Aqueous Zinc-ion Batteries Research Articles

Effective CuO/Cu7S4 nanospheres heterostructures for advanced “rocking-chair” zinc-ion battery

Rechargeable aqueous zinc-ion batteries (ZIBs) have attracted considerable attention for energy storage owing to their environmental friendliness and high safety. However, the adverse side reactions and unsatisfactory cycle life brought by Zn-metal anodes limit their large applications. Herein, CuO/Cu7S4 (CSO) heterostructured hollow nanospheres is proposed as an attractive conversion-type Zn-metal-free anode for “rocking-chair” ZIBs. The CSO/graphite self-supporting electrode delivers a high capacity of 271 mAh/g at current density of 0.1 A/g and a superior cyclic stability of 1200 cycles. Based on the excellent electrochemical performance of CSO/graphite electrode, we have constructed a self-powered pressure sensor integrated system using the “rocking-chair” zinc ion battery as the power source, demonstrating significant practicality. This work provides a high-performance conversion type anode material for aqueous multivalent metal ion batteries.

Experimental Validation of Density Functional Theory Predictions on Structural Water Impact in Vanadium Oxide Cathodes for Zinc-Ion Batteries.

This study combines experimental methods with density flooding theory (DFT) calculations to investigate the enhancement of the electrochemical performance of vanadium oxide cathodes for aqueous zinc ion batteries (AZIBs) through strategic water content management. DFT predictions indicated that a moderate presence of structural water optimizes electrical conductivity and facilitates zinc ion diffusion. These theoretical insights are empirically validated by synthesizing AlVO-1.6 H2O using a hydrothermal method, which exhibited superior electrochemical properties. This material demonstrated an impressive initial capacity of 316 mAh g-1 at 0.2 A g-1, with robust capacity retention after extended cycling. Remarkably, even at an elevated current density of 10 A g-1, it sustains a capacity of 161.6 mAh g-1, while maintaining a capacity retention of 97.6% over 2000 cycles. The results confirm that adjusting the structural water content in vanadium oxides significantly boosts their electrochemical capabilities, aligning experimental outcomes with computational forecasts and showcasing a novel approach for developing high-performance cathodes in energy storage technologies.

Sodium-Ion/Crystal Water Cointercalated δ-MnO2 with Improved Performance for Aqueous Zinc-Ion Batteries

Sodium-Ion/Crystal Water Cointercalated δ-MnO₂ with Improved Performance for Aqueous Zinc-Ion Batteries

The Introduction of a BaTiO3 Polarized Coating as an Interface Modification Strategy for Zinc-Ion Batteries: A Theoretical Study.

Aqueous zinc-ion batteries (AZIBs) have become a promising and cost-effective alternative to lithium-ion batteries due to their low cost, high energy, and high safety. However, dendrite growth, hydrogen evolution reactions (HERs), and corrosion significantly restrict the performance and scalability of AZIBs. We propose the introduction of a BaTiO3 (BTO) piezoelectric polarized coating as an interface modification strategy for ZIBs. The low surface energy of the BTO (110) crystal plane ensures its thermodynamic preference during crystal growth in experimental processes and exhibits very low reactivity toward oxidation and corrosion. Calculations of interlayer coupling mechanisms reveal a stable junction between BTO (110) and Zn (002), ensuring system stability. Furthermore, the BTO (110) coating also effectively inhibits HERs. Diffusion kinetics studies of Zn ions demonstrate that BTO effectively suppresses the dendrite growth of Zn due to its piezoelectric effect, ensuring uniform zinc deposition. Our work proposes the introduction of a piezoelectric material coating into AZIBs for interface modification, which provides an important theoretical perspective for the mechanism of inhibiting dendrite growth and side reactions in AZIBs.

