High-performance Aqueous Zinc-ion Batteries Research Articles

Selective control of sharp-edge zinc electrodes with (002) plane for high-performance aqueous zinc-ion batteries

This study introduces a novel ZnSE electrode fabrication method, stabilizing the (002) crystal plane to reduce Zn dendrite growth, lower HER, and enhance corrosion resistance.

Transition-metal ions intercalation chemistry enabled the manganese oxides-based cathode with enhanced capacity and cycle life for high-performance aqueous zinc-ion batteries.

Aqueous zinc-ion batteries (AZIBs) employing mild aqueous electrolytes are recognized for their high safety, cost-effectiveness, and scalability, rendering them promising candidates for large-scale energy storage infrastructure. However, the practical viability of AZIBs is notably impeded by their limited capacity and cycling stability, primarily attributed to sluggish cathode kinetics during electrochemical charge-discharge processes. This study proposes a transition-metal ion intercalation chemistry approach to augment the Zn2+ (de)intercalation dynamics using copper ions as prototypes. Electrochemical assessments reveal that the incorporation of Cu2+ into the host MnO2 lattice (denoted as MnO2-Cu) not only enhances the capacity performance owing to the additional redox activity of Cu2+ but also facilitates the kinetics of Zn2+ ion transport during charge-discharge cycles. Remarkably, the resulting AZIB employing the MnO2-Cu cathode exhibits a superior capacity of 429.4 mA h g-1 (at 0.1 A g-1) and maintains 50% capacity retention after 50 cycles, surpassing both pristine MnO2 (146.8 mA h g-1) and non-transition-metal ion-intercalated MnO2 (MnO2-Na, 198.5 mA h g-1). Through comprehensive electrochemical kinetics investigations, we elucidate that intercalated Cu2+ ions serve as mediators for interlayer stabilization and redox centers within the MnO2 host, enhancing capacity and cycling performance. The successful outcomes of this study underscore the potential of transition-metal ion intercalation strategies in advancing the development of high-performance cathodes for AZIBs.

Ce ions and polyaniline co-intercalation into MOF-derived porous V2O5 nanosheets with a synergistic energy storage mechanism for high-capacity and super-stable aqueous zinc-ion batteries

Layered vanadium oxides with highly open crystal structures and high theoretical capacity are regarded as the most promising cathode materials for high-performance aqueous zinc-ion batteries (ZIBs).

A covalent organic framework as a dual-active-center cathode for a high-performance aqueous zinc-ion battery.

Organic electrode materials have shown significant potential for aqueous Zn ion batteries (AZIBs) due to their flexible structure designability and cost advantage. However, sluggish ionic diffusion, high solubility, and low capacities limit their practical application. Here, we designed a covalent organic framework (TA-PTO-COF) generated by covalently bonding tris(4-formylbiphenyl)amine (TA) and 2,7-diaminopyrene-4,5,9,10-tetraone (PTO-NH2). The highly conjugated skeleton inside enhances its electron delocalization and intermolecular interaction, leading to high electronic conductivity and limited solubility. The open channel within the TA-PTO-COF provides ionic diffusion pathways for fast reaction kinetics. In addition, the abundant active sites (C[double bond, length as m-dash]N and C[double bond, length as m-dash]O) endow the TA-PTO-COF with a large reversible capacity. As a result, the well-designed TA-PTO-COF cathode delivers exceptional capacity (255 mA h g-1 at 0.1 A g-1), excellent cycling stability, and a superior rate capacity of 186 mA h g-1 at 10 A g-1. Additionally, the co-insertion mechanism of Zn2+/H+ within the TA-PTO-COF cathode is revealed in depth by ex situ spectroscopy. This study presents an effective strategy for developing high-performance organic cathodes for advanced AZIBs.

Advanced electrolytes for high-performance aqueous zinc-ion batteries.

