Rechargeable Zn-ion Batteries Research Articles

RETRACTED: Production of eco-friendly cathode materials from cellulose skeleton induced manganese dioxide to produce zinc ion battery: Physicochemical, morphological, and electrochemical study

Energy security is a universal issue since modern civilization cannot be imagined for a single moment without energy. Though lean fossil fuels are fighting against the current energy demand principally, these are linked to adverse environmental effects. Various energy storage technologies can resolve this issue in a sustainable eco-friendly manner. Rechargeable Zn-ion batteries (ZIBs) are emerging as potential candidates to meet the growing commercial demand with several advantages. As a part of this, the cellulose skeleton-induced manganese dioxide-based electroactive cathode materials have been prepared by an innovative route and characterized using UV–vis-NIR, FTIR, FESEM, EDS, and XRD analysis. Results suggested that the newly produced eco-friendly cathode materials have possessed outstanding physicochemical, morphological, and structural properties. While the finished product namely the coin cell of ZIBs has shown a good CV profile along with minimal charge transfer resistance in PEIS. Noteworthy that the newly prepared cathode materials have also been shown a significant capacity of 29 mAhg-1 at a 5 mA constant current charge-discharge rate. Thus, the method could be beneficially used in energy storage devices for its eco-friendly nature though some drawbacks have been noticed. The cyclic stabilities were somewhat low which can be increased in further studies.

Additive Manufacturing of Grid Reservoir-Integrated Anodes for Dendrite-Free, Safe, and Ultra-Low Voltage Zinc-Ion Batteries.

This work reports a novel 3D printed grid reservoir-integrated mesoporous carbon coordinatedsilicon oxycarbide hybrid composite (3DP-MPC-SiOC) to establish the zincophile interphase for controlling the dendrite formation. The customized 3D printed grid patterned structure inhibits Zn dendrite growth and achieves long-term stability with reduced voltage polarization due to homogeneous electric field distribution. The hybrid composite consisting of SiOC interpenetrated within carbon constructs a high zinc nucleation interphase, hence promoting uniform Zn2+ deposition and enhancing ionic diffusion with dendrite-free growth and a reduced nucleation energy barrier. As a result, the 3DP-MPC-SiOC@Zn symmetrical cell affords a highly reversible Zn plating/stripping and dendrite-free structure over 198h with an ultra-low voltage polarization. These inspiring performances endow the 3DP anode with a 3DP-VO cathode as a full battery, which shows a retention capacity of 78.8mAhg-1 (Coulombic efficiency: 94.04%) at 0.1Ag-1 and a large energy density of 41Whkg-1 at a power density of 1.2Wkg-1 (based on the total mass of electrode) after 120 cycles. This newly developed 3D printing of hybrid composite as an electrode is straightforward and scalable and provides a novel concept for realizing dendrite-free and stable rechargeable Zn-ion batteries.

Recycling Process of Spent Alkaline and Zn-C Batteries for the Re-Utilization in Rechargeable Zn-Ion Battery

The Zn, Mn and C extraction processes from spent primary batteries and the synthesis of recycled Zn film, MnO2 and MnO2/C for Zn-ion battery application were developed in the project. The Zn, Mn and C extraction process involved the acid leaching of Zn and Mn ions from the spent alkaline and Zn-C battery electrodes in the lab-scale was initially investigated using various leaching conditions. The acid leaching using 0.5-2 M HCl and H2SO4 at ambient temperature providing Zn extraction efficiencies in a range of 72.3-95.3%. By introducing an inexpensive reducing agent namely sodium sulfide (Na2S), sodium metabisulfite (Na2S2O5) or hydrogen peroxide (H2O2) in 2M H2SO4, the Mn extraction efficiency for Mn was increased from 21.9% (with no reducing agent) up to 48.4%, 82.8% and 98.9%, respectively. The upscale leaching study was subsequently performed in a 100-L pilot scale reactor demonstrated the Zn and Mn extraction efficiencies of 71% and 65%, respectively. Using the leaching solutions from the upscale hydrometallurgical route, Zn-film fabrication via electrodeposition process, and the MnO2 and MnO2/C synthesis via hydrothermal techniques were performed. Additionally, the one-step synthesis of MnO2/C via one-step hydrothermal method with no acid leaching was also explored in this study. The recycled Zn, MnO2, MnO2/C and C residual were subsequently used as the anode and cathode main components in the CR2032 and pouch-cell rechargeable Zn-ion batteries. The recycled MnO2 and MnO2/C provided similar performance as the commercial products, which indicating the recycled MnO2, MnO2/C could be effectively utilized in the Zn-ion battery, while the utilization of recycled Zn-film provided slightly lower performance compared to that of the commercial Zn foil.

Upgrading Gel Electrolytes Through Electrostatic-Induced Dual-Salt Paradigm for Superior Zn-Ion Battery Performance.

