High-performance Zinc-ion Batteries Research Articles

A Stable Triazole-Based Covalent Gel for Long-Term Cycling Zn Anode in Zinc-Ion Batteries.

In this work, a functional covalent gel material is developed to resolve the severe dendritic growth and hydrogen evolution reaction toward Zn/electrolyte interface in aqueous zinc-ion batteries (ZIBs). A covalent gel layer with superior durability forms homogeneously on the surface of Zn foil. The covalent gel with triazole functional groups can uniformize the transport of Zn2+ due to the interactions between Zn2+ ions and the triazole groups in the covalent gel. As a consequence, the symmetrical battery with triazole covalent gel maintains stable Zn plating/stripping for over 3000h at 1mAcm-2 and 1mAhcm-2 , and the full cell combined with a V2 O5 cathode operates steadily and continuously for at least 1800cycles at 5Ag-1 with a capacity retention rate of 67.0%. This work provides a train of thought to develop stable covalent gels for the protection of zinc anode toward high-performance ZIBs.

Dual-modification of oxygen vacancies and PEDOT coating on MnO2 nanowires for high-performance zinc ion battery

MnO2 has outstanding potential for application in cathode materials of zinc ion batteries (ZIBs). However, the poor electrical conductivity, poor ion diffusion kinetics, and structural instability greatly limit its rate performance, specific capacity, and cycling stability. Herein, we prepared PEDOT-coated MnO2 cathode material with oxygen vacancy defects, namely Vö-MnO2@PEDOT, by Dual-modification of MnO2 nanowires. The PEDOT coating optimizes the electron transfer capability of the material while inhibiting the dissolution of MnO2. The oxygen vacancies accelerate ion diffusion. Vö-MnO2@PEDOT possesses a joint energy storage mechanism, containing the insertion/extraction of H+/Zn2+ and dissolution/precipitation of MnO2. This joint energy storage mechanism explains the high specific capacity and the increase in capacity. The Vö-MnO2@PEDOT displays a high specific capacity of 400 mAh/g at 0.2 A/g. Besides, at 2 A/g, Vö-MnO2@PEDOT outputs a high capacity of 213 mAh/g after 2000 cycles. This research provides a feasible research idea for the performance optimization of manganese oxide cathode materials.

Integrated solution for a stable and high-performance zinc-ion battery using an electrolyte additive

Owing to their excellent safety, high capacity, eco-friendliness, and low cost, aqueous zinc-ion batteries (ZIBs) consisting of Zn anode and vanadium pentoxide cathode are considered as an attractive candidate for large-scale energy storage systems. However, the non-uniform dendrite growth and hydrogen evolution at the anode, as well as metal-ion dissolution at the cathode, caused by the utilization of acid electrolytes limit the capacity and cycle life of ZIBs. To address this, this study demonstrated the use of a stable and high-performance active material as the anode/cathode and vanadium (IV) oxide sulfate (VOSO4) as an electrolyte additive to fabricate high-energy performance ZIBs via a one-step process. The self-assembled passive layer on the anode surface enabled improved ion diffusion kinetics; thus, the ZIBs exhibited increased capacity (590 mAh g − 1 at 1 A g − 1) and rate capability (420 mAh g − 1 at 5 A g − 1). In addition, the inhibition of vanadium dissolution at the cathode extended the cycling performance of the battery for up to 400 cycles with a capacity retention of 77%. This strategy is a facile and feasible method to address the anode and cathode issues of ZIBs, thus providing new opportunities for the realization of stable and high-performance ZIBs.

Development of high-performance zinc-ion batteries: Issues, mitigation strategies, and perspectives

Zn-ion batteries (ZIBs) continue to attract attention for commercial grid storage systems and as alternatives to lithium-ion batteries owing to their safety, environmental friendliness, relatively high volumetric energy density, material availability, and lower production cost. Unfortunately, issues such as dendrite formation at the anode, cathode dissolution, and parasitic side reactions (such as hydrogen evolution and corrosion reactions) continue to plague this battery technology, thus hindering its practical application. In this review, we provide an in-depth understanding of the current issues that affect zinc-ion batteries and comprehensively discuss the issues affecting zinc anodes, cathodes, and electrolytes. Further, the current research focusing on mitigating these issues has been scrutinized. This review article presents recent perspectives on zinc-ion batteries regarding factors such as environmental friendliness, cost of development, and enhancing the cycle life of zinc-ion batteries to guide the future development of high-performance zinc-ion batteries.

