Development Of Zinc-ion Batteries Research Articles

An in-situ SbF3/Zn3Sb2 protective layer for dendrite-free zinc metal anode

Zinc-ion batteries are considered as one of the most promising electrochemical energy storage devices in the field of electrochemical energy storage due to their low cost and high safety. However, the development of zinc ion batteries using metal zinc anodes is limited by the existence of hydrogen evolution, dendrite growth, serious side reactions, low coulomb efficiency and poor cycling performance. In this work, an ultrathin ZnF2/Zn3Sb2 hybrid interfacial layer is constructed by spraying commercial Zn metal with SbF3 as the precursor. Due to the high Zn ionic conductivity of ZnF2 and Zn3Sb2, this interfacial layer can effectively enhance the uniform deposition of Zn ions and improve the stability of the solid electrolyte/anode interface. A low current density of 1 mA cm−2 and a high current density of 1 mA cm−2 can be obtained by assembling symmetric batteries with Zn@SbF3 as the anode for more than 500 h. In addition, the CuSCoS//Zn@SbF3 full battery maintains a CE rate of up to 99.2% after 1000 cycles at a current density of 2 A g−1. These results indicate that the modified Zn anode holds a large potential for Zinc-ion batteries applications.

Rational Design of Ni-Doped V2O5@3D Ni Core/Shell Composites for High-Voltage and High-Rate Aqueous Zinc-Ion Batteries.

Aqueous zinc-ion batteries (ZIBs) have significant potential for large energy storage systems because of their high energy density, cost-effectiveness and environmental friendliness. However, the limited voltage window, poor reaction kinetics and structural instability of cathode materials are current bottlenecks which contain the further development of ZIBs. In this work, we rationally design a Ni-doped V2O5@3D Ni core/shell composite on a carbon cloth electrode (Ni-V2O5@3D Ni@CC) by growing Ni-V2O5 on free-standing 3D Ni metal nanonets for high-voltage and high-capacity ZIBs. Impressively, embedded Ni doping increases the interlayer spacing of V2O5, extending the working voltage and improving the zinc-ion (Zn302+) reaction kinetics of the cathode materials; at the same time, the 3D structure, with its high specific surface area and superior electronic conductivity, aids in fast Zn302+ transport. Consequently, the as-designed Ni-V2O5@3D Ni@CC cathodes can operate within a wide voltage window from 0.3 to 1.8 V vs. Zn30/Zn302+ and deliver a high capacity of 270 mAh g-1 (~1050 mAh cm-3) at a high current density of 0.8 A g-1. In addition, reversible Zn2+ (de)incorporation reaction mechanisms in the Ni-V2O5@3D Ni@CC cathodes are investigated through multiple characterization methods (SEM, TEM, XRD, XPS, etc.). As a result, we achieved significant progress toward practical applications of ZIBs.

Critical Issues of Vanadium-Based Cathodes Towards Practical Aqueous Zn-Ion Batteries.

Aqueous zinc-ion batteries (ZIBs) are gaining significant attention for their numerous advantages, including high safety, high energy density, affordability, and environmental friendliness. However, the development of ZIBs has been hampered by the lack of suitable cathode materials that can store Zn2+with high capacity and reversibility. Currently, vanadium-based materials with tunnel or layered structures are widely researched owing to their high theoretical capacity and diversified structures. However, their long-term cycling stability is unsatisfactory because of material dissolution, phase transformation, and restrictive kinetics in aqueous electrolytes, which limits their practical applications. Different from previous reviews on ZIBs, this review specifically addresses the critical issues faced by vanadium-based cathodes for practical aqueous ZIBs and proposes potential solutions. Focusing on vanadium-based cathodes, their ion storage mechanisms, the critical parameters affecting their performance, and the progress made in addressing the aforementioned problems are also summarized. Finally, future directions for the development of practical aqueous ZIB are suggested.

