Rechargeable Aqueous Zinc-ion Batteries Research Articles

Ferroelectric-Enhanced cathode kinetics toward High-Performance aqueous Zinc-Ion batteries

Rechargeable aqueous zinc ion batteries (AZIBs) offer promising potential for large-scale energy storage systems due to their high affordability and safety. However, their practical applications are hindered by the undesired rate capability and cycling stability of the used cathode, attributed to sluggish ions kinetics during charge–discharge process. Herein, we propose an electric field balancing strategy to regulate the electrolyte ions behavior by constructing a ferroelectric interface on the cathode surface using a prototypical of MnO2-based cathode. An appropriate thickness coating of ferroelectric materials coating (i.e., β-PVDF) on the MnO2 surface is theoretically and experimentally demonstrated to enhance the ion kinetics due to the optimized electrical distribution during electrochemical operations. Further comprehensive electrochemical mechanism studies reveal that the ferroelectric interface on the MnO2@β-PVDF not only promotes the diffusion of Zn2+ but also reduces the electrochemical overpotential (17.6 mV), resulting in improved electrochemical reversibility and capacity performance. The resultant MnO2@β-PVDF cathode exhibits the highest capacity of 277.6 mAh g−1 (at 0.1 A g−1) and capacity retention of 68.6% after 120 cycles, surpassing both the pristine MnO2 and non-ferroelectric materials coated MnO2 electrodes. This success presents a new approach to enhance the overall electrochemical performance of the cathodes for the practical application of AZIBs.

Laminated Zinc-Copper Electrodes as Reversible and Dendrite-Free Anodes for Aqueous Rechargeable Zinc-Ion Batteries

Laminated Zinc-Copper Electrodes as Reversible and Dendrite-Free Anodes for Aqueous Rechargeable Zinc-Ion Batteries

Hydrogen peroxide promotes zinc deposition nucleation and boosts the reversibility of aqueous rechargeable zinc-ion batteries

Aqueous zinc-ion batteries are a promising option for rechargeable energy storage devices. However, their performance is limited by the growth of zinc dendrites that can cause short circuits. Our research shows that adding a certain percentage of hydrogen peroxide solution to the electrolyte can effectively inhibit the irregular and non-planar growth of zinc dendrite crystals. This additive alters the deposition pattern of zinc and reduces surface roughness. Our experimental results indicate that the electrolyte with H2O2 can increase the cycle life by about 13 times compared to the electrolyte without the additive, extending it to 1057 h. The mechanism analysis reveals that H2O2 replaces H2O in forming hydrated zinc ions and facilitates zinc deposition during charging. Additionally, H2O2 significantly lowers the over-potential for zinc dendrite nucleation and suppresses the tip effect, leading to a uniform zinc morphology. This simple and eco-friendly electrolyte additive provides a strategy to regulate the deposition behavior of zinc.

Spherical PDA@MnO2 cathode for rechargeable aqueous zinc ion batteries

The PDA@MnO2 with unique structure was prepared by reacting KMnO4 with spherical PDA, and used as the cathode material of aqueous zinc ion batteries. Electrochemical test results show that, the spherical PDA@MnO2 had an initial discharge capacity of 378.4 mAh g−1 at a current density of 0.2 A g−1, indicating the superior performance compared to that of irregular PDA@MnO2. The spherical structure is beneficial to improve the electrochemical performance of the diffusion control process and achieve the purpose of improving the utilization rate and mass specific capacity of irregular PDA@MnO2. This excellent performance and novel structure demonstrate that spherical PDA@MnO2 can find a wide range of applications in energy storage.