Controlled deposition via a bifunctional layer enables dendrite-free zinc metal batteries

Suppressing the Zn dendrites of the anode is regarded beneficial to constructing the high safe and long life Zn metal battery. However, it is still an austere challenge to realizing the even zinc nucleation and controllable growth. Herein, we reported a dendrite-free Zn anode based on the protection of Ag nanoparticles modified reduced graphene oxide (rGO/Ag@Zn). Among them, the parallelly aligned rGO layers drive the epitaxial deposition of Zn along (002) plane, while ultrafine Ag nanoparticles serve as the zincophilic seeds anchored on rGO to modulate uniform Zn-ion distribution and realize horizontally confined Zn deposition. Such synergisticeffect restrains the growth of Zn dendrites, enabling an ultra-stable Zn anode. Therefore, the rGO/Ag@Zn symmetric cell can steadily cycle over 2200 h with a lower voltage polarization of 33.1 mV at a high current density and areal capacity (10 mA cm−2 and 5 mA cm−2). Meanwhile, the full cell matched with V2O5 cathode delivers a high capacity of 157.5 mA h g−1 after 4000 cycles at 5 A/g. This bifunctional protection layer on Zn anode leads a dendrite-free Zn platting/stripping and provides a facile approach for high-performance zinc ion batteries.

Naphthoquinone-intercalated vanadium oxide for high-performance zinc-ion battery

Naphthoquinone-intercalated vanadium oxide for high-performance zinc-ion battery

Enhanced zinc-ion batteries through the coating of surface-functionalized graphene on the anode: A promising solution for uniform zinc plating

Aqueous zinc-ion batteries (ZIBs) have attracted attention as large-scale energy storage systems because of their excellent safety, high capacity, eco-friendliness, and low cost. However, the utilization of acid electrolytes in ZIBs causes non-uniform dendrite growth at the anode, which limits their capacity and cycle life. To solve this issue, an advanced anode with high electrical conductivity and good interfacial stability is required. In this study, surface-functionalized graphene was used as a protective layer on the anode surface. Specifically, the surface engineering using plasma treatment is employed to enhance the oxygen-functional groups of graphene layer. The resulting ZIB exhibited superior energy storage performance and reversibility, with an improved specific capacity of 260.0 mA h g−1 at 0.3 A g−1, and an excellent long-term stability and a specific capacity of 139.0 mA h g−1 during 150 cycles at 2.0 A g−1. The proposed method is an easy and feasible method for addressing the anode issues of ZIBs, thus providing new opportunities for stable and high-performance ZIBs.

Homogeneous regulation of arranged polymorphic manganese dioxide nanocrystals as cathode materials for high-performance zinc-ion batteries

Rechargeable aqueous zinc-ion batteries have emerged as attractive energy storage devices by virtue of their low cost, high safety and eco-friendliness. However, zinc-ion cathodes are bottlenecked by their vulnerable crystal structures in the process of zinc embedding and significant capacity fading during long-term cycling. Herein, we report the rational and homogeneous regulation of polycrystalline manganese dioxide (MnO2) nanocrystals as zinc cathodes via a surfactant template-assisted strategy. Benefiting from the homogeneous regulation, MnO2 nanocrystals with an ordered crystal arrangement, including nanorod-like polyvinylpyrrolidone-manganese dioxide (PVP-MnO2), nanowire-like sodium dodecyl benzene sulfonate-manganese dioxide and nanodot-like cetyltrimethylammonium bromide-manganese dioxide, are obtained. Among these, the nanorod-like PVP-MnO2 nanocrystals exhibit stable long-life cycling of 210 mAh g−1 over 180 cycles at a high rate of 0.3 A g−1 and with a high capacity retention of 84% over 850 cycles at a high rate of 1 A g−1. The good performance of this cathode significantly results from the facile charge and mass transfer at the interface between the electrode and electrolyte, featuring the crystal stability and uniform morphology of the arranged MnO2 nanocrystals. This work provides crucial insights into the development of advanced MnO2 cathodes for low-cost and high-performance rechargeable aqueous zinc-ion batteries.

