High-performance Zinc-ion Batteries Research Articles

Fast and efficient in-situ construction of low crystalline PEDOT-intercalated V2O5 nanosheets for high-performance zinc-ion battery

Layered vanadium oxides have recently emerged as ideal cathode materials for aqueous zinc-ion batteries (ZIBs) due to their high theoretical capacity and low cost. However, their inherent shortages of narrow interlayer distance and poor electric conductivity cause sluggish reaction kinetics and low structure stability, leading to battery performance deterioration. Herein, we developed a novel strategy to simultaneously realize the intercalation of conductive polymer into V2O5 polyhedrons and exfoliation of the V2O5 into ultrathin nanosheets. The strategy is realized by in-situ polymerization of 3,4-ethylene-dioxythiophene (EDOT) monomers in the interlayer of the V2O5 polyhedrons that were derived from the annealing of vanadium-based metal–organic frameworks (MIL-100(V)) in air. The MIL-100-derived V2O5 polyhedrons assembled into porous microspheres (PVO) with abundant porosity and small particle size, which facilitates the penetration of EDOT molecules into the interior of the PVO during in-situ intercalation and polymerization processes, ultimately leading to the V2O5 polyhedrons exfoliating into ultrathin nanosheets. The uniform poly(3,4-ethylene-dioxythiophene) (PEDOT) layer and abundant oxygen vacancies in PVO@PEDOT nanosheets can accelerate the diffusion of electrons and zinc ions, which are evidenced by dynamic analysis, ex-situ characterizations, and density functional theory (DFT) calculations, revealing the synergetic effect of PEDOT and oxygen vacancies. Therefore, the PVO@PEDOT cathode exhibits high specific capacity (403.7 mAh g-1 at 0.2 A g-1), superior rate capability (312.8 mAh g-1 at 10 A g-1), and long-term stability (92.8% of the initial capacity remained after 3000 cycles), which is superior to the majority of ion intercalation improved V2O5.

Recent Advances in Graphene-Based Materials for Zinc-Ion Batteries.

Zinc-ion batteries (ZIBs) are a promising alternative for large-scale energy storage due to their advantages of environmental protection, low cost, and intrinsic safety. However, the utilization of their full potential is still hindered by the sluggish electrode reaction kinetics, poor structural stability, severe Zn dendrite growth, and narrow electrochemical stability window of the whole battery. Graphene-based materials with excellent physicochemical properties hold great promise for addressing the above challenges foe ZIBs. In this review, the energy storage mechanisms and challenges faced by ZIBs are first discussed. Key issues and recent progress in design strategies for graphene-based materials in optimizing the electrochemical performance of ZIBs (anode, cathode, electrolyte, separator and current collector) are then discussed. Finally, some potential challenges and future research directions of graphene-based materials in high-performance ZIBs are proposed for practical applications.

In situ prepared amorphous VOH-Polyaniline@Carbon cloth as cathodes for high performance zinc ion batteries

Vanadium-based compounds are promising cathode materials for aqueous zinc ion batteries (AZIBs) while suffering from notorious poor conductivity and structural instability, leading to severe performance degradation.Herein, we grew polyaniline intercalated VOH nanoarrays on conductive carbon cloth (VOH-PANI@CC) via one-step electrochemical deposition route. Owing to the advantageous nature of amorphous structure of VOH, good conductivity of PANI and the strong synergistic effect between two components, the VOH-PANI@CC free-standing electrodes showed abundant ion diffusion paths, plentiful ion storage sites and high conductivity. The electrode thus achieves an initial charging capacity up to 500 mAh g−1 at 0.1 A g−1 and can still maintain 117.4 mAh g−1 for 500 cycles at 0.5 A g−1. Furthermore, ex-situ XRD and XPS studies revealed the zinc storage process of VOH-PANI@CC and underlying mechanism of the enhanced performance. This work provides a universality design strategy for designing advanced high-performance V-based cathodes for AZIBs.

Constructing ultra-stable and high-performance zinc-ion batteries through Mn doped vanadium oxide nanobelt cathode

In this study, analysis of density functional theory calculations shows that the Mn2+ doping between VO6 layers functions as a “structural pillar,” and Mn2+ in the layer can boost the conductivity of VO2·0.2H2O and hold high specific capacity.