Strontium titanate modified separator regulates ion flux to stabilize aqueous zinc ion battery anodes

Zinc (Zn) metal is an ideal anode material for aqueous zinc ion batteries (ZIBs), but the development of ZIBs is limited by the severe dendrite growth of Zn anode. Herein, a strontium titanate (SrTiO3) coated separator is prepared to solve this issue, concretely, the SrTiO3 (STO) modified separator exhibits special dielectric properties and well-filling of surface pores, enabling homogenize ion flux and inducing uniform deposition of Zn2+. The electrochemical measurements indicate that the Zn||Cu asymmetric cell with STO separator can stably cycled 780 cycles with an average Coulombic efficiency of 99.7%. Meanwhile, the Zn||Zn symmetric cell displays a long cycle life of 1800 h at a current density of 1 mA cm−2 and an area capacity of 0.5 mAh cm−2. Therefore, this study presents a novel approach that improves the deposition behavior of Zn2+ and represses Zn dendrite to achieve steady and long-life ZIBs.

Challenges and Strategies in the Development of Zinc-Ion Batteries.

Although promising, the practical use of zinc-ion batteries (ZIBs) remains plagued with uncontrollable dendrite growth, parasitic side reactions, and the high intercalation energy of divalent Zn2+ ions. Hence, much work has been conducted to alleviate these issues to maximize the energy density and cyclic life of the cell. In this holistic review, the mechanisms and rationale for the stated challenges shall be summarized, followed by the corresponding strategies employed to mitigate them. Thereafter, a perspective on present research and the outlook of ZIBs would be put forth in hopes to enhance their electrochemical properties in a multipronged approach.

Cobalt-doped molybdenum disulfide with rich defects and extended layered structure for rechargeable zinc-ion batteries

Zinc-ion batteries (ZIBs) have become potential energy storage devices due to its low cost, environmentally friendly and high safety. The development of ZIBs is facing huge challenges especially in cathode materials. Here, we report a strategy of doping Co into MoS 2 to get Co x Mo 1−x S 2 nanosheets with rich dislocation-defects and expanded layer spacing. MoS 2 itself has poor Zn 2+ diffusivity and low specific capacity due to small layer spacing. The diffusion of Zn 2+ is greatly improved by doping of Co. When Co x Mo 1−x S 2 nanosheets are used as positive electrode in ZIBs, the capacity increased from 31.3 mA h g −1 to 164.1 mA h g −1 , which is increased by more than five times. What’s more, even if the current is increased ten times, it still has high capacity (about 40% capacity retention). In addition, the peaks of the Zn 2+ intercalation/deintercalation in the Co x Mo 1−x S 2 electrode have been effectively improved, which indicates a much more efficiency Zn 2+ intercalation kinetic. Therefore, its capacity has been greatly improved. This research provides a general and effective strategy to reduce the embedding energy barrier of Zn 2+ to increase the diffusion rate of Zn 2+ and the capacity of ZIBs. • The addition of Co leads to dislocations defects and extending the layer spacing. • The transition metal doping method is convenient and efficient. • The rapid diffusion of Zn 2+ is achieved and the capacity is increased.

Facile large-scale preparation of vanadium pentoxide -polypyrrole composite for aqueous zinc-ion batteries

Aqueous zinc-ion batteries (ZIBs) have been noted as promising large-scale energy storage systems owing to their cost-effective and environmentally friendly merits. However, the further development of ZIBs is limited by suitable cathodes, which normally suffer from the challengers of cathode dissolution, poor electronic conductivity, and low ion diffusion coefficient. Herein, we adopted a simpler, prone largescale preparation strategy of in situ polymerization at room temperature to prepare V2O5-polypyrrole (V2O5-PPy) nanobelt composite that the V2O5 act as an oxidant for pyrrole (Py) polymerization, and Py in situ polymerized on the V2O5. The V2O5-PPy nanobelt composite contributes to preventing the dissolution of vanadium elements, improving electronic conductivity, and forming oxygen vacancies (Vö). As a result, an excellent initial discharge capacity of 441 mAh g−1 at 0.1 A g−1 and 291 mAh g−1 at a high current density of 5 A g−1 was realized. More importantly, a capacity retention rate of 95.92% after the long-term 2000 cycles at a high current density of 5 A g−1 was achieved. The capacitance control is dominant and accounts for 80.76% at 0.5 mV s−1, and the zinc ion diffusion coefficient during the cycle is 4.4 × 10−8-1.62 × 10−9 cm2 S−1, indicating good kinetics. Our work provides a feasible strategy for the large-scale fabrication of V2O5-PPy for ZIBs.