NASICON-structured Na3Ti0.8V1.2(PO4)3/C as a high-performance cathode for aqueous sodium-zinc hybrid batteries

Phosphate cathode materials have a stable and open backbone structure and are expected to be one of the ideal cathode materials for aqueous zinc ion batteries (ZIBs). In this work, a new compound Na3Ti0.8V1.2(PO4)3 is synthesised by sol-gel method and used as a cathode material for ZIBs. The battery delivered a reversible and stable capacity of 120.1 mA h g−1 over 100 cycles at 0.5 C. Impressively, the battery demonstrated exceptional cycling performance and outstanding rate performance, maintaining a capacity retention of 95.6 % after 1000 cycles at 5.0 C. It is demonstrated that the dissolution of V in water is effectively inhibited by partial Ti ion occupancy at the V site, which accelerates the ion diffusion rate and greatly improves the electrochemical performance. In this work, the charging and discharging process of NASICON structured Na3Ti0.8V1.2(PO4)3 cathode was investigated to show the mechanism of Na+ and Zn2+ co-doping. This discovery offers a novel phosphate cathode material for ZIBs, as well as a fresh approach to enhancing the specific capacity and stability of phosphate cathode materials.

Eco-friendly multi-function electrolyte additive enabling dendrite-free Zn anodes for rechargeable aqueous zinc batteries

Aqueous zinc ion batteries (AZIBs) are increasingly developing on account of their safety, high energy density, affordability and scalability. Nevertheless, the zinc anode encounters notable obstacles, including disruptive side reactions, unregulated dendrite growth and persistent hydrogen evolution. These challenges present barriers to the widespread adoption of AZIBs technology in practical applications. This study incorporates aspartame (ASPT) into the aqueous electrolyte to establish a novel interface between the anode and electrolyte, improve steric effects, and adjust the solvation structure of Zn2+. Theoretical computations elucidate how the ASPT additive interacts with both the electrolyte and Zinc anode. Experimental findings additionally validate the significant role of ASPT in concurrently managing the chemistry between the electrolyte environment and Zinc interface. Accordingly, Zn//Zn symmetric cells exhibit an enduring operational lifespan exceeding 3600 hours under a current of 1 mA cm−2 and 1 mA cm−2. Moreover, Zn//Ti asymmetric cells demonstrate prolonged durability with highly efficient Zn deposition and dissolution processes sustained over more than 300 cycles. Finally, the Zn//MnO2 full cells, upon assembly, demonstrate consistent cycling stability and retain high capacity throughout their operational cycle.

High-entropy strategy to suppress volumetric strain and enhance diffusion rate of Na3V2(PO4)2F3 cathode for durable and high-areal-capacity zinc-ion battery pouch cells

Aqueous zinc-ion batteries are pivotal contributors to the global energy transformation. Cathode materials with NASICON-type structures are promising candidates for zinc-ion batteries but are hindered by their low electrical conductivity, sluggish ionic diffusion, and structural instability. This work introduces a high-entropy, carbon-coated NASICON-type Na3V2(PO4)2F3 (HE-NVPF@C) cathode by incorporating five metal elements (Al, Zn, Mn, Cr, and Nb) mainly into the V sites of the VO4F2 octahedral structure. Systematic experimental and simulation studies of the Zn2+ storage mechanism in high-entropy NASICON-type cathode are presented for the first time. The high-entropy doping strategy contributes to significantly enhanced cycling stability by suppressing Jahn-Teller distortion, reducing lattice change during Zn2+ extraction and insertion, and decreasing the Zn2+ migration energy barrier. As a result, the HE-NVPF@C cathode demonstrates exceptional cycling stability over 6000 cycles at 20 C with a capacity loss of a mere 0.0031 % per cycle and a high areal capacity retention of 2.17 mAh cm−2. In addition, the pouch cell provides a long cycling lifespan with 90.8 % capacity retention at 5 C after 200 cycles. This feasible high-entropy approach broadens the perspective for developing practical zinc-ion batteries with a long cycle lifespan and high areal capacity.

Fully Printed and Sweat-Activated Micro-Batteries with Lattice-Match Zn/MoS2 Anode for Long-Duration Wearables.

