High-performance Zinc-ion Batteries Research Articles

In situ synthesis of a self-supported MnO2-based cathode for high-performance zinc-ion batteries by K+ pre-intercalation

Aqueous zinc-ion batteries (ZIBs) have attracted extensive research interest due to their multiple advantages, such as high safety, low cost, environmental friendliness, and suitability for large-scale energy storage systems. However, the further development and application of ZIBs is hindered by the sluggish reaction kinetics, low electrical conductivity, and unstable crystal structure of cathode materials. Here, a self-supporting cathode of K+ intercalated MnO2 on three-dimensional layered carbon-based conductive substrate (LGP) (LGP@K0.15MnO2) without binder and conductive agent was synthesized by two simple steps. The synergistic effect of the three-dimensional layered carbon conductive network and pre-intercalated K+ ions in LGP@K0.15MnO2 can effectively stabilize the material structure, promote electrical conductivity, and facilitate ion diffusion. Therefore, the obtained LGP@K0.15MnO2 exhibited a high specific capacity and excellent cycling stability, which delivered 358.9 mAh/g for the first cycle at a current density of 200 mA/g, and maintained 92.5% of the capacity after 100 cycles. In addition, a capacity retention rate of 83.3% after 1000 cycles at 1000 mA/g was obtained. It was also found that the pre-intercalation of excess K+ ions would adversely affect the crystal structure and electrochemical performance of cathode materials.

The Synthesis of Manganese Hydroxide Nanowire Arrays for a High-Performance Zinc-Ion Battery.

The morphology, microstructure as well as the orientation of cathodic materials are the key issues when preparing high-performance aqueous zinc-ion batteries (ZIBs). In this paper, binder-free electrode Mn(OH)2 nanowire arrays were facilely synthesized via electrodeposition. The nanowires were aligned vertically on a carbon cloth. The as-prepared Mn(OH)2 nanowire arrays were used as cathode to fabricate rechargeable ZIBs. The vertically aligned configuration is beneficial to electron transport and the free space between the nanowires can provide more ion-diffusion pathways. As a result, Mn(OH)2 nanowire arrays yield a high specific capacitance of 146.3 Ma h g−1 at a current density of 0.5 A g−1. They also demonstrates ultra-high diffusion coefficients of 4.5 × 10−8~1.0 × 10−9 cm2 s−1 during charging and 1.0 × 10−9~2.7 × 10−11 cm−2 s−1 during discharging processes, which are one or two orders of magnitude higher than what is reported in the studies. Furthermore, the rechargeable Zn//Mn(OH)2 battery presents a good capacity retention of 61.1% of the initial value after 400 cycles. This study opens a new avenue to boost the electrochemical kinetics for high-performance aqueous ZIBs.

In Situ Construction of Protective Films on Zn Metal Anodes via Natural Protein Additives Enabling High-Performance Zinc Ion Batteries.

The strong activity of water molecules causes a series of parasitic side reactions on Zn anodes in the aqueous electrolytes. Herein, we introduce silk fibroin (SF) as a multifunctional electrolyte additive for aqueous zinc-ion (Zn-ion) batteries. The secondary structure transformation of SF molecules from α-helices to random coils in the aqueous electrolytes allows them to break the hydrogen bond network among free water molecules and participate in Zn2+ ion solvation structure. The SF molecules released from the [Zn(H2O)4(SF)]2+ solvation sheath appear to be gradually adsorbed on the surface of Zn anodes and in situ form a hydrostable and self-healable protective film. This SF-based protective film not only shows strong Zn2+ ion affinity to promote homogeneous Zn deposition but also has good insulating behavior to suppress parasitic reactions. Benefiting from these multifunctional advantages, the cycle life of the Zn||Zn symmetric cells reaches over 1600 h in SF-containing ZnSO4 electrolytes. In addition, by adopting a potassium vanadate cathode, the full cell shows excellent cycling stability for 1000 cycles at 3 A g-1. The in situ construction of a protective film on the Zn anode from natural protein molecules provides an effective strategy to achieve high-performance Zn metal anodes for Zn-ion batteries.

Facile and Rapid Synthesis of Porous Hydrated V2O5 Nanoflakes for High-Performance Zinc Ion Battery Applications.