Aqueous zinc-ion batteries (AZIBs) have garnered significant attention in the realm of large-scale and sustainable energy storage, primarily owing to their high safety, low cost, and eco-friendliness. Aqueous electrolytes, serving as an indispensable constituent, exert a direct influence on the electrochemical performance and longevity of AZIBs. Nonetheless, conventional aqueous electrolytes often encounter formidable challenges in AZIB applications, such as the limited electrochemical stability window and the zinc dendrite growth. In response to these hurdles, a series of advanced aqueous electrolytes have been proposed, such as "water-in-salt" electrolytes, aqueous eutectic electrolytes, molecular crowding electrolytes, and hydrogel electrolytes. This comprehensive review commences by presenting an in-depth overview of the fundamental compositions, principles, and distinctive characteristics of various advanced aqueous electrolytes for AZIBs. Subsequently, we systematically scrutinizes the recent research progress achieved with these advanced aqueous electrolytes. Furthermore, we summarizes the challenges and bottlenecks associated with these advanced aqueous electrolytes, along with offering recommendations. Based on the optimization of advanced aqueous electrolytes, this review outlines future directions and potential strategies for the development of high-performance AZIBs. This review is anticipated to provide valuable insights into the development of advanced electrolyte systems for the next generation of stable and sustainable multi-valent secondary batteries.

An interactive dual energy storage mechanism boosts high-performance aqueous zinc-ion batteries.

Organic materials are promising cathodes for aqueous zinc-ion batteries (AZIBs) due to their cost-effectiveness, environmental friendliness, and tunable structures. However, the energy density of AZIBs remains limited by the inherently low capacity and output voltage of organic cathode materials. To address this challenge, we develop a Mn ion-doped polyaniline (PAM) by harnessing the joint merits of the highly reversible doping process of the conjugated backbone and the unique dissolution-deposition behavior of Mn2+ in ZnSO4 electrolyte. The incorporation of Mn2+ into the PANI backbone facilitates the stabilization of PAM at high potentials by lowering the lowest unoccupied molecular orbital (LUMO) energy level, resulting in enhanced output voltage and cycling stability. This new interactive dual energy storage mechanism, illustrated by density functional theory calculations and ex situ characterization, contributes to the improved capacity by employing a dissolution-deposition storage mechanism. The battery showcases a maximum specific capacity of 496.7 mA h g-1 at an ultra-high working voltage of 2.4 V. And the capacity is 213.2 mA h g-1 when the current density reaches 20 A g-1. This molecular design of the pre-doped PANI cathode and the insight into the groundbreaking dual energy storage mechanism offer a new alternative host for high-performance Zn-organic batteries.

Carbothermal reduction-induced oxygen vacancies in spinel cathodes for high-performance aqueous zinc-ion batteries

The defect-engineering of low-valent vanadium spinel cathode boost the charge storage performance of aqueous zinc-ion battery.

Tailoring vanadium oxide crystal orientation for high-performance aqueous zinc-ion batteries.

Due to the increasing demand for higher security and low-cost energy storage systems, the main research focus has been developing a suitable substitute for lithium-ion batteries. Aqueous zinc ion batteries (AZIBs) are considered the best alternative to lithium-ion batteries in large-scale energy storage devices. Owing to its high capacity, vanadate is a promising cathode material for AZIBs. The crystallographic orientation of cathode materials dramatically influences the rate performance and cycling life. Here, Mg0.57V5O12·2.3H2O (MgVO) with favorable (001) crystal orientation and significantly improved electrochemical performance is prepared by a simple stirring method. The crystal growth orientations of MgVO are altered by adjusting the aging time of the reactant solution. The (001)-orientated grain growth of MgVO delivers a 232.5 mA h g-1 capacity at 5 A g-1 with a 94% capacity retention rate after 1400 cycles. The zinc ion storage performance of MgVO demonstrates that the orientation-controlled method can design effective cathode materials for high-performance ZIBs.