Aqueous zinc-ion batteries with superior operational safety have great promise to serve as wearable energy storage devices. However, the poor cycling stability and low output voltage limited their practical applications. Here, fully printable Zn/MoS2-MnO2 micro-batteries are developed and demonstrated significantly enhanced cycling stability with sweat activation. 2D MoS2 is utilized to enable lattice-matching with Zn powders to realize printed Zn anodes with desirable stability and promote electron/ion transfer. Interestingly, the mild acid epidermal sweat also contributed to eliminating the MnO2 cathode by-products and compensating for the hydrogel electrolytes' water loss. The Zn/MoS2-MnO2 micro-batteries achieve a high specific capacity of 318.9µAhcm-2 at the current density of 0.16mAcm-2, and an energy density of 424.6µWhcm-2, with remarkable cycle stability of ≈90% after 250 cycles. In-battery electrochromic display of capacity level and feasible electronics charging are demonstrated. The as-printed micro-batteries with innovative sweat activation would inspire the advances of sustainable power supply for wearables.

Zincophilic Tellurium Interface Layer Enables Fast Kinetics for Ultralow Overpotential and Highly Reversible Zinc Anode

AbstractCorrosion, hydrogen evolution, and dendrite formation seriously affect the Zn anode, significantly limiting the practical application of aqueous zinc ion batteries. Herein, the Zn anode surface is innovatively reconstructed by decorating a zincophilic tellurium layer (Te@Zn) to enhance the Zn deposition kinetics. Theoretical calculations and experimental characterizations demonstrate that the zincophilic Te provides an abundance of anchoring sites for Zn nucleation and homogenizes the interface electric field to suppress dendrite growth. The Te@Zn anode exhibits an ultralow overpotential of 14.8 mV at 1.0 mA cm−2 and 1.0 mAh cm−2 with high Coulombic efficiency, and maintains ultra‐stable operation for over 3600 h at 0.2 mA cm−2 and 0.2 mAh cm−2. The Te@Zn||KVOH full cells and soft–pack batteries also deliver a brilliant rate capability and long cycling stability. The interfacial manipulation strategy using the Te layer on Zn anode surface paves the way for large‐scale energy storage applications.

Unraveling the Anionic Redox Chemistry in Aqueous Zinc‐MnO2 Batteries

AbstractActivating anionic redox reaction (ARR) has attracted a great interest in Li/Na‐ion batteries owing to the fascinating extra‐capacity at high operating voltages. However, ARR has rarely been reported in aqueous zinc‐ion batteries (AZIBs) and its possibility in the popular MnO2‐based cathodes has not been explored. Herein, the novel manganese deficient MnO2 micro‐nano spheres with interlayer “Ca2+‐pillars” (CaMnO‐140) are prepared via a low‐temperature (140 °C) hydrothermal method, where the Mn vacancies can trigger ARR by creating non‐bonding O 2p states, the pre‐intercalated Ca2+ can reinforce the layered structure and suppress the lattice oxygen release by forming Ca−O configurations. The tailored CaMnO‐140 cathode demonstrates an unprecedentedly high rate capability (485.4 mAh g−1 at 0.1 A g−1 with 154.5 mAh g−1 at 10 A g−1) and a marvelous long‐term cycling durability (90.6 % capacity retention over 5000 cycles) in AZIBs. The reversible oxygen redox chemistry accompanied by CF3SO3− (from the electrolyte) uptake/release, and the manganese redox accompanied by H+/Zn2+ co‐insertion/extraction, are elucidated by advanced synchrotron characterizations and theoretical computations. Finally, pouch‐type CaMnO‐140//Zn batteries manifest bright application prospects with high energy, long life, wide‐temperature adaptability, and high operating safety. This study provides new perspectives for developing high‐energy cathodes for AZIBs by initiating anionic redox chemistry.

Unraveling the Anionic Redox Chemistry in Aqueous Zinc-MnO2 Batteries.

