive and release zinc ions, thus showing good electrochemical performance. This work provides new view for the design of high-performance ZIBs electrode materials.

Dual-modification of manganese oxide by heterostructure and cation pre-intercalation for high-rate and stable zinc-ion storage

Zinc-ion batteries (ZIBs) possess great advantages in terms of high safety and low cost, and are regarded as promising alternatives to lithium-ion batteries (LIBs). However, limited by the electrochemical kinetics and structural stability of the typical cathode materials, it is still difficult to simultaneously achieve high rates and high cycling stability for ZIBs. Herein, we present a manganese oxide (SnxMnO2/SnO2) material that is dual-modified by SnO2/MnO2 heterostructures and pre-intercalated Sn4+ cations as the cathode material for ZIBs. Such modification provides sufficient hetero-interfaces and expanded interlayer spacing in the material, which greatly facilitates the insertion/extraction of Zn2+. Meanwhile, the “structural pillars” of Sn4+ cations and the “pinning effect” of SnO2 also structurally stabilizes the MnO2 species during the repeated Zn2+ insertion/extraction, leading to ultra-high cycling stability. Due to these merits, the SnxMnO2/SnO2 cathode exhibits a high reversible capacity of 316.1 mAh g−1 at 0.3 A g−1, superior rate capability of 179.4 mAh g−1 at 2 A g−1, and 92.4% capacity retention after 2000 cycles. Consequently, this work would provide a promising yet efficient strategy by combining heterostructures and cations pre-intercalation to obtain high-performance cathodes for ZIBs.

Investigation of zinc storage capacity of WS2 nanosheets for rechargeable aqueous Zn-ion batteries

Rechargeable aqueous zinc ion batteries (ZIBs) are highly desired for future energy storage due to their low cost and high safety, yet the development of suitable cathode materials for ZIBs is still a main challenge. Herein, for the first time, we demonstrate 1T-WS2 nanosheets can be a promising cathode candidate for rechargeable ZIBs. Benefiting from the large inter-layer spacing and high conductivity of 1T phase, the as-synthesized WS-200 delivers reversible discharge capacities of 233.26, 206.25 and 179.99 mAh/g at the current densities of 50, 100 and 200 mA/g, respectively, while the discharge capacity of commercial WS2 is only ~ 22 mAh/g (current density: 200 mA/g). Even at a high current density of 1000 mA/g, WS2-200 still exhibits the initial discharge capacity of 85.11 mAh/g. Moreover, the zinc ion’s storage mechanism was analyzed by electrochemical impedance spectra (EIS) and cyclic voltammetry (CV) measurements. On the one hand, WS2-200 with 1T phase displays the improved ion diffusion. On the other hand, the small diameter of nanosheets and expanded inter-layer spacing increases the capacitive capacity of WS2. This work lays the foundation for the research of WS2, which is expected to become one of the competitive cathode materials for zinc-ion batteries.

The Study of Mn2O3 As a Cathode Material for Zinc-Ion Batteries

Energy and the environment are two of the most critical problems related to human survival and development in society. The ever-increasing demands [1] for energy have led to increasing development of alternative energy systems, such as wind, solar, tidal, and geothermal. These systems are intermittent and require suitable means of energy storage. Among available storage choices, electrochemical methods, such as batteries, are competitive in terms of specific energy, flexibility, and scalability. Aqueous zinc-ion batteries (ZIBs) are receiving increasing interest due to their low cost, safe operation, and reasonable efficiency.Manganese is one of the most abundant metallic elements on earth. Manganese oxide is widely used in various industries, for applications such as deoxidization and desulfurization, catalysis, and batteries, due to the different oxidation states (2+, 3+, and 4+) of manganese. For battery electrode materials, the diversity of manganese oxide compositions and crystal structures make it attractive [2,3]. Manganese (4+) oxide (MnO2) has been widely used as the cathode material in ZIBs. Other oxides with different valence states, such as Mn3O4 (2+/3+) and Mn2O3 (3+), are possible cathode candidates.In this work, high-crystalline, nanosize Mn2O3 powder is synthesized via a precipitation and calcination method for utilization as the cathode in ZIBs. The cathode is fabricated by producing a slurry of the Mn2O3 powder, carbon black (conductive agent) and polyvinylidene fluoride (PVDF, binder), and applying as a paste to a porous carbon substrate. The resultant electrodes are characterized using electrochemical techniques (e.g., cyclic voltammetry (CV) and galvanostatic charge discharge (GCD) method) and microstructural methods (e.g., scanning electron microscopy (SEM) and x-ray diffraction (XRD)) to determine the mechanisms associated with charge and discharge. Battery cycling tests are also performed using zinc foil as the anode and compared with previous studies of Mn2O3 electrodes [4,5]. A specific capacity of 211 mAh/g is achieved after 200 cycles at a current density of 500 mA/g. Also, 70% capacity retention can be reached after 1100 cycles at a current density of 2000 mA/g. Dincer, I. Renewable Energy and Sustainable Development: a Crucial Review. Renewable and Sustainable Energy Reviews 2000, 4(2), 157–175.Ingale, N. D.; Gallaway, J. W.; Nyce, M.; Couzis, A.; Banerjee, S. Rechargeability and Economic Aspects of Alkaline Zinc–Manganese Dioxide Cells for Electrical Storage and Load Leveling. Journal of Power Sources 2015, 276, 7–18.Song, M.; Tan, H.; Chao, D.; Fan, H. J. Recent Advances in Zn-Ion Batteries. Advanced Functional Materials 2018, 28 (41), 1802564.Jiang, B.; Xu, C.; Wu, C.; Dong, L.; Li, J.; Kang, F. Manganese Sesquioxide as Cathode Material for Multivalent Zinc Ion Battery with High Capacity and Long Cycle Life. Electrochimica Acta 2017, 229, 422–428.Mao, M.; Wu, X.; Hu, Y.; Yuan, Q.; He, Y.-B.; Kang, F. Charge Storage Mechanism of MOF-Derived Mn2O3 as High Performance Cathode of Aqueous Zinc-Ion Batteries. Journal of Energy Chemistry 2021, 52, 277–283.