High rate and ultralong life flexible all-solid-state zinc ion battery based on electron density modulated NiCo2O4 nanosheets

The development of zinc ion batteries (ZIBs) with large capacity, high rate, and durable cathode material is a crucial and urgent task. NiCo2O4 (NCO) has received ever-growing interest as a potential cathode material for ZIBs, owing to the high theoretical capacity, rich source, cost-effective, and versatile redox nature. However, due to the slow dynamics of the NCO electrodes, its practical application in high-performance systems is severely limited. Herein, we report an electron density modulated NCO nanosheets (N-NCO NSs) with high-kinetics Zn2+-storage capability as an additive-free cathode for flexible all-solid-state (ASS) ZIBs. By virtue of the enhanced electronic conductivity, improved reaction kinetics, and increased active sites, the optimized N-NCO NSs electrode delivers a high capacity of 357.7 mAh g−1 at 1.0 A g−1 and a superior rate capacity of 201.4 mAh g−1 at 20 A g−1. More importantly, a flexible ASS ZIBs device is manufactured using a solid polymer electrolyte of a poly (vinylidene fluoride hexafluoropropylene) (PVDF-HFP) film. The flexible ASS ZIBs device shows superb durability with 80.2% capacity retention after 20,000 cycles and works well in the range of −20–70 °C. Furthermore, the flexible ASS ZIBs achieves an impressive energy density as high as 578.1 W h kg−1 with a peak power density of 33.6 kW kg−1, substantially outperforming those latest ZIBs. This work could provide valuable insights for constructing high-kinetics and high-capability cathodes with long-term stability for flexible ASS ZIBs.

Host-guest supramolecular interaction behavior at the interface between anode and electrolyte for long life Zn anode

The hydrogen evolution reaction (HER) and dendrite growth associated with Zn anode have become the main bottlenecks for the further development of zinc ion batteries (ZIBs). In this work, the electrochemical activity of H3O+ is inhibited by the supramolecular host–guest complex composed of H3O+ as guest and 18-crown-6 as host. The even Zn plating is induced by the host–guest complex electrostatic shielding layer on Zn anode, as detected by in-situ optical microscopy. The lamellar Zn is plated which profits from the improved Zn plating behavior. Density functional theory (DFT) calculation presents the stable structure of complex. The less produced H2 content is monitored online by a mass spectrometer during Zn plating/stripping, which indicates HER can be hampered by the host–guest behavior. Thus, the ZIBs with long life and high Coulombic efficiency are achieved via introducing 18-crown-6. The proposed host–guest supramolecular interaction is expected to facilitate the furthermore development of Zn batteries.

Two‐Dimensional Cathode Materials for Aqueous Rechargeable Zinc‐Ion Batteries†

Comprehensive SummaryRechargeable aqueous zinc‐ion batteries (ZIBs) featuring low cost, superior performance, and environmental benignity have attracted dramatic attention as a promising alternative energy storage system to lithium‐ion batteries. Nevertheless, the development of ZIBs is still hindered by the limited selection of cathode materials due to the large solvation sheath and charge density of Zn2+. Two‐dimensional (2D) materials have attracted extraordinary attention owing to the unique layered structure bonded by weak van der Waals’ forces, which makes them promising host materials for Zn2+ intercalation/de‐intercalation. In this review, the synthesis and properties of 2D materials for cathodes in ZIBs are discussed. Meanwhile, various reports on 2D materials as ZIBs cathodes are summarized. Three key strategies to elicit improved Zn2+ storage abilities: defect engineering, heterostructure engineering, and interlayer engineering, are highlighted. Finally, this review ends with perspectives relating to the challenges and opportunities of 2D materials‐based ZIBs.