Activating anionic redox reaction (ARR) has attracted a great interest in Li/Na-ion batteries owing to the fascinating extra-capacity at high operating voltages. However, ARR has rarely been reported in aqueous zinc-ion batteries (AZIBs) and its possibility in the popular MnO2-based cathodes has not been explored. Herein, the novel manganese deficient MnO2 micro-nano spheres with interlayer "Ca2+-pillars" (CaMnO-140) are prepared via a low-temperature (140 °C) hydrothermal method, where the Mn vacancies can trigger ARR by creating non-bonding O 2p states, the pre-intercalated Ca2+ can reinforce the layered structure and suppress the lattice oxygen release by forming Ca-O configurations. The tailored CaMnO-140 cathode demonstrates an unprecedentedly high rate capability (485.4 mAh g-1 at 0.1 A g-1 with 154.5 mAh g-1 at 10 A g-1) and a marvelous long-term cycling durability (90.6 % capacity retention over 5000 cycles) in AZIBs. The reversible oxygen redox chemistry accompanied by CF3SO3 - (from the electrolyte) uptake/release, and the manganese redox accompanied by H+/Zn2+ co-insertion/extraction, are elucidated by advanced synchrotron characterizations and theoretical computations. Finally, pouch-type CaMnO-140//Zn batteries manifest bright application prospects with high energy, long life, wide-temperature adaptability, and high operating safety. This study provides new perspectives for developing high-energy cathodes for AZIBs by initiating anionic redox chemistry.

Multifunctional Self-Assembled Bio-Interfacial Layers for High-Performance Zinc Metal Anodes.

Rechargeable aqueous zinc-ion (Zn-ion) batteries are widely regarded as important candidates for next-generation energy storage systems for low-cost renewable energy storage. However, the development of Zn-ion batteries is currently facing significant challenges due to uncontrollable Zn dendrite growth and severe parasitic reactions on Zn metal anodes. Herein, we report an effective strategy to improve the performance of aqueous Zn-ion batteries by leveraging the self-assembly of bovine serum albumin (BSA) into a bilayer configuration on Zn metal anodes. BSA's hydrophilic and hydrophobic fragments form unique and intelligent ion channels, which regulate the migration of Zn ions and facilitate their desolvation process, significantly diminishing parasitic reactions on Zn anodes and leading to a uniform Zn deposition along the Zn (002) plane. Notably, the Zn||Zn symmetric cell with BSA as the electrolyte additive demonstrated a stable cycling performance for up to 2400 hours at a high current density of 10 mA cm-2. This work demonstrates the pivotal role of self-assembled protein bilayer structures in improving the durability of Zn anodes in aqueous Zn-ion batteries.

Unravelling the performance of lead-free perovskite cathodes for rechargeable aqueous zinc-ion batteries

The quest for efficient and sustainable energy storage solutions has led to the emergence of zinc-ion batteries (ZIBs) as a promising candidate, offering numerous advantages in terms of cost-effectiveness, safety, and performance. The key to commercialising ZIBs lies in developing cathode materials that offer high specific capacity and prolonged cycle performance. The present study demonstrates the capability of environmentally friendly, lead-free inorganic perovskites for high-rate rechargeable aqueous zinc-ion batteries with enhanced stability and excellent rate performance. The battery exhibits a high specific capacity of 220 mAh/g at a current density of 1000 mA/g and a quite stable capacity of 50 mAh/g and a good cycling stability of 20000 cycles at a very high rate of 20 A/g. The caesium bismuth iodide perovskite emerges as a promising candidate for cathode material in Zn-ion batteries, exhibiting high specific capacity and superior rate cyclability. Furthermore, incorporation of Ag in CsBi3I10 is found to enhance the specific capacity and exhibits superior cycling stability. This study marks a significant advancement in the utilisation of perovskite materials as new cathodes for high-rate ZIBs.

Dual Redox Reactions of Silver Hexacyanoferrate Prussian Blue Analogue Enable Superior Electrochemical Performance for Zinc-ion Storage.