Hydrated V2O5 with unique physical and chemical characteristics has been widely used in various function devices, including solar cells, catalysts, electrochromic windows, supercapacitors, and batteries. Recently, it has attracted extensive attention because of the enormous potential for the high-performance aqueous zinc ion battery cathode. Although great progress has been made in developing applications of hydrated V2O5, little research focuses on improving current synthesis methods, which have disadvantages of massive energy consumption, tedious reaction time, and/or low efficiency. Herein, an improved synthesis method is developed for hydrated V2O5 nanoflakes according to the phenomenon that the reactions between V2O5 and peroxide can be dramatically accelerated with low-temperature heating. Porous hydrated V2O5 nanoflake gel was obtained from cheap raw materials at 40 °C in 30 min. It shows a high specific capacity, of 346.6 mAh/g, at 0.1 A/g; retains 55.2% of that at 20 A/g; and retains a specific capacity of 221.0 mAh/g after 1800 charging/discharging cycles at 1 A/g as an aqueous zinc ion battery cathode material. This work provides a highly facile and rapid synthesis method for hydrated V2O5, which may favor its applications in energy storage and other functional devices.

Synergistic Optimization Strategy Involving Sandwich-like MnO2@rGO and Laponite-Modified PAM for High-Performance Zinc-Ion Batteries and Zinc Dendrite Suppression.

Optimization of the cathode structure and exploration of a novel electrolyte system are important approaches for achieving high-performance zinc-ion batteries (ZIBs) and zinc dendrite suppression. Herein, a quasi-solid-state ZIB combining a sandwich-like MnO2@rGO cathode, a laponite (Lap)-modified polyacrylamide (PAM) hydrogel electrolyte, and an electrodeposited zinc anode is designed and constructed by a synergistic optimization strategy. The MnO2 composite prepared through the intercalation of rGO shows developed mesopores, providing accessible ion transport channels and exhibiting a high electrical conductivity. Thanks to the high dispersion of Lap nanoplates in the hydrogel and good charge-averaging effect, the Zn//PAM-5%Lap//Zn symmetrical battery exhibits a consistent low-voltage polarization of less than 60 mV within 2000 h without a short-circuit phenomenon or any over-potential rise, indicating a stable zinc peeling/plating process. The optimized quasi-solid-state ZIB delivers a high reversible capacity of 291 mA h g-1 at a current density of 0.2 A g-1 due to the synergistic effect of each component of ZIB. Even at a high rate of 2 A g-1, it still maintains a high reversible capacity of 97 mA h g-1 after 2000 cycles, indicating its excellent electrochemical performance. Furthermore, the assembled flexible battery performs excellently in terms of damage and bending resistance.

Unsaturated Ni/V centers and short Ni·V/Ni distances in nickel vanadate for high-performance zinc-ion battery

Ni0.22V2O5(H2O)0.94 (NiVO) nanobelts were synthesized via a facile one-step hydrothermal method, which exhibited a 3D framework built by [Ni(H2O)6]2+ pillars connecting 2D V-O-V layers. Upon subsequent annealing, Ni0.22V2O5 (o-NiVO) nanobelts with a large d spacing of 9.2 Å were obtained. 3D rotation electron diffraction (cRED), Rietveld refinement and spherical aberration-corrected TEM reveal that o-NiVO displays a novel 3D framework. Annealing led to atom arrangement and partial Ni2+ ions entered into 2D V-O-V layer of o-NiVO with unsaturated Ni/V centers and short Ni ··· V (2.463 Å)/Ni ···Ni distances (2.401 Å), which can facilitate the electron transfer from O → Ni and improve the electron conductivity with a low Zn2+ migration barrier (0.64 eV) in o-NiVO, as evidenced by DFT calculations. Therefore, o-NiVO can deliver a high initial capacity of 445 mAh g−1 at 0.1 A g−1 with good rate capability and fast Zn2+ diffusion kinetics. Meanwhile, o-NiVO also possesses excellent long-term durability with capacity retention of 99.8 % over 1500 discharge/charge cycles. The fully discharged o-NiVO nanobelts was characterized by cRED, which disclosed the structural integrity of o-NiVO during the discharge process. A series of ex situ characterizations of the o-NiVO electrode reveal a co(de)intercalation mechanism of Zn2+/H+ along with partial phase transformation of o-NiVO → Zn3(OH)2V2O7(H2O)2.