Dendrite-Free Zinc Deposition Induced by an Artificial Layer of Strontium Titanate for Stable Zinc Metal Anode

Rechargeable aqueous zinc ion batteries, featuring as high specific capacity, low cost and high safety, are considered one of the most promising alternatives to lithium-ion batteries for the next-generation energy storage system. Nevertheless, the undesired dendrite formation and serious side reaction of Zn metal anode significantly hinder the usage of Zn-based metal batteries. Here, we propose a nanosized SrTiO3 film as a highly self-adapting protective coating to facilitate fast Zn2+ kinetics and guarantee even ion flux, leading to endow homogeneous Zn deposition under the SrTiO3 layer. Consequently, the symmetric batteries equipped with SrTiO3-coated Zn electrodes obtain a long-term cycling lifespan for 1000h with a fixed capacity of 1 mA h cm−2 without the formation of zinc dendrites. Furthermore, the Zn@SrTiO3||MnO2 full battery displays excellent cycling stability and rate performance. This study emphasizes the important role of SrTiO3 layer in designing the interfacial stability during zinc redox process for stable aqueous Zn metal batteries.

MnOx@porous silicon as cathode material for aqueous rechargeable zinc-ion battery

MnOx@porous silicon as cathode material for aqueous rechargeable zinc-ion battery

Na3V2O2(PO4)2F nanoparticles@reduced graphene oxide: a high-voltage polyanionic cathode with enhanced reaction kinetics for aqueous zinc-ion batteries

Na3V2O2(PO4)2F is characterized by a high theoretical specific capacity, high-voltage plateaus, large ion diffusion channels, and stable three-dimensional structure, which is a promising cathode candidate for rechargeable aqueous zinc-ion batteries (AZIBs). Nevertheless, the low electronic conductivity hinders its cycling and rate performance. In this work, a facile microwave-assisted solvothermal approach with postheat treatment has successfully produced Na3V2O2(PO4)2F nanoparticles with the dimension of 20–50 nm wrapped by reduced graphene oxide (rGO). The high pseudocapacitive contribution, high diffusion coefficient, low electrochemical impedance, favorable electrode wettability, and stable structure can be obtained by optimizing the chemical components of electrolyte and the content of rGO, facilitating the Zn2+ storage performance. Hence, Na3V2O2(PO4)2F@rGO delivers excellent electrochemical properties such as a high capacity of 127.0 mAh g−1 at 0.5C, a stable capacity of 63.9 mAh g−1 at 30C after 5000 cycles, and a high average voltage plateau of 1.50 V in hybrid aqueous electrolyte (2 M zinc trifluoromethane sulfonate (Zn(OTf)2) and 4 M lithium trifluoromethane sulfonate (LiOTf)). Furthermore, exceptional cycling performance in the soft-pack batteries with the size of 3 × 3.5 cm2 includes a reversible capacity of 84.1 mAh g−1 at 10C after 1000 cycles. In situ X-ray diffraction, ex situ X-ray photoelectron spectroscopy, transmission electron microscopy, and scanning electron microscopy reveal reversible Zn2+ insertion/extraction process.

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.

Chelate-Capped Nano-AgZn3 Dual Interphase Remodeling the Local Environment for Reversible Dendrite-Free Zinc Anode.

Rechargeable aqueous zinc-ion batteries (AZIBs) are among the most promising candidates for next-generation energy-storage devices. However, the large voltage polarisation and infamous dendrite growth hinder the practical application of AZIBs owing to their complex interfacial electrochemical environment. In this study, a hydrophobic zinc chelate-capped nano-silver (HZC-Ag) dual interphase is fabricated on the zinc anode surface using an emulsion-replacement strategy. The multifunctional HZC-Ag layer remodels the local electrochemical environment by facilitating the pre-enrichment and de-solvation of zinc ions and inducing homogeneous zinc nucleation, thus resulting in reversible dendrite-free zinc anodes. The zinc deposition mechanism on the HZC-Ag interphase is elucidated by density functional theory (DFT) calculations, dual-field simulations, and in situ synchrotron X-ray radiation imaging. The HZC-Ag@Zn anode exhibited superior dendrite-free zinc stripping/plating performance and an excellent lifespan of >2000h with ultra-low polarisation of ≈17mV at 0.5mA cm-2 . Full cells coupled with a MnO2 cathode showed significant self-discharge inhibition, excellent rate performance, and improved cycling stability for >1000 cycles. Therefore, this multifunctional dual interphase may contribute to the design and development of dendrite-free anodes for high-performance aqueous metal-based batteries.