Prussian blue analogues (PBAs) have been employed as host materials of aqueous zinc-ion batteries (ZIBs), however, they suffer from low capacity and poor cycling stability due to limited electron transfer and the presence of interstitial water in PBAs. Herein, a vacancy and water-free silver hexacyanoferrate K0.95Ag3.05Fe(CN)6 (AgHCF-3) was synthesized by adjusting the ratio of K and Ag in the framework. It offers nearly four electrons involving two sequential redox reactions, namely, Fe3+/Fe2+ and Ag+/Ag0, to deliver a large capacity of 179.6 mAh g-1 at 20 mA g-1 with Coulomb efficiency of ~100%. The Zn//AgHCF-3 cell delivers an estimated energy density of 200 Wh kg-1, surpassing reported PBAs-based ZIBs. The formation of Ag0 in the cycling process merits favorable rate performance of AgHCF-3 (156.4 mAh g-1 at 200 mA g-1 with 80.3% capacity retention after 100 cycles). This investigation paves new pathways for high-capacity PBA cathodes.

High-Performance All-Inorganic Aqueous Zinc-Ion Battery for Wide-Temperature Operation (−70 to 60 °C)

High-Performance All-Inorganic Aqueous Zinc-Ion Battery for Wide-Temperature Operation (−70 to 60 °C)

Nitrogen and Oxygen Co‐Doped Graphene Quantum Dots as a Trace Amphipathic Additive for Dendrite‐Free Zn Anodes

AbstractThe practical implementation of aqueous zinc‐ion batteries (AZIBs) has encountered obstacles stemming from the limited reversibility of the zinc anode, primarily due to dendrite proliferation and water‐induced reactions occurring. In this investigation, a novel bifunctional interphase is proposed by integrating nitrogen and oxygen group graphene quantum dot (N‐O‐GQD) additives into the electrolyte. Experimental results and theoretical calculations demonstrate that the amphipathic N‐O‐GQD additive enhances the stability of the electrode by forming a protection layer on Zn surface. The zincophilic and hydrophobic nitrogen function groups stick to the surface of Zn electrodes to form a hydrophobic layer that shields water molecules from the electrode and promotes the uniform deposition of Zn. The hydrophilic hydroxyl function groups are exposed to the electrolyte to improve the compatibility at the electrode/electrolyte interface. As a result, the amphipathic N‐O‐GQD additive enables a robust cycling performance at high depth of discharge (DOD). Significantly, cells incorporating N‐O‐GQDs demonstrate a remarkable Coulombic efficiency of 99.7% over 900 cycles and sustain dendrite‐free cycling for 564 h (DOD = 51%). Particularly noteworthy is the performance of the modified Zn||ZnVO full cell with robust cycling behavior, enduring 4 000 cycles at 10 A g−1.

Layered MnO2@PDA as cathode material toward high-performance aqueous zinc-ion batteries

Aqueous zinc-ion batteries (AZIBs) can benefit from a deep understanding of the electrochemical reaction mechanism of cathode materials, which can assist in resolving issues such as cathode dissolution and electrostatic interactions. We reported a straightforward two-step synthesis of polydopamine coated MnO2 (MnO2@PDA) and revealed the energy storage mechanisms in AZIBs. The layered structure of MnO2 creates a generous passage for the insertion of H+/Zn2+ ions. Simultaneously, the plethora of functional groups within PDA exerts a robust desolvation effect, bolstering the transfer rate of H+/Zn2+. This effect significantly enhances the overall efficiency and performance of cathode. The AZIBs, incorporating MnO2@PDA cathode material, consequently exhibit a satisfactory cycling capacity (412 mAh g−1 at 0.1 A g−1) and a superb specific energy (561.6 Wh kg−1 at 136.34 W kg−1). This work provides a new path for design strategies and catalytic mechanisms of MnO2@PDA cathode.

Dynamically Favorable Ion Channels Enabled by a Hybrid Ionic-Electronic Conducting Film toward Highly Reversible Zinc Metal Anodes.