An integrated Janus hydrogel with different hydrophilicities and gradient pore structures for high-performance zinc-ion batteries

A pioneering achievement is made in developing integrated Janus hydrogel electrolytes featuring gradient pores in cross-section and varying hydrophilicities on surfaces. This novel hydrogel enables Zn-ion batteries to exhibit excellent performance.

A B-doped layered VOPO4·2H2O cathode for high-performance zinc-ion batteries with an H+/Zn2+ co-insertion mechanism

B-doping engineering provides a strategy to increase the content of V4+ in VOPO4·2H2O and improve its H+/Zn2+ co-intercalation capacitance as a cathode for zinc-ion batteries.

Te hexagonal nanotubes with fast 1-dimensional Zn ion diffusion for high-performance zinc-ion battery cathodes

The need for advanced next-generation secondary batteries have been urgently demanded for improved, sustainable, and eco-friendly energy storage systems. Aqueous rechargeable zinc ion batteries (ARZIBs) have garnered substantial attention as a substitute for lithium-ion batteries owing to their exceptional stability, environmentally friendly features, and cost-effectiveness. In this study, it is found that tellurium hexagonal nanotubes with a unique crystal growth orientation of [001] are of promising cathode materials for enhancing the performance of zinc ion batteries owing to their outstanding reaction kinetic properties. Additionally, the hollow interior of the nanotubes effectively mitigates the volume changes of tellurium during the charging and discharging processes. These research findings are expected to solidify the potential of tellurium hexagonal nanotubes as reliable cathode materials, significantly contributing to the commercialization of zinc ion battery technology in the future.

A Fluorinated Solid-state-electrolyte Interface Layer Guiding Fast Zinc-ion Oriented Deposition in Aqueous Zinc-ion Batteries.

Aqueous zinc ion batteries are gaining popularity due to their high energy density and environmental friendliness. However, random deposition of zinc ions on the anode and sluggish migration of zinc ions on the interface would lead to the growth of zinc dendrites and poor cycling performance. To address these challenges, we developed a fluorinated solid-state-electrolyte interface layer composed of Ca5 (PO4 )3 F/Zn3 (PO4 )2 via an in situ ion exchange strategy to guide zinc-ion oriented deposition and fast zinc ion migration on the anode during cycling. The introduction of Ca5 (PO4 )3 F (FAP) can increase the nucleation sites of zinc ions and guide the oriented deposition of zinc ions along the (002) crystal plane, while the in situ formation of Zn3 (PO4 )2 during cycling can accelerate the migration of zinc ions. Benefited from our design, the assembled Zn//V2 O5 ⋅ H2 O batteries based on FAP-protected Zn anode (FAP-Zn) achieve a higher capacity retention of 84 % (220 mAh g-1 ) than that of bare-Zn based batteries, which have a capacity retention of 23 % (97 mAh g-1 ) at 3.0 A g-1 after 800 cycles. This work provides a new solution for the rational design and development of the solid-state electrolyte interface layer to achieve high-performance zinc-ion batteries.

Hybrid Superlattice-Triggered Selective Proton Grotthuss Intercalation in δ-MnO2 for High-Performance Zinc-Ion Battery.

A great deal of attention has been paid on layered manganese dioxide (δ-MnO2 ) as promising cathode candidate for aqueous zinc-ion battery (ZIB) due to the excellent theoretical capacity, high working voltage and Zn2+ /H+ co-intercalation mechanism. However, caused by the insertion of Zn2+ , the strong coulomb interaction and sluggish diffusion kinetics have resulted in significant structure deformation, insufficient cycle stability and limited rate capability. And it is still far from satisfactory to accurately modulate H+ intercalation for superior electrochemical kinetics. Herein, the terrace-shape δ-MnO2 hybrid superlattice by polyvinylpyrrolidone (PVP) pre-intercalation (PVP-MnO2 ) was proposed with the state-of-the-art ZIBs performance. Local atomic structure characterization and theoretical calculations have been pioneering in confirming the hybrid superlattice-triggered synergy of electron entropy stimulation and selective H+ Grotthuss intercalation. Accordingly, PVP-MnO2 hybrid superlattice exhibits prominent specific capacity (317.2 mAh g-1 at 0.125 A g-1 ), significant rate performance (106.1 mAh g-1 at 12.5 A g-1 ), and remarkable cycle stability at high rate (≈100 % capacity retention after 20,000 cycles at 10 A g-1 ). Therefore, rational design of interlayer configuration paves the pathways to the development of MnO2 superlattice for advanced Zn-MnO2 batteries.