Vanadium oxide cathode with synergistic engineering of calcium-ion intercalation and polyaniline coating for high performance zinc-ion batteries

Vanadium oxide cathode with synergistic engineering of calcium-ion intercalation and polyaniline coating for high performance zinc-ion batteries

Amino-functionalized carbon nanotubes stimulating γ-MnO2 to achieve high-performance zinc-ion batteries

With suitable operating voltage and high capacity, manganese dioxide (MnO2) shows great potential for the cathode of aqueous zinc ion batteries. However, its cycling stability is severely limited by the unstable host structure and inevitable dissolution of Mn2+. Herein, the amino-functionalized carbon nanotubes (MWCNTs-NH2) are introduced to construct the MWCNTs-NH2/γ-MnO2 nanocomposite (NCM) to significantly stimulate the cyclic stability of γ-MnO2. On the one hand, MWCNTs-NH2 can give impetus for stable integral structure and good overall electrical conductivity to γ-MnO2 through homogeneous three-dimensional mechanical and conductive networks. On the other hand, the amino groups of MWCNTs-NH2 can participate in the storage of Zn2+/H+ and, most importantly, boost the deposition of Mn2+ ions from the electrolyte to the cathode to inhibit the loss of active substance in the long-term cycle. Driven by these advantageous effects, the NCM cathode exhibits an ultra-high capacity of 417.9 mAh g−1 at 0.2 A g−1 and a long cycling life over 3500 cycles at 3.0 A g−1 with 91.4% capacity retention. This study reveals the importance of promoting Mn2+ deposition in Zn-MnO2 batteries and presents an effective strategy for achieving stable cycling of MnO2 cathodes.

A design of MnO-CNT@C3N4 cathodes for high-performance aqueous zinc-ion batteries

Manganese oxides have been regarded as one of the most promising candidates in rechargeable aqueous zinc ion batteries due to their high specific capacity, high operating voltage, low cost and no-toxicity. Nevertheless, the grievous dissolution of manganese and the sluggish Zn2+ ions diffusion kinetics deteriorate the long cycling stability and the rate performance. Herein, we propose a combination of hydrothermal and thermal treatment strategy to design a MnO-CNT@C3N4 composite cathode material where MnO cubes are coated by carbon nanotubes (CNTs) and C3N4. Owing to the enhanced conductivity by CNTs and the alleviation of the dissolution of Mn2+ from the active material by C3N4, the optimized MnO-CNT@C3N4 exhibits an excellent rate performance (101 mAh g−1 at a large current density of 3 A g−1) and a high capacity (209 mAh g−1 at a current density of 0.8 A g−1), which is much better than its MnO counterpart. The energy storge mechanism of MnO-CNT@C3N4 is confirmed to be the co-insertion of H+/Zn2+. The present work provides a viable strategy for the design of advanced cathodes for high-performance zinc ion batteries.

Bimetallic MnMoO4 nanostructures on carbon fibers as flexible cathode for high performance zinc-ion batteries

Aqueous zinc ion batteries (ZIBs) are promising energy storage devices due to the advantageous features of Zn. However, developing suitable cathode materials with high performance is still an urgent task for the development of ZIBs. In this work, we report on the preparation of a flexible cathode for ZIBs consisting of carbon fiber supported MnMoO4 nanostructures protected with N-doped carbon coatings (CF/MnMoO4@NCs). The N-doped carbon coating on MnMoO4 nanostructures can buffer volume expansion of MnMoO4, and the CF and NCs with good electronic conductivity can facilitate quick electrons transportation in the CF/MnMoO4@NCs system. The optimized CF/MnMoO4@NCs cathode exhibits high capacity and good rate capability. Specifically, it delivers an outstanding discharge capacity of 663 mA h g−1 at a current density of 0.1 A/g after 100 cycles, and at a current density of 2 A/g, the cathode can still achieve a discharge capacity of 212 mA h g−1. This work expands the choice of cathode material and provides constructive direction on designing high-performance cathode materials for ZIBs.