Ion-Molecule Co-Confining Ammonium Vanadate Cathode for High-Performance Aqueous Zinc-Ion Batteries.

Vanadium-based cathode materials have attracted great attention in aqueous zinc-ion batteries (AZIBs). However, the inferior ion transport and cyclic stability due to the strong Coulomb interaction between Zn2+ and the lattice limit their further application. In this work, CO2 molecules are in situ embedded in the interlayer structure of NH4V4O10 by decomposing excess H2C2O4·2H2O in the main framework, obtaining an ion-molecule co-confining NH4V4O10 for AZIB cathode material. The introduced CO2 molecules expanded the interlayer spacing of NH4V4O10, broadened the diffusion channel of Zn2+, and stabilized the structure of NH4V4O10 as the interlayer pillars together with , which effectively improved the Zn2+ diffusion kinetics and cycle stability of the electrode. In addition, the binding between and the host framework is stabilized via hydrogen bonds with CO2 molecules. NVO-CO2-0.8 exhibited excellent specific capacity (451.1mAhg-1 at 2 Ag-1), cycle stability (214.0mAhg-1 at 10Ag-1 after 1000 cycles) and rate performance. This work provides new ideas and approaches for optimizing vanadium-based materials with high-performance AZIBs.

Rare earth metals ion intercalated hydrated vanadium oxides for high-performance aqueous zinc-ion batteries

Hydrated vanadium oxide (V2O5·nH2O) is promising cathode candidates for aqueous rechargeable Zn-ion batteries (ZIBs) owing to its high theoretical specific capacity, abundant resources and environmentally friendly. However, the higher charge density of Zn2+ lead to its structural instability, cyclic degradation and sluggish Zn2+ diffusion kinetics. Herein, rare earth metal ions intercalated into the interlayer of V2O5·nH2O materials (abbreviated as RE-VOH) are successfully synthesized to expand interlayer spacing and stabilize the layered structure via a simple sol-gel method, among, the yttrium ion intercalated V2O5·nH2O (Y–VOH) exhibits a honeycomb porous microstructure and a remarkably enlarged interlayer distance (13.6 Å), which can not only increase the contact area between the electrode material and the electrolyte but also offer rapid diffusion channel for Zn2+. Meanwhile, the problem of vanadium dissolution of cathode materials is inhibited by the electrolyte additive strategy through adding suitable vanadium oxide sol to aqueous electrolyte, furthermore, the zinc anode modification strategy in electroplating process inhibits the formation of zinc dendrites. Benefitting from the synergistic effect of modification design for the ZIBs systems of cathode, electrolyte and anode, the overall electrochemical performance of Y–VOH electrode is significantly improved, delivering a large specific capacity of 337 mAh g−1 at the current density of 500 mA g−1 and excellent rate capability of 170 mAh g−1 at 10 A g−1, along with an outstanding capacity retention of 90 % over 3000 cycles. Additionally, systematical ex situ characterizations prove the (de)intercalation reversibility of Zn2+ storage mechanism for the Y–VOH cathode. This research may provide a new way for exploiting high performance vanadium-based materials for aqueous ZIBs.

Hydrolysis of Solid Buffer Enables High-Performance Aqueous Zinc Ion Battery.

Aqueous zinc (Zn) ion batteries (AZIBs) have not yet fulfilled their talent of high safety and low cost since the anode/electrolyte interface (AEI) has long been impeded by hydrogen evolution, surface corrosion, dendritic growth, and by-product accumulation. Here, the hydrolysis of solid buffers is elaborately proposed to comprehensively and enduringly handle these issues. Take 2D layered black phosphorus (BP) as a hydrolytic subject. It is reported that the phosphoric acid generated by hydrolysis in an aqueous electrolyte produces a zinc phosphate (ZPO) rich solid electrolyte interphase (SEI) layer, which largely inhibits the dendrite growth, surface corrosion, and hydrogen evolution. Meanwhile, the hydrolytic phosphoric acid stabilizes the pH value near AEI, avoiding the accumulation of alkaline by-products. Notably, compared with the disposable ZPO engineerings of anodic SEI pre-construction and electrolyte additive, the hydrolysis strategy of BP can realize a dramatically prolonged protective effect. As a result, these multiple merits endow BP modified separator to achieve improved stripping/plating stability toward Zn anode with more than ten times lifespan enhancement in Zn||Zn symmetrical cell. More encouragingly, when coupled with a V2 O5 ·nH2 O cathode with ultra-high loadings (34.1 and 28.7mg cm-2 ), the cumulative capacities are remarkably promoted for both coin and pouch cells.