High-loading and high-performance zinc ion batteries enabled by electrochemical conversion of vanadium oxide cathodes

Zinc ion batteries (ZIBs) have become highly competitive in large-scale energy storage applications due to their safety, low cost, and environmental friendliness. However, the cathode materials reported in the literature have the problem of low load (generally less than 3 mg cm‒2), which is difficult to meet the needs of industrial production. In this study, a three-dimensional network structure of calcium ion intercalated vanadium oxide cathode (CaVOH) is grown on carbon cloth (CC) by the one-step hydrothermal method. The cathode has a unique three-dimensional network structure and high mass load (∼ 7 mg cm‒2), high specific capacity (228.5 mAh g‒1 at 1 A g‒1 current density), excellent rate performance, and qualified cycle performance (70 % residual after 800 cycles). In Zn(CF3SO3)2 electrolyte, CaVOH@CC is transformed into Zn2(V3O8)2@CC (ZVO@CC) cathode by electrochemical induction. Compared with vanadium oxide cathode synthesized on carbon cloth (VOH@CC), ZVO@CC cathode has lower charge transfer resistance and higher capacitance contribution, which means that it has a better specific capacity, rate performance, and cycle stability. This work provides a new idea for the mechanical explanation of ZIB and a feasible scheme for the design of industrial ZIBs.

Fabrication of V3O7·H2O/graphene cathode for high performance zinc-ion batteries

In this paper, V3O7·H2O and V3O7·H2O/Graphene were prepared by hydrothermal synthesis method as cathode materials of aqueous zinc-ion batteries (ZIBs). Compared with bare V3O7·H2O, V3O7·H2O/Graphene cathode material exhibits higher specific capacity (463.4 mAh g−1 after 100 cycles at 1 A g−1), more excellent rate performance and longer cycle life (342.9 mAh g−1 after 2000 cycles at 10 A g−1). The enhanced performance should be ascribed to the improved conductivity of graphene. This work provides a promising cathode material (V3O7·H2O/Graphene) with great advantages and prospects in the field of large-scale energy storage.

Electrolyte Engineering Enables High Performance Zinc-Ion Batteries.

Zinc-ion batteries (ZIBs) feature high safety, low cost, environmental-friendliness, and promising electrochemical performance, and are therefore regarded as a potential technology to be applied in large-scale energy storage devices. However, ZIBs still face some critical challenges and bottlenecks. The electrolyte is an essential component of batteries and its properties affect the mass transport, energy storage mechanisms, reaction kinetics, and side reactions of ZIBs. The adjustment of electrolyte formulas usually has direct and obvious impacts on the overall output and performance. In this review, advanced electrolyte strategies are overviewed for optimizing the compatibility between cathode materials and electrolytes, inhibiting anode corrosion and dendrite growth, extending electrochemical stability windows, enabling wearable applications, and enhancing temperature tolerance. The underlying scientific mechanisms, electrolyte design principles, and recent progress are presented to provide a better understanding and inspiration to readers. In addition, a comprehensive perspective about electrolyte design and engineering for ZIBs is included.

Unsaturated coordination modes of Mn/V in manganese vanadate: Inner capture and surface migration of zinc ions for high performance zinc-ion battery

It was synthesized Mn0·2V2O5(H2O)·H2O (MnVO) porous microflowers and Ti0·055V2O5(H2O)2·H2O (TiVO) nanosheets. Rietveld refinements and high-angle annular dark-field (HAADF)-scanning transmission election microscope (STEM) reveal they are both constructed by two-dimensional (2D) V-O-V monolayers, lamellar hydrated metal ions and uncoordinated water molecules, in which all the V centers exhibit unsaturated coordination modes. Density functional theory (DFT) calculation proves that the exposed unsaturated V centers on the MnVO (001) surface can boost Zn2+ migration along the surface with a low barrier of 0.61 eV. Therefore, MnVO shows a dominant surface-controlled capacity. MnVO displays excellent Zn2+ storage behavior (435 mAh g-1 at 0.1 A g-1) with a capacity retention of 96.4 % after 1000 discharge/charge cycles at 5 A g-1, which is superior to TiVO. And MnVO and TiVO both show higher capacities than the commercial V2O5. Ex situ characterizations of MnVO discover a conversion of MnVO → Znm(MnVO) and a partial phase transformation mechanism of MnVO → Zn3(OH)2V2O7·2H2O during discharge/charge process. And DFT calculations reveal the intercalation of Zn2+ into some sites in the inner channel of MnVO is irreversible, leading to the accumulation of Zn2+ with almost unchanged interlayer spacing.