Mnco2o4 spinel microsphere assembled with flake structure as a cathode for high-performance zinc ion battery

Aqueous rechargeable zinc-ion batteries (ZIBs) with manganese-based materials as a cathode have suffered from limitations in energy density and life cycle performance. Materials for use as cathodes for ZIBs are constantly being researched in order to achieve high electrochemical performance. Herein, a spinel MnCo2O4 microsphere assembled with the interconnected micro- and nanoflake structures has been successfully synthesized via hydrothermal method. The dynamic electrochemistry properties of a zinc-ion battery with a MnCo2O4 cathode are demonstrated through the study of charge/discharge process. The constructed zinc foil anode with the MnCo2O4 cathode reveals the discharge capacity of 595.3 mAh g−1 at 0.05 A g−1. The Zn//MnCo2O4 battery achieves energy density values in the range of 714 to 207 Wh kg−1 with power density values in the range of 60 to 1200 W kg−1. The good cycle stability of 85 % retention capacity after 250 cycles at 0.2 A g−1 is reported. Additionally, the structural development during cycling at the atomic level is examined by ex-situ measurement, indicating that the activation process of MnCo2O4 was primarily developed through the development of Mn2+/Mn3+ and Co2+/Co3+ electron states, inducing the electro-capacity properties of ZIBs.

Agar-based hydrogel polymer electrolyte for high-performance zinc-ion batteries at all climatic temperatures

Aqueous zinc-ion batteries (ZIBs) have received numerous attention because of their inherent safety and low cost. However, ZIBs are highly sensitive to temperature; the realization of full-temperature ZIBs is of great importance. In this study, an agar-based composite hydrogel polymer electrolyte (AG-HGPE) with the blend of agar and polyacrylamide (PAM) was prepared. It has a non-porous homogeneous structure, and shows various merits, e.g., strong liquid absorption rate, good mechanical properties, and large Zn2+ transference number. The corresponding Zn-symmetric cells possess reversible zinc stripping/plating phenomenon up to 500h at a current density of 1mA cm-2 and an areal capacity of 1 mAh cm-2. The Zn/AG-HGPE/V2O5 cells exhibit good rate performance and stable cyclic behaviors at -25°C, 25°C and 50°C, as well as excellent adaptability to the changes of ambient temperature. The research paves a new route for developing green energy storage devices running in wide temperature range.

Enhancing interfacial and internal reaction of sulfide electrode with zinc ions by synergistic effect of phase and structure engineering

Although zinc-ion batteries express superior advantages included great safety and cost-effectiveness for grid-level energy storage, the electrode materials are still suffering from structural collapse and depressed kinetics. Fortunately, these defects can be effectively improved by the combination of structure engineering and composition regulation, which is an effective strategy for improving electrochemical reaction kinetics and structure tolerance. Thereof, the Mo-doped Bi2S3 materials with nanorod-linked spherical framework have been constructed in this work. The introduction of Mo-heteroatom can optimize the electronic structure of Bi2S3 for strengthening its conductivity, which contributes to obtain the enhanced reaction kinetics. Furthermore, this trend can be boosted by the design of nanorod-assembled sphere, which effectually reduces the ion diffusion path. In addition, the shaggy sphere possesses the ability of stress dispersion, contributing to maintain the structure integrity during charging/discharging process. As expected, this designed electrode materials exhibit a superior reversibility capacity of 51.0 mA h g − 1 over 1000 cycles at 2000 mA g − 1, and a prominent high-rate capacity of 93.7 mA h g − 1 at the enlarged rate of 6000 mA g − 1. Importantly, this present research will enlighten the combined modification strategy to engineering metal sulfides for high-performance zinc-ion batteries.

Unveiling the effect of structural water on Zn-ion storage of polyoxovanadate for high-rate and long-life aqueous zinc ion battery

Aqueous zinc-ion batteries (ZIBs) are promising for grid-scale energy storage because of their low cost, high theoretical energy density, and high safety; however, the rational design of advanced cathode materials with stable internal structures and sufficient Zn2+ diffusion channels remains a challenge. To date, most studies have focused on the structural water of electrode materials to improve their electrochemical kinetics without considering its possible negative effects. Herein, we develop the polyoxovanadates of Na6[V10O28]·nH2O with controllable structural water (denoted as NVO-n, n = 18, 2.6 and 0) as cathodes for Zn2+ storage, which provide model objects to study the effects of water molecules on electrochemical properties. Results reveal that an appropriate amount of structural water improves ion transport by shielding the effective charge of Zn2+ ions while reducing the hindrance to the migration of Zn2+ ions, enabling fast Zn2+ storage. Moreover, the NVO-2.6 possesses multi-electron redox ability and high structural stability, which ensures the highly reversible Zn2+ intercalation/de-intercalation at a high working voltage (0.98 V) and small volumetric strain upon cycling. Consequently, the optimized NVO-2.6 delivers a high specific capacity of 228.5 mAh g−1 at 0.1 A g−1 and a long-term cyclability with 89.7% capacity retention after 3000 cycles at 10 A g−1. This study paves a new direction for the design of polyoxovanadate-based cathodes toward high-performance ZIBs.