Elaborate artificial construction of porous biomass carbon interfacial layer on the surface of zinc anode toward high performance aqueous zinc-ion batteries

Aqueous zinc ion batteries (AZIBs) have emerged as one of the most promising candidates for large-scale energy storage and other fields owing to their low cost, high safety and environmental friendliness. However, the dendritic issue and side reactions induced by the zinc anode-electrolyte interface have always been the major obstacles hindering their development. Herein, porous biomass carbon (BCK) is artificially designed via a simple method to act as an ex-situ surface coating on the zinc anode to resolve the above problems. The interface coating effectively reduces the interface area of direct contact between the zinc anode and electrolyte, thereby suppressing dendrite growth and parasitic reactions. Especially, BCK has a rich pore structure and zincophilic oxygen-containing functional groups, providing sufficient active sites, which can adsorb Zn2+ and preferentially nucleate on the surface of BCK, thus eliminating the tip effect and making the surface of the zinc sheet uniform and flat. In addition, the large specific surface area of BCK can promote the transport and nucleation kinetics of Zn2+, guide the formation of a uniform surface electric field on the zinc anode, enhance the deposition rate of Zn2+ at the anode-electrolyte interface, which helps to guide the uniform nucleation, growth, and deposition of Zn2+. Benefiting from these advantages, the assembled symmetric cells have lower voltage hysteresis and longer cycling performance than bare Zn cells, and the full cell delivers a capacity of 166.5 mAh g−1 and the capacity retention rate of 61.5 % after 1000 cycles at 1 A g−1, which is significantly higher than that of bare Zn assembled full cell.

Manganese vanadium oxide composite as a cathode for high-performance aqueous zinc-ion batteries

The development of clean renewable energy and energy storage devices is of great significance under the present energy crisis and environmental pollution background. Aqueous zinc-ion battery (ZIB) has become one of the most promising energy storage devices due to its high capacity, safety and low cost. However, the application of ZIB cathode is usually limited by low capacity and poor stability. Herein, we propose a novel heterostructure MnO/MnV2O4 composite material composed of MOF derivatives and spinel with dual active components as cathode for ZIBs. Benefited from substantial framework of MOF derivatives and the synergistic effect of heterostructures, MnO/MnV2O4 exhibits excellent rate performance (342 mAh/g at 0.1 A/g, 261 mAh/g at 15 A/g) and cycling performance (198.9 mAh/g at 10 A/g after 2000 cycles) in 3 mol/L Zn(CF3SO3)2 electrolytes. This work extends the range of developing high-performance cathodes for ZIBs under high current density and is expected to enlighten the optimization of commercial energy storage devices.

Synergistically regulating the separator pore structure and surface property toward dendrite-free and high-performance aqueous zinc-ion batteries