Aqueous zinc ion batteries show great promise for future applications due to their high safety and ecofriendliness. However, nonuniform dendrite growth and parasitic reactions on the Zn anode have severely impeded their use. Herein, a hybrid ionic-electronic conducting ink composed of graphene-like carbon nitride (g-C3N4) and conductive polymers (CP) of poly(3,4ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) is introduced to Zn anode using a scalable spray-coating strategy. Notably, the g-C3N4 promotes a screening effect, disrupting the coulombic interaction between the PEDOT+ segments and PSS- chains within CP, thereby reducing interfacial resistance and homogenizing the surface electric field distribution of the Zn anode. Furthermore, the abundant N-containing species and ─SO3 - groups in g-C3N4/CP exhibit strong zincophilicity, which accelerates the diffusion of Zn2+ and disrupts the solvation structure of Zn(H2O)6 2+, thus improving the Zn2+ transfer capability. Consequently, the g-C3N4/CP can powerfully stabilize the Zn2+ flux and thus enable a high coulombic efficiency of 99.47% for 1500 cycles and smooth Zn plating/stripping behaviors more than 3000h at a typical current density of 1mA cm-2. These findings shed new light on the Zn electrodeposition process under the mediation of g-C3N4/CP and offer sustainability considerations in designing more stable Zn-metal anodes with enhanced reversibility.

Ab initio investigation of ZnV2O4, ZnV2S4, and ZnV2Se4 as cathode materials for aqueous zinc-ion batteries

Zinc-ion batteries (ZIBs) employing aqueous electrolytes have emerged as one of the most promising alternatives to lithium-ion batteries (LIBs). Nonetheless, the development of ZIBs is hindered by the scarcity of cathode materials with suitable electrochemical properties. In this work, we investigate the unique properties of zinc vanadate oxide (ZnV2O4, ZVO) and zinc vanadate sulfide (ZnV2S4, ZVS) compounds as cathode materials, focusing on their crystal structures, electrochemical performance, spectroscopic features and potential applications in ZIBs. Additionally, we investigate a new cathode material, zinc vanadate selenide (ZnV2Se4, ZVSe), constructed by replacing sulfur with selenium in the ZVS cubic structure. Our findings reveal that these compounds exhibit distinct electronic and electrochemical properties, although they have similar magnetic properties due to the fact that vanadium has the same oxidation state in all three compounds. On average, ZVS stands out as the most promising candidate for ZIBs cathodes, followed by ZVO. ZVSe, shows lower electrochemical performance and also has the obvious drawback of being more costly than the sulfur- and oxygen-based compounds. Our theoretical results align closely with available experimental data, both for electrochemical properties as well as x-ray and photoelectron spectroscopy, where a comparison can be made.

Zinc-tin binary alloy interphase for zinc metal batteries

Aqueous zinc ion batteries are rapidly developing as the most propitious energy storage system due to their high security, high specific capacity and low cost, etc. However, zinc anodes suffered from dendrite growth and hydrogen evolution reactions during cycling, so it is of utmost importance to upgrade zinc anode properties. In this study, the homogeneous layer of ZnSn alloy interphase was formed by introducing metallic tin to the anode surface using an ion sputtering technique. ZnSn alloy can reduce the hydrogen evolution over-potential of anode and the corrosion current, inhibiting the occurrence of hydrogen evolution and corrosion reaction. Moreover, the ZnSn alloy anode can provide uniform nucleation sites and uniformize the electric field on the anode surface, promote the uniform deposition of Zn2+, thus inhibiting the formation of zinc dendrites. Notably, compared to the Zn foil//Zn foil cell (400 h), the ZnSn alloy symmetric cell showed excellent cycling performance by cycling for 1000 h at 0.5 mA cm−2. Furthermore, even at current density of 1 A/g, the capacity retention of the ZnSn alloy//MnO2 full cell was up to 89.5 % compared to only 32.3 % for Zn foil//MnO2 cell. The preparation of this ZnSn alloy anode may provide new ideas for future alloying strategies.