Interfacial Reconstruction for Regulating Zn2+ Deposition toward Ultrastable Zn Metal Anodes.

Rechargeable aqueous zinc-ion batteries (AZIBs) are attracting much attention as high-density energy storage systems owing to their fascinating features with low cost, high safety, and simple manufacturing process. However, the commercialization of Zn anodes is hindered by uncontrollable dendrite growth and water-induced side reactions. Herein, a spontaneous reconstruction of a honeycomb-structural hopeite layer (ZPO) on a Zn metal anode (Zn@ZPO) is rationally developed as a functional protection interface by the liquid-phase deposition strategy. The formed ZPO layer not only promotes ion/charge transport and restrains Zn corrosion but also modulates the preferred deposition orientation of the Zn(002) nanosheet for the dendrite-free Zn anode. Accordingly, the Zn@ZPO symmetric cell exhibits satisfactory cycle lifespans of 1500 h at 1 mA·cm-2/1 mAh·cm-2 and 1400 h at 5 mA m-2/1 mAh·cm-2. When assembled with the (NH4)2V10O25·8H2O (NVO) cathode, the Zn@ZPO||NVO full cell delivers an ultrastable cycling lifespan for 25 000 cycles with a discharge capacity retention of 86.6% at 5 A·g-1. Therefore, this work will pave a novel avenue for constructing dendrite-free AZIBs.

Graphene oxide-assisted fabrication of mesoporous oxygen-deficient VO2 nanobelts for enhanced Zn2+ storage

Rechargeable aqueous zinc-ion batteries (ZIBs) are regarded as promising devices for large-scale stationary energy storage. However, developing ideal cathode materials confronts great challenges. Herein, a novel graphene oxide (GO)-assisted strategy is proposed to synthesis mesoporous VO2/G nanobelts with abundant oxygen defects for high-performance Zn2+ storage. The oxygen vacancies and mesopores facilitate Zn2+ insertion/extraction process. After an in-situ electrochemical activation at around 1.5 V, the monoclinic VO2 transforms to layered V2O5·nH2O, delivering an extremely high reversible capacity of 731 mAh/g (0.1 A/g). In addition, superior high-rate and cycling performances are also achieved.

An efficient electrolyte additive of 1,3,6-hexanetricarbonitrile for high performance aqueous zinc-ion batteries

The growth of Zn dendrites and parasitic side reactions between electrode and electrolyte are major obstacles to the development of rechargeable aqueous zinc-ion batteries. To address these critical issues, the use of nitrile organic compounds as electrolyte additives holds great promise. Herein, for the first time, we prepared a small volume concentration (x) of 1,3,6-Hexanetricarbonitrile (HTCN-x) as additives into zinc trifluoromethanesulphonate (Zn(OTF)2) electrolyte and studied their electrochemical properties in Zn||ZnxV2O5·nH2O (Zn||ZVO) cells. It was found that the strong interaction between H2O and HTCN could significantly reduce the population of solvated H2O outside the solvation sheath, leading to reduced side reactions in the aqueous Zn(OTF)2 electrolyte. Moreover, the HTCN additive also facilitates the formation of strong and stable solid electrolyte interphase (SEI) film on the surface of the Zn anode, which effectively prevents the growth of Zn dendrites and the anode corrosion caused by the electrolyte. As a result, the HTCN-x (x = 0.3) electrolyte enabled the symmetrical Zn||Zn cell to cycle over 950 h at a current of 1 mA cm−2 with a limited capacity of 1 mAh cm−2. When the HTCN-0.3 electrolyte was used in Zn||ZVO cell, the cell delivered a high initial capacity of 355.6 mAh g−1 at 0.1 A g−1 and maintained a high capacity of 330.0 mAh g−1 at 1 A g−1 after 465 cycles.