A study on the properties of hexagonal Zn3(OH)2V2O7·2H2O as cathode material for zinc-ion battery

A study on the properties of hexagonal Zn3(OH)2V2O7·2H2O as cathode material for zinc-ion battery

Ni-doped δ-MnO2 as a cathode for Zn-ion batteries

Among the cathode materials for zinc-ion batteries, manganese oxides have been extensively studied. Thermal decomposition method was adopted to synthesize the Ni-doped δ-MnO2 material, called as NixMn1-xO2. The electrochemical performance and energy storage mechanism of NixMn1-xO2 were studied in 2M ZnSO4 + 0.2M MnSO4 electrolyte. Nickel doping can significantly improve the electrochemical activity of δ-MnO2. Therefore, Ni-doped δ-MnO2 shows better electrochemical cycling performance than δ-MnO2. At 100 mA g−1, NixMn1-xO2 (x=0.2) the specific capacity of 280mAh g−1 in the second circle, and the corresponding voltage platform is 1.36V and 1.23 two discharge voltage platforms. After 100 cycles, the specific capacity of NixMn1-xO2 (x=0.2) still maintain 167 mAh g−1 at a current density of 100 mA g−1. In addition, we also proved that Zn2+ and H+ are co-intercalated into NixMn1-xO2 during the process of charge and discharge and the electrochemical reaction is highly reversible. This research broadens the thinking of exploring ZIBs cathode materials with good specific capacity and cycle performance.

Preparation and electrochemical properties of α-MnO2/rGO-PPy composite as cathode material for zinc-ion battery

Preparation and electrochemical properties of α-MnO2/rGO-PPy composite as cathode material for zinc-ion battery

Intimately coupled Mn3O4 nanocrystalline@3D honeycomb hierarchical porous network scaffold carbon for high-performance cathode of aqueous zinc-ion batteries

Herein, 3D honeycomb hierarchical porous network scaffold carbon is synthesized by a unique PVP-SiO2-boiling method with the boiling bubbles as soft template and SiO2 nanospheres as hard template. Then MnO2 nanosheets intimately grow on the carbon matrix and are further decomposed to Mn3O4 nanocrystalline with size of 7–9 nm. The obtained Mn3O4 nanocrystalline@3D honeycomb hierarchical porous network scaffold carbon has abundant mesopores and large specific surface area (92 m2 g−1). When used as a cathode material for zinc-ion batteries, the synthesized composites exhibit high reversible capacity (546.2 mAh g−1 at 0.5 A g−1), remarkable cycling stability (discharge capacity of 97.8 mAh g−1 at 3 A g−1 after 600 cycles) and superior rate capability (15.7 mAh g−1 at 10 A g−1). The kinetics analyses indicate zinc storage mechanism includes diffusion process and capacitive process of Zn2+ and H+ ions, and the capacitive storage is dominant. The outstanding zinc storage performance benefits from the structural advantages. The unique carbon matrix improves electronic conductivity of Mn3O4, facilitates penetration of electrolyte, and well supports Mn3O4 nanocrystalline. The small size and large specific surface area of Mn3O4 nanocrystalline induce significant capacitive storage effect.

Enhancing the Electrochemical Performances by Wet Ball Milling to Introduce Structural Water into an Electrolytic MnO2/Graphite Nanocomposite Cathode for Zinc-Ion Batteries

The introduction of structural water in cathode materials of zinc-ion batteries can reduce electrostatic interactions to promote zinc-ion diffusion. However, it is difficult to introduce structural...