Scalable Spray Drying Production of Amorphous V2 O5 -EGO 2D Heterostructured Xerogels for High-Rate and High-Capacity Aqueous Zinc Ion Batteries.

Rechargeable aqueous zinc-ion batteries (ZIBs) are promising in stationary grid energy storage due to their advantages in safety and cost-effectiveness, and the search for competent cathode materials is one core task in the development of ZIBs. Herein, the authors design a 2D heterostructure combining amorphous vanadium pentoxide and electrochemically produced graphene oxide (EGO) using a fast and scalable spray drying technique. The unique 2D heterostructured xerogel is achieved by controlling the concentration of EGO in the precursor solution. Driven by the improved electrochemical kinetics, the resultant xerogel can deliver an excellent rate capability (334mAhg-1 at 5Ag-1 ) as well as a high specific capacity (462mAhg-1 at 0.2Ag-1 ) as the cathode material in ZIB. It is also shown that the coin cell constructed based on spray-dried xerogel can output steady, high energy densities over a broad power density window. This work provides a scalable and cost-effective approach for making high performance electrode materials from cheap sources through existing industrialized materials processing.

Designing Zinc Deposition Substrate with Fully Preferred Orientation to Elude the Interfacial Inhomogeneous Dendrite Growth

The development of zinc-ion batteries with high energy density remains a great challenge due to the uncontrollable dendrite growth on their zinc metal anodes. Film anodes plated on the substrate have attracted increasing attention to alleviate these dendrite issues. Herein, we first point out that both the random crystal orientation and the low metal affinity of the substrate are important factors of zinc dendrite formation. Accordingly, the (1 0 1) fully preferred tin interface layer with high zinc affinity was fabricated by chemical tin plating on (1 0 0) oriented copper. This tin decorated copper substrate can realize high reversible zinc plating/stripping behavior, and full cell using this zinc plated substrate can be operated for more than 1000 cycles with high capacity retention (85.3%) and low electrochemical impedance. The proposed strategy can be also applied to lithium metal batteries, which demonstrates that the substrate orientation regulation and metal affinity design are the promising approaches to achieve dendrite-free metal anode and overcome the challenges of highly reactive metal anodes.

Tuning electronic structure of ultrathin V6O13 nanobelts via nickel doping for aqueous zinc-ion battery cathodes

Zinc-ion batteries (ZIBs) have gained significant attention for their high theoretical capacity, safe operation and low cost. However, the sluggish kinetics of Zn2+ diffusion in cathode materials hampers the further development of ZIBs. In this study, the interlayer spacing of V6O13 crystals was tuned by doping with Ni2+ to obtain Ni-doped V6O13 (NixV6-xO13) nanobelts with high performance for cathodes in ZIBs. The effect of the amount of Ni precursors on the morphology and the electrochemical properties of the NixV6-xO13 nanobelts was also investigated. The NixV6-xO13 nanobelt cathodes exhibited a high discharge capacity of 302.6 mAh g−1 at 1 A g−1 as well as an excellent specific capacity of 96.5 mAh g−1 after 10,000 cycles at high current density of 8.0 A g−1. By combining various in-situ and ex-situ characterization technologies, the electrochemical mechansims of the NixV6-xO13 nanobelt cathode were revealed. This work offers fundamental guidelines for tuning the electrochemical activities of cathodes in ZIBs.

Nanohybrid engineering of the vertically confined marigold structure of rGO-VSe2 as an advanced cathode material for aqueous zinc-ion battery

The development of Zinc-ion batteries (ZIBs) has been in focus for quite some time compelled by poor effectiveness and lower cycle stability, primarily due to slow ion diffusion kinetics and design deformity of cathode materials. Developing innovative cathode materials with high conductivity and stability may be an alternative means of solving these issues. Here, a basic one-step hydrothermal approach is used to synthesize marigold-like reduced graphene oxide (rGO) and VSe2 nanohybrids. The highly conductive rGO wraps VSe2 to suppress the electrostatic stacking of nanosheets, and at the same time serves as a template to form a marigold-like nanohybrid structure. Moreover, the diffusion path of electrolyte ions is reduced and the strongly conductive graphene provides a 3D highway for electron transfer with improved reaction kinetics. The rGO- VSe2 nanohybrid was used as a cathode for ZIBs, which exhibited a good reversible potential of 221.5mAhg−1 at 0.5 A g−1, and has excellent conversion efficiency with good cycling stability (~91.6% retention after 150 cycles). These empowering developments provide a better way to explore high-capacity, high-performance electrode materials.