Synergistic engineering of oxygen-defect and heterojunction boosts Zn2+ (De)intercalation kinetics in vanadium oxide for high-performance zinc-ion batteries

Aqueous zinc-ion batteries (AZIBs) show tremendous potential in practical applications but are impeded by the limited comprehensive performance of cathode materials. Herein, an oxygen-defective vanadium oxide encapsulated by a thin-layer of amorphous carbon (denoted as Od-VO@C) nanocomposite with a pea-like core–shell architecture that integrates oxygen defect engineering and heterojunction engineering has been prepared. For the first time, an electrochemically anodic oxidation method is employed to create oxygen defects for vanadium oxide, which can not only offer additional active sites to Zn2+ storage processes, but also aid in improving electronic conductivity of the host. Simultaneously, coating carbon materials on the surface of vanadium oxide nanoparticles to construct the heterojunction structure powerfully protects them from aggregation and effectively alleviates capacity fading. The elaborately designed porous microstructure endows the material with highly accessible active surface and abundant short migration pathways for reversible Zn2+ storage reactions. Consequently, the Od-VO@C-based AZIB delivers comprehensive performance including an ultrahigh specific capacity up to ∼ 700 mAh·g−1, impressive rate capability and decent cycling property. Such a reliable strategy that utilizing the synergistic engineering of oxygen-defect and heterojunction via electrochemical induce promotes the booming development of transition-metal oxides for various aqueous metal-ions storage.

Electrochemically induced phase transition in a nanoflower vanadium tetrasulfide cathode for high-performance zinc-ion batteries

Aqueous zinc-ion batteries (AZIBs) are promising contenders for large-scale energy storage with the merits of their low cost, high safety, environmental friendliness, and competitive gravimetric energy density. Nevertheless, suitable cathode materials with long cycle life and adequate capacity are still rare. Herein, we report a nanoflower vanadium tetrasulfide/carbon nanotubes (VS4/CNTs) cathode with high Zn-storage performance. We propose a phase transition reaction mechanism from VS4 to zinc pyrovanadate in the initial cycles and a reversible intercalation mechanism for Zn2+ in zinc pyrovanadate during subsequent cycles. As a result, the cathode delivers a high discharge capacity of 265 mAh g−1 at 0.25 A g−1 and 182 mAh g−1 at 7 A g−1. In addition, the cathode exhibits a long-term cyclability with 93% capacity retention over 1200 cycles at 5 A g−1. VS4/CNTs with superior electrochemical performance is a hopeful cathode material in AZIBs.

A Li+ and PANI co-intercalation strategy for hydrated V2O5 to enhance zinc ion storage performance

Li+ and polyaniline (PANI) co-intercalated hydrated V2O5 with an enlarged spacing of 14.4 Å is successfully synthesized as cathode materials for high performance zinc ion batteries.

Advances in the structure and composition design of zinc anodes for high performance zinc ion batteries

In this review, we classify in detail the recent achievements in structural and composition design, including intrinsic zinc metal anodes, metal-based anodes, alloy-based anodes, carbon-based anodes, MXene-based anodes and some novel composite anodes.

Aluminium vanadate with unsaturated coordinated V centers and oxygen vacancies: surface migration and partial phase transformation mechanism in high performance zinc-ion batteries

Aluminium vanadate with unsaturated coordinated V centers and oxygen vacancies shows excellent Zn2+ storage due to the low Zn2+ migration barrier along the (001) surface, the co-(de)intercalation mechanism of H+/Zn2+ and the partial transformation.

Deposition behavior regulated by an SPSF@PMIA nanofiber separator for high-performance zinc ion batteries

The non-uniform ion deposition of zinc anodes forming zinc dendrites and the side reactions hinder the large-scale application of zinc ion batteries (ZIBs).

Vertically Aligned Mos2 Nanosheets on Monodisperse Mxene as Electrolyte-Philic Cathode for High-Performance Zinc Ion Battery

Vertically Aligned Mos2 Nanosheets on Monodisperse Mxene as Electrolyte-Philic Cathode for High-Performance Zinc Ion Battery

Stabilizing Zn Anodes by Constructing Pegma-Based Protecting Layers for High-Performance Zinc-Ion Batteries

Stabilizing Zn Anodes by Constructing Pegma-Based Protecting Layers for High-Performance Zinc-Ion Batteries

In Situ Construction of Barium-Induced Cathode Electrolyte Interphase to Enable Mechanostable High-Performance Zinc-Ion Batteries

In Situ Construction of Barium-Induced Cathode Electrolyte Interphase to Enable Mechanostable High-Performance Zinc-Ion Batteries

Stabilizing Zn Anodes by Constructing Pegma-Based Protecting Layers for High-Performance Zinc-Ion Batteries

Stabilizing Zn Anodes by Constructing Pegma-Based Protecting Layers for High-Performance Zinc-Ion Batteries