Gel electrolytes are gaining attention for rechargeable Zn-ion batteries because of their high safety, high flexibility, and excellent comprehensive electrochemical performances. However, current gel electrolytes still perform at mediocre levels due to incomplete Zn salts dissociation and side reactions. Herein, an electrostatic-induced dual-salt strategy is proposed to upgrade gel electrolytes to tackle intrinsic issues of Zn metal anodes. The competitive coordination mechanism driven by electrostatic repulsion and steric hindrance of dual anions promotes zinc salt dissociation at low lithium salt addition levels, improving ion transport and mechanical properties of gel electrolytes. Li+ ions and gel components coordinate with H2O, reducing active H2O molecules and inhibiting associated side reactions. The dual-salt gel electrolyte enables excellent reversibility of Zn anodes at both room and low temperatures. Zn||Polyaniline cells using the dual-salt gel electrolyte exhibit a high discharge capacity of 180mAhg-1 and long-term cycling stability over 180 cycles at -20°C. The dual-salt strategy offers a cost-effective approach to improving gel electrolytes for high-performance flexible Zn-ion batteries.

Green Plasma Enhanced Synthesis of Multi-Phase NiMnO3 Cathode for Aqueous Zn-Ion Batteries

Rechargeable Zn-ion batteries have the potential to address the need for cheap and widely accessible energy storage. Metal-doped manganese oxide cathodes are a common and effective choice for Zn-ion batteries. Zn-ion battery development can be advanced by overcoming the poor cycle life that many metal-doped Mn-oxide cathodes suffer from. Plasma-treated water (PAW) is created using low input power of 0.145 kWh per liter of PAW and is used to accelerate the reduction and precipitation of MnO4 − and nickel acetate (Ni(Ac)) to form a multiphase NiMnO3 electrode with Ni2+ and Ni3+ doped into the MnO6 octahedra, which exhibits capacitance dominated charge storage mechanisms. The electrode shows initial specific capacitance of 60.1 F g−1 and a capacitance retention of 100.8% after 10,000 cycles and 92.2% after 12,000 cycles. The beneficial layer of nanoflake morphology is formed during cycling, which causes a rapid increase in specific capacitance due to the larger electrochemically active surface area and the associated surface adsorption-based (pseudo-capacitive) type charge storage. We also demonstrate the capability of our multiphase NiMnO3 electrode to be coupled with a Zn metal anode in a battery cell which exhibits 330 mAh g−1 peak specific capacity and capacity retention of 63.8% after 380 cycles.

Regulating the inner Helmholtz plane structure at the electrolyte-electrode interface for highly reversible aqueous Zn batteries

The development of aqueous Zn batteries is limited by parasitic water reactions, corrosion, and dendrite growth. To address these challenges, an inner Helmholtz plane (IHP) regulation method is proposed by employing low-cost, non-toxic maltitol as the electrolyte additive. The preferential adsorption behavior of maltitol can expel the water from the inner Helmholtz plane, and thus hinder the immediate contact between Zn metal and H2O. Meanwhile, strong interaction between maltitol and H2O molecules can restrain the activity of H2O. Besides, the “IHP adsorption effect” along with the low LUMO energy level of maltitol-CF3SO3- can promote the in-situ formation of an organic–inorganic complex solid electrolyte interface (SEI) layer. As a result, the hydrogen/oxygen evolution side reaction, corrosion, and dendrites issues are effectively suppressed, thereby leading to highly reversible and dendrite-free Zn plating/stripping. The Zn||I2 battery with hybrid electrolytes also demonstrates high electrochemical performance and ultralong cycling stability, showing a capacity retention of 75% over 20000 charge-discharge cycles at a large current density of 5 A g−1. In addition, the capacity of the device has almost no obvious decay over 20000 cycles even at −30 °C. This work offers a successful electrolyte regulation strategy via the IHP adsorption effect to design electrolytes for high-performance rechargeable Zn-ion batteries.

Nutrient for Inhibiting the Activity of H2O and Optimizing Interfacial Chemistry for Aqueous Rechargeable Zn-Ion Batteries

Nutrient for Inhibiting the Activity of H₂O and Optimizing Interfacial Chemistry for Aqueous Rechargeable Zn-Ion Batteries

Novel composite cathode material α-MnO2@ZIF-67 for high performance aqueous rechargeable Zn-ion battery

As a promising cathode material for aqueous zinc ion batteries, manganese dioxide (α-MnO2) faces several challenges such as low ionic conductivity and significant volume expansion during charging and discharging. Coating is an effective method to improve the electrochemical performance, and the composition and structure of the coating layer play a key role in the electrochemical properties of the materials. In this work, we employed a room temperature in situ growth strategy to fabricate composites comprising α-MnO2 nanorods and Zeolite Imidazolium Framework-67 (ZIF-67) nanoparticles. The porous ZIF-67 improves the ionic/electronic conductivity and provides more active sites. The α-MnO2@ZIF-67 composites show a high specific capacity of 313.4 mAh g−1 at 100 mA g−1 and good long-term cycling stability, with a capacity retention of 65 % after 1500 cycles at 1000 mA g−1. The above results indicate that it is an effective technique to improve the electrochemical performance of manganese-based oxide materials by compositing with porous MOFs.

TEMPO-oxidized cellulose nanofiber hydrogel electrolyte for rechargeable Zn-ion batteries.