A facile coating strategy for high stability aqueous zinc ion batteries: Porous rutile nano-TiO2 coating on zinc anode

Rechargeable aqueous zinc ion batteries have attracted significant attention because of their non-toxicity, high theoretical capacity, and low cost. However, many challenges regarding zinc anodes have hindered the development of zinc ion batteries, such as the growth of zinc dendrites, passivation and hydrogen evolution. In this study, a simple strategy based on porous rutile nano-TiO2 coating was used to guide uniform deposition of zinc ions to inhibit the formation of zinc dendrite. The TiO2 coated zinc anode shows excellent electrochemical performance. Therefore, for ZnZn symmetric cell, the zinc anode protected by TiO2 coating shows reduced voltage hysteresis (50 mV at 0.4 mA cm−2). Moreover, for Zn-MnO2 full cell, the cell with TiO2 coating also shows excellent cycling performance. The discharge capacity of Zn-MnO2 full cell is only 27.69 mAh g−1 after 500 cycles, while discharge capacity of Zn@TiO2-MnO2 full cell is up to 89.14 mAh g−1. This excellent electrochemical performance may be attributed to improved wettability of TiO2 coated zinc anode, the uniform deposition of Zn2+ and reduction of Zn dendrites. Overall, this study provides a simple and beneficial strategy for future development of rechargeable aqueous zinc ion batteries.

Constructing PEDOT:PSS/Graphene sheet nanofluidic channels to achieve dendrite-free Zn anode

Despite the great progress on the development of zinc ion batteries (ZIBs) in recent years, the issue of zinc corrosion in aqueous media and the associated dendrite growth of the electrode remains a major challenge for achieving high-performance anode materials with long-term stability. Herein, we report a facile, yet, effective interfacial optimization of zinc (Zn) anode using a nanofluidic channel (NC) layer made up of Poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) decorated graphene sheets (GSs) produced by electrochemical exfoliation. The NCs effectively modulated the Zn ion distribution density, inhibited dendrite growth, and restrained other side reactions due to its tunable channel size and the surface functional groups. Moreover, the extra conductive polymer (PEDOT:PSS) on the NC layer curbed the polarization problem by enhancing the electric field on the Zn anode. As a result, PEDOT:PSS/GS@Zn anode demonstrated prolonged cycling stability for 8000 cycles with substantial improvements in specific discharge capacity due to the enhanced electron transit efficiency. In summary, our work proposes a scalable technological approach to fabricate dendrite-free Zn anodes and provides a universal inspiration to restrain dendrite formation during the ion electroplating processes.

Three-dimensional hydrated vanadium pentoxide/MXene composite for high-rate zinc-ion batteries

Aqueous zinc-ion batteries (ZIBs) have been considered to be potential energy storage devices because of their cost-effectiveness and environmental friendliness. However, most of the cathode materials reported in ZIBs exhibit poor electrochemical performances like capacity fading during cycling and inferior performance at high current densities, which significantly hinder the further development of ZIBs. Here, we reported a novel three-dimensional hydrated vanadium pentoxide (V2O5·nH2O)/MXene composite via a simple one-step hydrothermal method. Owing to the unique structure and high electrical conductivity of MXene, V2O5·nH2O/Ti3C2Tx MXene shows a remarkable electrochemical performance with a reversible capacity of 323 mAh g−1 at 0.1 A g−1 and exceptional rate capability (262 mAh g−1 at 1 A g−1 and 225 mAh g−1 at 2 A g−1) when used as the cathode for aqueous ZIBs. This work offers a new insight into fabricating novel vanadium oxide-based cathode material for aqueous ZIBs.

