High-performance Zinc-ion Batteries Research Articles

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.

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.

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.

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.