Regulating interfacial ion migration with pillar effect in layer-by-layer inter-embedded MoS2/Ti3C2 for high-performance zinc-ion batteries

Two-dimensional (2D) layered materials have promising prospects for Zn-storage due to their flexible and adjustable interlayer architecture. The strong electrostatic interaction and high diffusion energy barrier, however, lead to slow diffusion kinetics of Zn-ions between the 2D interfaces, limiting its widespread application. Herein, Ti3C2 MXene is introduced into the MoS2 interlayer by the “pillar effect” to assemble a layer-by-layer inter-embedded structure (L-MoS2/Ti3C2), which provides sufficient diffusion channels for Zn-ions. DFT computations and GITT confirm that the L-MoS2/Ti3C2 exhibits superior Zn-ions migration kinetics. Therefore, L-MoS2/Ti3C2 shows excellent long-term cycling stability (75.6% capacity retention after 7000 cycles at 15 A g-1) and glorious high-rate capability (107 mAh g-1 at 20 A g-1). In addition, the practical application of this material is demonstrated by evaluating the performance of L-MoS2/Ti3C2 in flexible quasi-solid-state aqueous zinc ion batteries under various extreme bending conditions, which exhibits good stability under 180° during the 4000 cycles with a capacity retention of 80.5% at 2.0 A g-1.

Decorating carbon quantum dots onto VO2 nanorods to boost electron and ion transport kinetics for high–performance zinc–ion batteries

Rechargeable aqueous Zn–ion batteries (RAZIBs) are regarded as attractive alternatives for large–scale energy storage. V–based cathode materials have gained great attention due to the merits of rich valence states, controllable morphology, diverse crystal structures, and controllable chemical compositions. However, the development of high–performance V–based cathode is still impeded by sluggish electron/ion transport kinetics. To address this issue, this work reveals that the electrochemical performance of the VO2 cathode can be significantly boosted by decorating carbon quantum dots (CQDs) onto the VO2 nanorods via a facile hydrothermal reaction. The VO2/CQDs sample is characterized to have strong interface interaction with the presence of CO bond. Compared to the CQD–free counterpart, the obtained VO2/CQDs sample exhibits higher specific surface area (18.7 vs 4.4 m2 g−1), better electrolyte wettability (53° vs 114° for contact angle), reduced charge–transfer resistance (1.8 vs 19.9 Ω), and facilitated ion diffusion coefficient (1.66 × 10−10 vs 4.56 × 10−11 cm2 s−1). Benefiting from these features, a high attainable capacity of 427 mAh g−1 at 0.2 A g−1 can be reached for VO2/CQDs, corresponding to the specific energy of 333 Wh kg−1 (based on the mass of VO2/CQDs). When the current density increases to 8 A g−1, VO2/CQDs can still deliver 309 mAh g−1, showing great promise for high–rate capability. Moreover, the VO2/CQDs cathode renders stable cycle performance with retaining 229 mAh g−1 after 2000 cycles. By contrast, the unmodified sample demonstrates moderate electrochemical performance (373 and 186 mAh g−1 at 0.2 and 8 A g−1, respectively). The results highlight the importance of the CQDs decoration strategy, which can effectively boost electron/ion transport in oxide–based cathodes for high–performance RAZIBs.

Operando crystal-amorphous transformation cathode for enhanced zinc storage

Aqueous zinc-ion batteries have obtained broad attention due to their high safety, eco-friendliness, and low cost. However, they are still in the developing stage considering the limited candidate of high-performance cathode materials. Furthermore, the intrinsic storage zinc mechanism is also needed to uncover. Here, we propose an operando crystal-amorphous transformation of tunnel-type VOOH and the obtained amorphous V2O5 serves as a high-performance zinc-ion battery cathode. In-situ X-ray diffraction corroborates the unique operando crystal-amorphous transformation of VOOH during the initial charging process. X-ray photoelectron spectroscopy and transmission electron microscopy further demonstrate the element valence evolution and the lattice structure change, respectively. The operando electrochemical crystal-amorphous transformation allows the obtained amorphous V2O5 to achieve the high capacity of ∼ 350.7 mAh g−1, rate performance (151.2 mAh g−1 at 6.4 A g−1), energy and power densities (137 Wh kg−1 at 6831 W kg−1), unveiling a promising approach of cathode materials via operando crystal-amorphous transformation to achieve the enhanced zinc storage.