As an emerging electrochemical device, aqueous zinc-ion batteries (ZIBs) present promising potential in safe and large-scale energy storage. However, the large pores of commercial glass fiber (GF) separators result in uneven Zn2+ ion flux, leading to severe dendrite growth issues of Zn metal anodes. Herein, we integrated a multifunctional layer on the GF separator that can synergistically regulate the pore feature and surface property of commercial GF separators. Such modification layer, composed of nanocellulose and SiO2 nanoparticles, exhibited uniform nanoporous structure and abundant negatively charged polar functional groups. These features allow regulating the distribution of Zn2+ ions at the separator-anode interface, facilitating stable and uniform Zn nucleation and growth. Moreover, the electrostatic interaction between the negatively charged functional groups and Zn2+ ions enhanced the Zn2+ ion transport kinetics, preventing the Zn dendrites formation and adverse reactions. Consequently, the modified electrolyte-filled GF separator showed an increased Zn2+ ion transference number of 0.65. The symmetric Zn//Zn batteries utilizing such a separator achieved an impressive cycling life of 500 h at a high current density/capacity of 10 mA cm−2/4 mAh cm−2, nearly nine times longer than the battery using the unmodified GF separator (<55 h). The superior electrochemical performance was verified in both Zn//AC and Zn//LiMn2O4 full battery evaluations. This work presents a novel synergistic modification strategy for developing advanced separators for aqueous ZIBs.

Pre-intercalation of Ammonium Ions in Layered δ-MnO2 Nanosheets for High-Performance Aqueous Zinc-Ion Batteries.

Layered manganese dioxide is a promising cathode candidate for aqueous Zn-ion batteries. However, the narrow interlayer spacing, inferior intrinsic electronic conductivity and poor structural stability still limit its practical application. Herein, we report a two-step strategy to incorporate ammonium ions into manganese dioxide (named as AMO) nanosheets as a cathode for boosted Zn ion storage. K+ -intercalated δ-MnO2 nanosheets (KMO) grown on carbon cloth are chosen as the self-involved precursor. Of note, ammonium ions could replace K+ ions via a facile hydrothermal reaction to enlarge the lattice space and form hydrogen-bond networks. Compared with KMO, the structural stability and the ion transfer kinetics of the layered AMO are enhanced. As expected, the obtained AMO cathode exhibits remarkable electrochemical properties in terms of high reversible capacity, decent rate performance and superior cycling stability over 10000 cycles.

Synergistically Stabilizing Zinc Anodes by Molybdenum Dioxide Coating and Tween 80 Electrolyte Additive for High-Performance Aqueous Zinc-Ion Batteries.

Recently, aqueous zinc-ion batteries (ZIBs) have become increasingly attractive as grid-scale energy storage solutions due to their safety, low cost, and environmental friendliness. However, severe dendrite growth, self-corrosion, hydrogen evolution, and irreversible side reactions occurring at Zn anodes often cause poor cyclability of ZIBs. This work develops a synergistic strategy to stabilize the Zn anode by introducing a molybdenum dioxide coating layer on Zn (MoO2@Zn) and Tween 80 as an electrolyte additive. Due to the redox capability and high electrical conductivity of MoO2, the coating layer can not only homogenize the surface electric field but also accommodate the Zn2+ concentration field in the vicinity of the Zn anode, thereby regulating Zn2+ ion distribution and inhibiting side reactions. MoO2 coating can also significantly enhance surface hydrophilicity to improve the wetting of electrolyte on the Zn electrode. Meanwhile, Tween 80, a surfactant additive, acts as a corrosion inhibitor, preventing Zn corrosion and regulating Zn2+ ion migration. Their combination can synergistically work to reduce the desolvation energy of hydrated Zn ions and stabilize the Zn anodes. Therefore, the symmetric cells of MoO2@Zn∥MoO2@Zn with optimal 1 mM Tween 80 additive in 1 M ZnSO4 achieve exceptional cyclability over 6000 h at 1 mA cm-2 and stability (>700 h) even at a high current density (5 mA cm-2). When coupling with the VO2 cathode, the full cell of MoO2@Zn∥VO2 shows a higher capacity retention (82.4%) compared to Zn∥VO2 (57.3%) after 1000 cycles at 5 A g-1. This study suggests a synergistic strategy of combining surface modification and electrolyte engineering to design high-performance ZIBs.