High-Performance Layered CaV4O9-MXene Composite Cathodes for Aqueous Zinc Ion Batteries.

Due to their reliability, affordability and high safety, rechargeable aqueous zinc ion batteries (ZIBs) have garnered a lot of attention. Nevertheless, undesirable long-term cycle performance and the inadequate energy density of cathode materials impede the development of ZIBs. Herein, we report a layered CaV4O9-MXene (Ti3C2Tx) composite assembled using CaV4O9 nanosheets on Ti3C2Tx and investigate its electrochemical performance as a new cathode for ZIBs, where CaV4O9 nanosheets attached on the surface of MXene and interlamination create a layered 2D structure, efficiently improving the electrical conductivity of CaV4O9 and avoiding the stacking of MXene nanosheets. The structure also enables fast ion and electron transport. Further discussion is conducted on the effects of adding MXene in various amounts on the morphology and electrochemical properties. The composite shows an improved reversible capacity of 274.3 mA h g-1 at 0.1 A g-1, superior rate capabilities at 7 A g-1, and a high specific capacity of 107.6 mA h g-1 can be delivered after 2000 cycles at a current density of 1 A g-1. The improvement of the electrochemical performance is due to its unique layered structure, high electrical conductivity, and pseudo capacitance behavior.

Stable structure and fast ion diffusion: N-doped VO2 3D porous nanoflowers for applications in ultrafast rechargeable aqueous zinc-ion batteries

Aqueous rechargeable zinc-ion batteries (ARZIBs) are promising candidates for fast-charging energy-storage systems. The issues of stronger interactions between Zn2+ and the cathode for ultrafast ARZIBs can be partially addressed by enhancing mass transfer and ion diffusion of the cathode. Herein, via thermal oxidation for the first time, N-doped VO2 porous nanoflowers with short ion diffusion paths and improved electrical conductivity were synthesized as ARZIBs cathode materials. The introduction of nitrogen derived from the vanadium-based-zeolite imidazolyl framework (V-ZIF) contributes to enhanced electrical conductivity and faster ion diffusion, while the thermal oxidation of the VS2 precursor assists the final product in exhibiting a more stable three-dimensional nanoflower structure. In particular, the N-doped VO2 cathode shows excellent cycle stability and superior rate capability with the delivered capacities of 165.02 mAh g−1 and 85 mAh g−1, at 10 A g−1 and 30 A g−1, and the capacity retention of 91.4% after 2200 cycles and 99% after 9000 cycles, respectively. Remarkably, the battery takes less than 10 s to be fully charged at 30 A g−1. Hence, this work provides a new avenue for designing unique nanostructured vanadium oxides and developing electrode materials suitable for ultrafast charging.

Synthesis of Zn Intercalated Zn–V@Mo–V Nanorods-based Cathodes for Prolonged Cyclic Stability of Rechargeable Aqueous Zinc-Ion Batteries

Synthesis of Zn Intercalated Zn–V@Mo–V Nanorods-based Cathodes for Prolonged Cyclic Stability of Rechargeable Aqueous Zinc-Ion Batteries

Enhanced electrochemical performance of ammonium vanadate (NH4V4O10) cathode for rechargeable aqueous zinc-ion batteries by altering pH regulators