Inhibition of Zinc Dendrite Growth by WC-Cellulose Separators for High-Performance Zinc-Ion Batteries

Inhibition of Zinc Dendrite Growth by WC-Cellulose Separators for High-Performance Zinc-Ion Batteries

Electrochemical Performance and Mechanism of Bimetallic Organic Framework for Advanced Aqueous Zn Ion Batteries.

Widespread interest has been generated by aqueous zinc batteries (AZIBs), which have excellent theoretical capacities (820 mA h g-1), a low redox potential (-0.76 V vs SHE of Zn metal), and high security. Suitable cathodes for constructing high performance AZIBs are of great signification. Metal-organic frameworks (MOFs) with adjustable structure via metals and organic units show great potential in AZIBs. In this work, ZnMn-Squaric acid (ZnMn-SQ) was synthesized using squaric acid through coprecipitation and served as the cathode for AZIBs. The ZnMn-SQ electrode demonstrated a high capacity of 489.1 mA h g-1 at 0.2 A g-1. Meanwhile, ZnMn-SQ can obtain 80.7 mA h g-1 after 1300 cycles, showing an outstanding long cycle life. More importantly, ex situ characterizations of XRD, XPS, and FT-IR revealed that ZnMn-SQ undergoes a structural transformation from the initial ZnMn-SQ framework to manganese oxide accompanied by Zn-SQ and then reduced to MnOOH, ZnMn2O4, and Zn4SO4(OH)6·5H2O (ZHS) in subsequent cycles. In addition, a modified zinc anode using cubic porous Zn-SQ-3d was used to construct ZnMn-SQ // Zn-SQ-3d@Zn(Zn-SQ-3d-coated Zn) high performance AZIBs, the capacity of which reaches 171.3 mA h g-1 at 1 A g-1 after 660 cycles. This work provided chances for constructing high-performance zinc ion batteries using MOF compounds.

High-performance zinc-ion batteries cathode material ZnMn2O4 modified by polypyrrole and reduced graphene oxide

Spinel zinc manganate has great prospects due to its advantages of a high voltage platform, non-toxicity, low cost, and abundant resources as a cathode material for ZIBs. However, its inherent poor conductivity and unsatisfactory long-term cyclic stability seriously restrict its commercial applications. Herein, the highly conductive polymer polypyrrole-coated ZnMn2O4 nanoparticles anchored on reduced graphene oxide with strong interfacial interaction (ZMO/rGO-PPy composite) were successfully synthesized. Compared with the pure ZnMn2O4 nanoparticles, ZMO/rGO-PPy composite displays increased conductivity of 3.89 × 103 S m−1 and higher discharge capacity of 269.6 mAh g−1 at 0.2 A g−1, as well as better rate capability and long-term cycling stability (after 900 cycles at a high current density of 1 A g−1 the specific capacity remains at 147.4 mAh g−1, with a capacity retention rate of 88.7%). The excellent performance is attributed to the shortened ion diffusion pathway, improved electrical conductivity and good structure stability. Furthermore, electrochemical analyses reveal that favorable reaction kinetics towards efficient zinc ion storage is achieved in the composite. These results suggest ZMO/rGO-PPy composites could be a competitive cathode material for ZIBs.

Self-assembled VS2 microflowers buffering volume change during charging and discharging towards high-performance zinc ion batteries

VS2 has attracted increasing attention as a cathode material for aqueous zinc ion batteries because of its proper large layer spacing, weak interlayer interactions, multiple valence states of V, and excellent electrical conductivity, but its large volume change during charging and discharging leads to poor cycling stability. Herein, we report a one-step hydrothermal synthesis of VS2 microflowers with proper lamellar spacing, which provides a stable framework for the insertion/deinsertion of zinc ions and enhances the cycling stability, delivering an initial charge capacity of 128.3 mAh g−1 at 3 A g−1 and maintains a charge capacity of 100.1 mAh g−1 after 900 cycles. In addition, the optimized VS2 cathode shows specific capacities of 215.7 and 150.5 mAh g−1 at the current densities of 0.1 and 2 A g−1, respectively, demonstrating that the microflower structure with a high specific surface area and a short diffusion distance also significantly enhances the rate performance.

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.