Electrodeposition of polypyrrole for high-performance zinc ion battery

Electrodeposition of polypyrrole for high-performance zinc ion battery

Two-Dimensional VO2 Nanosheets with a Controllable Crystalline-Preferred Orientation for High-Performance Zinc-Ion Batteries

Due to the environmental friendliness, cost-effectiveness and inherent safety, rechargeable aqueous zinc ion batteries have attracted much interest as a promising energy storage device. VO2 is one of the most common materials for rechargeable zinc ion batteries. The insertion/extraction of zinc ions within VO2 is highly anisotropic, with different channel sizes along different axes. Therefore, it is quite important to control the orientation of VO2 crystals so as to manipulate the transportation of Zn2+ ions more effectively and sufficiently. Herein, a novel intercalation-type two-dimensional VO2 nanosheet with preferred orientation (PO-VO2) of the c-axis was prepared. Benefitting from the structural merits, the PO-VO2 nanosheets demonstrate an attractive capacity of 511.6 mAh g−1 at a current density of 0.05 A g−1 in a voltage of 0.2–1.6 V, which is obviously better than that of many vanadium oxide-based cathodes reported until now. The PO-VO2//Zn aqueous zinc ion full cell exhibits a high energy density of 290.5 Wh kg−1 at a power density of 38.4 W kg−1 (based on the mass of the VO2 cathode electrode). The outstanding energy storage behavior, together with the facile and affordable synthesis route, endows the PO-VO2 nanosheets with promising applications for aqueous zinc ion batteries.

In-situ construction of barium-induced cathode electrolyte interphase to enable mechanostable high-performance zinc-ion batteries

Vanadium-based compounds with open frameworks are recently the subject of intensive research as cathodes for aqueous zinc-ion batteries (AZIBs) with the advantages of high safety and high energy density. However, the spontaneous vanadium dissolution from a cathode and the formation of by-products in aqueous electrolytes are challenging issues that must be addressed as they cause substantial capacity degradation and inadequacy in cycle life. Here, we develop an efficient way to suppress vanadium dissolution via an in-situ formed cathode electrolyte interface (CEI) by incorporating barium ions in the vanadium framework. Such barium ions increase the interlayer structure and act as a sacrificial agent to form an in-situ BaSO4 CEI that reduces vanadium dissolution while enhancing the diffusion kinetics. As a cathodic active material, Ba–V6O13 nanobelts show a specific capacity of 305 mAh g−1 at 0.1 A g−1 and an energy density of 213 Wh/kg, offering excellent reversible capacity retention of 99.94% per cycle. Besides, it operates stably even after physically cutting the device and exhibits excellent interfacial stability. This work presents an innovative strategy to accelerate the commercialization of safe, flexible AZIBs.

Constructing 2D Sandwich-like MOF/MXene Heterostructures for Durable and Fast Aqueous Zinc-Ion Batteries.

Two-dimensional metal-organic frameworks (2D MOFs) can be used as the cathodes for high-performance zinc-ion battery due to their large one-dimensional channels. However, the conventionally poor electrical conductivity and low structural stability hinder their advances. Herein, we report an alternately stacked MOF/MX heterostructure, exhibiting the 2D sandwich-like structure with abundant active sites, improved electrical conductivity and exceptional structural stability. Ex situ characterizations and theoretical calculations reveal a reversible intercalation mechanism of zinc ions and high electrical conductivity in the 2D heterostructure. Electrochemical tests confirm excellent Zn2+ migration kinetics and ideal pseudocapacitive behaviors. As a consequence, Cu-HHTP/MX shows a superior rate performance (260.1 mAh g-1 at 0.1 A g-1 and 173.1 mAh g-1 at 4 A g-1 ) and long-term cycling stability of 92.5 % capacity retention over 1000 cycles at 4 A g-1 .