Trimetallic-Organic Framework-Derived Ni-Doped MnO/PC as cathodes for High-Performance aqueous zinc-ion batteries

Manganese-based materials are frequently employed as the cathodes of aqueous zinc ion batteries (AZIBs) due to the merits of low cost, eco-friendliness and high operating voltage. However, their inherent low conductivity and poor structural stability often lead to an insufficient rate capacity and therefore limit their application in AZIBs. Herein, we use the trimetallic-organic framework precursor to synthesize a Ni nanoparticle doped MnO composite uniformly anchored on porous carbon (Ni-MnO/PC) by a simple hydrothermal and annealing method. Electrochemical evaluation indicates that the Ni-MnO/PC composite electrode exhibits excellent zinc storage performance, mainly due to the synergistic effect of Ni nanoparticles doping and porous carbon, which enhances adsorption energy of zinc ions and also increases structure stability. The Zn || Ni-MnO/PC batteries represent not only an outstanding discharge capacity of 347.4 mAh/g at 100 mA g−1, but also an ultra-long cycle stability. Even in 3000 mA g−1, the Ni-MnO/PC electrode holds a high-capacity retention of 91.1 % after 6000 cycles. The various ex-situ tests reveal that co-intercalation of H+ and Zn2+ in Ni-MnO/PC electrode is the major mechanism for storing zinc. Finally, quasi solid-battery assembled with Ni-MnO/PC cathode can also withstand stress at different bending states. This work will promote the application of metal nanoparticles doping strategies for AZIBs and provide views for the development of durable flexible energy storage devices.

Tailoring the solvation shells of dual metal ions for high-performance aqueous zinc ion batteries

For a long time, the issue of dendrites in neutral/mild electrolyte-based aqueous zinc-ion batteries (AZIBs) has been a matter of concern. The dendrites resulting from this problem lead to short-circuit faults and significantly reduce the cycle life, which is quite troublesome. Here, we induce uniform Zn deposition by utilizing the enhanced electrostatic shielding effect of a hybrid additive of Na2SO4 and EDTA. The limited tip-blocking effect of Na+ is due to the higher exchange reaction rate constant (kex) of water molecules in the solvation shell. The coordination of EDTA can provide a more stable solvation shell for Na+, ensuring a stronger blocking effect on Zn deposition at the tip. This enhanced electrostatic shielding effect effectively suppresses the growth of Zn dendrites. In addition, EDTA also enters the solvation shell of Zn2+ and displaces some coordinated water molecules, allowing for more reversible Zn plating/stripping without significant side reactions occurring at the Zn anode.

Tuning [VO6] Octahedron of Ammonium Vanadates via F Incorporation for High-Performance Aqueous Zinc Ion Batteries.

The electrochemical properties of vanadium-based materials as cathode materials for aqueous zinc ion batteries are still restricted by low conductivity, sluggish reaction kinetics, and poor structural stability. Herein, the [VO6] octahedron, as the basic unit of vanadium-oxide layer of ammonium vanadates (NH4V4O10, denoted as NVO), is incorporated by F atoms to regulate the coordinated environment of vanadium. Density functional theory (DFT) calculations and experimental results show that both physicochemical and electrochemical properties of NVO are improved by F-doping. The enhanced electronic conductivity accelerates the electron transfer and the expanded interlayer spacing expedites the diffusion kinetics of zinc ions. As a result, the F-doped NVO (F-NVO) electrode shows a high discharge capacity (465 mAh g-1 at 0.1 A g-1), good rate capability (260 mAh g-1 at 5 A g-1), and long-term cycling stability (88% capacity retention over 2000 cycles at 4 A g-1). The reaction kinetics and energy storage mechanism of F-NVO are further validated by in situ and ex situ characterizations.

Constructing oxygen deficiency-rich V2O3@PEDOT cathode for high-performance aqueous zinc-ion batteries

Constructing oxygen deficiency-rich V2O3@PEDOT cathode for high-performance aqueous zinc-ion batteries