Ammonium vanadate (NH4V4O10: NVO) as cathode for rechargeable aqueous zinc-ion batteries (AZIBs) have drawn extensive concern due to its high specific capacity and long cycle life. The controllable synthesis of high-performance NH4V4O10 is greatly desirable for the development of AZIBs but still remains a significant challenge. In this work, sulfuric acid, hydrochloric acid, and nitric acid were used as pH regulators to prepare NVO via a simple one-step hydrothermal route. The resulting NVO product (NVO-1) based on sulfuric acid pH regulator has the optimal overall performance for its favorable structure stability originated from the high crystallinity and wonderful 3D cross-linked nanowire morphology, contributing to fast electron transfer in the (de)intercalation process of Zn2+. Consequently, NVO-1 electrode exhibits excellent rate capability and cyclic stability, delivering high reversible capacities of 418.9 and 257.1 mAh g−1 at current densities of 0.1 and 2 A g−1, respectively, and demonstrating a discharge capacity of 105.7 mAh g−1 as well as superior long-term durability with an ultra-high capacity retention of 119.7 % at a large current density of 5 A g−1 after 2000 cycles. Investigation on the electrochemical kinetics reveals that surface capacitive behavior plays a significant role in the highly reversible Zn2+ storage in NVO electrode.

An effective cellulose triacetate interlayer to construct a dendrite-free zinc anode for advanced aqueous zinc-ion batteries

For Zn anodes of aqueous rechargeable zinc-ion batteries, the poor electrochemical performance caused by undesirable zinc dendritic formation and side reactions limit their practical application. Herein, a Zn2+ redistributor is created to reduce dendrites growth by inserting a cellulose triacetate (CTA) film as an interlayer between the zinc anode and the separator. The zinc dendritic formation and side reactions can be suppressed by the CTA interlayer. Consequently, the Zn anode covered by CTA interlayer exhibits highly reversible plating/stripping behavior with lifetime exceeding 2500 h and 600 h at current densities of 1 and 5 mA cm−2, respectively. In particular, the electrochemical performance of the full cells is investigated by using VO2 as the cathode and the CTA as interlayer. The Zn + CTA||VO2 full cells exhibit superior performance including high reversible capacity (490.2 mAh g−1 at 0.2 A g−1), excellent cycle performance (60.2% and 71.5% capacity retention after 5000 cycles at 5 A g−1 and 10 A g−1) and superior rate performance. This work demonstrates that designing a CTA interlayer is considered a cost-effective strategy to light up the practical application of aqueous zinc-ion batteries.

Towards the commercialization of rechargeable aqueous zinc ion batteries: The challenge of the zinc electrodeposition at the anode

The low efficiency of the electrodeposition of metallic zinc from mild-acidic electrolytes in realistic operating conditions currently represents the main challenge hindering the commercialization of aqueous Zn-ion batteries (ZIBs). These devices offer good environmental compatibility, low production costs and high powder densities, thus are considered as a viable energy storage solution for stationary applications. The electrodeposition of metallic zinc is generally affected by dendrites, spontaneous evolution of gaseous hydrogen, and precipitation of insulating passivation products on the electrode surface. The recent scientific literature has provided many strategies addressing the zinc electrodeposition through the optimization of the electrode, of the aqueous electrolyte or of the electrode-electrolyte interface. However, industrially relevant requirements such as realistic values of anode usage, current densities and capacity limits, must be implemented in the future research studies.

Hierarchical Flower-Like VS2 Nanosheets Cathode for High-Performance Aqueous Zn-ion Batteries

Aqueous rechargeable zinc-ion batteries (ZIBs) are an attractive alternative to lithium-ion batteries because of their superior safety and inexpensive price. However, the main challenge faced by ZIBs is the search for high-capacity materials that can hold large-diameter Zn ions. Herein, hierarchical flower-like VS2 nanosheets are synthesized as high-performance anode materials for ZIBs. The special hierarchical flower-like structure and morphology afford a large contact area and short Zn2+ ion diffusion distance. Therefore, VS2 nanosheets displays a reversible specific capacity (218.3 mAh g−1 at 100 mA g−1) and stable cyclic stability (87.7% capacity retention). VS2 nanosheets have a superior electrochemical performance, enabling a novel design approach for other ZIBs cathode materials.

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.