High‐Voltage Zinc‐Ion Batteries: Design Strategies and Challenges

AbstractRechargeable zinc‐ion batteries (ZIBs) have recently attracted attention for applications in energy storage systems owing to their intrinsic safety, low cost, environmental compatibility, and competitive gravimetric energy density. To enable the practical applications of ZIBs, their energy density must be equivalent to the existing commercial lithium‐ion batteries. To acquire high‐energy density, increasing the operating voltage of the battery is undoubtedly an effective method, which demands cathode material to exhibit a high voltage versus Zn2+/Zn, while matching a highly reversible anode and an electrolyte with a sufficiently wide electrochemical stability window. This review focuses on the design strategies and challenges towards high‐voltage ZIBs. First, the basic electrochemistry of ZIBs and the recent progress in various high‐voltage cathode materials for ZIBs, including Prussian blue analogs, polyanionic compounds, and metal‐based oxides are introduced. The challenges and corresponding countermeasures of these materials are discussed, while strategies to further improve the cathode operating voltage, influence factors of voltage in the redox reaction, and energy storage mechanism are also illustrated. The following section describes the strategies towards high‐performance Zn anode, and summarizes the electrolytes that can help increase the battery voltage. The final section outlines the potential development in ZIBs.

Electrochemical Injection Oxygen Vacancies in Layered Ca2Mn3O8 for Boosting Zinc-Ion Storage.

Manganese-based compounds have emerged as attractive cathode materials for zinc-ion batteries owing to their high operating voltage, large specific capacity, and no pollution. However, the structural collapse and sluggish kinetics of manganese-based compounds are major obstacles that hinder their practical applications. Here, a kind of novel layered Ca2Mn3O8 with a low ion diffusion barrier and high structural stability has been achieved through an electrochemical charging process with in situ injecting oxygen vacancies. This greatly increases the electrochemical active area and improves the Zn ions diffusion coefficient by 2 orders of magnitude, which significantly enhances the reaction kinetics, pseudocapacitance properties, and capacity. As a result, the cathode containing oxygen vacancies present an impressive reversible capacity of 368 mAh g-1, an unprecedented energy density of 512 Wh kg-1, and superior capacity retention of 92.3% at a high current density of 5 A g-1 after 3000 cycles. This work unveils an effective method for vacancy regulation of electrode materials, paving a new way to improve the electrochemical performance of zinc-ion batteries.

High-performance zinc-ion batteries enabled by electrochemically induced transformation of vanadium oxide cathodes

Rechargeable aqueous zinc-ion batteries (ZIBs) have become a research hotspot in recent years, due to their huge potential for high-energy, fast-rate, safe and low-cost energy storage. To realize good electrochemical properties of ZIBs, cathode materials with prominent Zn2+ storage capability are highly needed. Herein, we report a promising ZIB cathode material based on electrochemically induced transformation of vanadium oxides. Specifically, K2V6O16·1.5H2O nanofibers were synthesized through a simple stirring method at near room temperature and then used as cathode materials for ZIBs in different electrolytes. The cathode presented superior Zn2+ storage capability in Zn(OTf)2 aqueous electrolyte, including high capacity of 321 mAh/g, fast charge/discharge ability (96 mAh/g delivered in 35 s), high energy density of 235 Wh/kg and good cycling performance. Mechanism analysis evidenced that in Zn(OTf)2 electrolyte, Zn2+ intercalation in the first discharge process promoted K2V6O16·1.5H2O nanofibers to transform into Zn3+xV2O7(OH)2·2H2O nanoflakes, and the latter served as the Zn2+-storage host in subsequent charge/discharge processes. Benefiting from open-framework crystal structure and sufficiently exposed surface, the Zn3+xV2O7(OH)2·2H2O nanoflakes exhibited high Zn2+ diffusion coefficient, smaller charge-transfer resistance and good reversibility of Zn2+ intercalation/de-intercalation, thus leading to superior electrochemical performance. While in ZnSO4 aqueous electrolyte, the cathode material cannot sufficiently transform into Zn3+xV2O7(OH)2·2H2O, thereby corresponding to inferior electrochemical behaviors. Underlying mechanism and influencing factors of such a transformation phenomenon was also explored. This work not only reports a high-performance ZIB cathode material based on electrochemically induced transformation of vanadium oxides, but also provides new insights into Zn2+-storage electrochemistry.

V2O3@Amorphous Carbon as a Cathode of Zinc Ion Batteries with High Stability and Long Cycling Life

Zinc ion batteries (ZIBs) have the advantages of environmental friendliness, safety, and simple assembly and have strong application potential in the field of energy storage. In this work, an amorphous carbon-loaded V₂O₃ (V₂O₃@AC) material is prepared by calcination and used as a cathode material for ZIBs. The V₂O₃@AC cathode has excellent stability and long life, which maintains 94.8 and 90.7% capacity retention after 180 cycles at 0.1 A g–¹ and after 1600 cycles at 1 A g–¹, respectively. By scanning electron microscopy (SEM) characterization, V₂O₃@AC is composed of small irregular nanoparticles, which have a lot of space for electrolyte penetration and ion transmission, and the kinetic studies also confirm this transport capability. The mechanism of zinc storage is studied by ex situ X-ray powder diffraction, X-ray photoelectron spectroscopy, and SEM technology, and they confirm that V₂O₃ will undergo phase transition and become V₁₀O₂₄·12H₂O during the first charge process. Due to the high stability and cycle life of V₂O₃, we believe that it has competitive potential in zinc ion batteries and can play an important role in large-scale energy storage in the future.