Nickel@Nickel Oxide Dendritic Architectures with Boosted Electrochemical Reactivity for Aqueous Nickel–Zinc Batteries

AbstractRechargeable alkaline zinc‐ion batteries (ZIBs) have gained extensive attention on account of their inexpensiveness, and high levels of safety and output voltage, but the lack of suitable cathode materials with high energy storage property and long cycle stability limits further development of ZIBs. Herein, we report an effective two‐step electrochemical approach to prepare Ni@NiO core‐shell dendritic architectures as cathode material for rechargeable alkaline ZIBs. Benefiting from the highly active NiO shell and unique core‐shell structure, this Ni@NiO electrode shows an excellent discharge capacity (0.112 mAh cm−2, at 4 mA cm−2) and a high rate capability (63.7 % capacity retention at 40 mA cm−2). Furthermore, the alkaline ZIBs with this Ni@NiO cathode also displays a high energy density of 0.193 mWh cm−2 and a remarkable power density of 65.0 mW cm−2.

Tunable Layered (Na,Mn)V8O20·nH2O Cathode Material for High-Performance Aqueous Zinc Ion Batteries.

Rechargeable aqueous zinc‐ion batteries (ZIBs) show promise for use in energy storage. However, the development of ZIBs has been plagued by the limited cathode candidates, which usually show low capacity or poor cycling performance. Here, a reversible Zn//(Na,Mn)V8O20·nH2O system is reported, the introduction of manganese (Mn) ions in NaV8O20 to form (Na,Mn)V8O20 exhibits an outstanding electrochemical performance with a capacity of 377 mA h g−1 at a current density of 0.1 A g−1. Through experimental and theoretical results, it is discovered that the outstanding performance of (Na,Mn)V8O20·nH2O is ascribed to the Mn2+/Mn3+‐induced high electrical conductivity and Na+‐induced fast migration of Zn2+. Other cathode materials derived from (Na,Mn)V8O20·nH2O by substituting Mn with Fe, Co, Ni, Ca, and K are explored to confirm the unique advantages of transition metal ions. With an increase in Mn content in NaV8O20, (Na0.33,Mn0.65)V8O20 ·nH2O can deliver a reversible capacity of 150 mA h g−1 and a capacity retention of 99% after 1000 cycles, which may open new opportunities for the development of high‐performance aqueous ZIBs.

Synergistic H+/Zn2+ dual ion insertion mechanism in high-capacity and ultra-stable hydrated VO2 cathode for aqueous Zn-ion batteries

Rechargeable aqueous zinc ion batteries (ZIB) with near-neutral electrolytes are a promising candidate for stationary energy storage owing to their high-energy-density, high-safety, low-cost and environmental-friendliness. However, the development of ZIBs is currently hindered by the lack of high-performance cathode materials and a good understanding of the true ionic storage mechanism in cathodes. Herein, using a promising ZIB cathode, hydrated VO2 (denoted as H-VO2), as a model material, we carried out a systematic experimental and theoretical work to elucidate the ionic storage mechanisms. We show strong evidence that H+ and Zn2+ are synergistically involved in the ionic storage in H-VO2. The H+-insertion/extraction, which leads to a pH swing of the electrolyte, can be viewed as an indirect Zn2+-storage through a reversible precipitation/dissolution of Zn(OH)2 on the surface of H-VO2 cathode. The first-principles DFT calculations further reveal that H+ and Zn2+ have their own favorable insertion sites and migration pathways, but H+-insertion predominates in the initial discharge stage whereas Zn2+-insertion controls in the late discharge stage. Because of the synergetic H+/Zn2+ co-insertion, H-VO2-based ZIB exhibits a high capacity and stability at both low and high rates, e.g. 410 and 200 ​mAh g-1, 88% and 70% retention rate for 200 (~1500 ​h) and 3000 cycles (~215 ​h) at 0.1 and 5.0 ​A ​g-1, respectively. The new fundamental insights gained from this study deepen the understanding of aqueous Zn-ion battery chemistry for future development of advanced ZIB cathodes.