A hydrogel composed of TEMPO-oxidized cellulose and zinc perchlorate is proposed as an electrolyte for rechargeable Zn-ion battery. The non-flowable solid-like electrolyte has strong shear-thinning behavior, room temperature conductivity of ∼10-1 S cm-1, and stable Zn/electrolyte interphase. The Zn-ion gel-battery with a β-MnO2 cathode delivers over 100 mA h g-1 at 1.5 V allowing safe energy storage.

Double-sided engineering for space-confined reversible Zn anodes

Zn anodes with double-sided engineering are rationally designed and facilely constructed, which generates a space-confined reversible Zn deposition behavior, thus enabling stable Zn anode working at high depth of discharge with high energy density.

Peptide Gel Electrolytes for Stabilized Zn Metal Anodes.

The rechargeable aqueous Zn ion battery (AZIB) is considered a promising candidate for future energy storage applications due to its intrinsic safety features and low cost. However, Zn dendrites and side reactions (e.g., corrosion, hydrogen evolution reaction, and inactive side product (Zn hydroxide sulfate) formation) at the Zn metal anode have been serious obstacles to realizing a satisfactory AZIB performance. The application of gel electrolytes is a common strategy for suppressing these problems, but the normally used highly cross-linked polymer matrix (e.g., polyacrylamide (PAM)) brings additional difficulties for battery assembly and recycling. Herein, we have developed a gel electrolyte for Zn metal anode stabilization, where a peptide matrix, a highly biocompatible material, is used for gel construction. Various experiments and simulations elucidate the sulfate anion-assisted self-assembly gel formation and its effect in stabilizing Zn metal anodes. Unlike polymer gel electrolytes, the peptide gel electrolyte can reversibly transform between gel and liquid states, thus facilitating the gel-involved battery assembly and recycling. Furthermore, the peptide gel electrolyte provides fast Zn ion diffusion (comparable to conventional liquid electrolyte) while suppressing side reactions and dendrite growth, thus achieving highly stable Zn metal anodes as validated in various cell configurations. We believe that our concept of gel electrolyte design will inspire more future directions for Zn metal anode protection based on gel electrolyte design.

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.

Dendrite-Free Zinc Anodes Enabled by Exploring Polar-Face-Rich 2D ZnO Interfacial Layers for Rechargeable Zn-Ion Batteries.

Zinc metal is a promising candidate for anodes in zinc-ion batteries (ZIBs), but its widespread implementation is hindered by dendrite growth in aqueous electrolytes. Dendrites lead to undesirable side reactions, such as hydrogen evolution, passivation, and corrosion, causing reduced capacity during prolonged cycling. In this study, an approach is explored to address this challenge by directly growing 1D zinc oxide (ZnO) nanorods (NRs) and 2D ZnO nanoflakes (NFs) on Zn anodes, forming artificial layers to enhance ZIB performance. The incorporation of ZnO on the anode offers both chemical and thermal stability and leverages its n-type semiconductor nature to facilitate the formation of ohmic contacts. This results in efficient electron transport during Zn ion plating and stripping processes. Consequently, the ZnO NFs-coated Zn anodes demonstrate significantly improved charge storage performance, achieving 348 mAh g-1, as compared to ZnO NRs (250 mAh g-1) and pristine Zn (160 mAh g-1) anodes when evaluated in full cells with V2O5 cathodes. One significant advantage of ZnO NFs lies in their highly polar surfaces, promoting strong interactions with water molecules and rendering them exceptionally hydrophilic. This characteristic enhances the ability of ZnO NFs to desolvate Zn2+ ions, leading to improved charge storage performance.

Two-pronged approach to achieving high-capacity and long stable-life aqueous Zn-ion batteries

Rechargeable Zn-ion batteries (ZIBs) have attracted much attention due to their high energy density, high safety, and low cost. Nevertheless, the practical implementation of ZIBs has been dreadfully hindered by the lack of stable high-capacity cathode candidate and serious dendritic growth in Zn anode. Superior device-level performance can only be achieved by simultaneously addressing the fatal shortcomings of both electrodes. Herein, we explore a two-pronged approach to achieving high-capacity, long-life stable ZIBs via synergistic design in both anodes and cathodes. Specifically, hierarchical accordion-like ZnV2O4@C (A-ZVO@C) framework derived from multi-layered V2CTx is fabricated and endowed with high electronic/ionic conductivities and structural/chemical stability, exhibiting striking high-rate capacities/stability when utilized as a cathode. Meanwhile, a dendrite-free Zn with an artificial protective layer of zincophilic ZnO/C hollow spheres affords outstanding Zn plating-stripping stability with a prolonged lifespan, which reduces local current density, homogenizes Zn2+ ion diffusion/deposition, and suppresses volume changes during long-term plating/stripping. As a result, the assembled full ZIBs deliver a high-rate capacity of 232.2 mAh g−1 at 8 A g−1, and superb stability with capacity degradation of 7.8 % over 3000 consecutive cycles at 15.0 A g−1. More meaningfully, the contribution here provides an essential guidance for rationally designing next-generation ZIBs.

In-situ grown hydrophilic-zinophilic ZnCr2O4 protective layer to guide horizontal Zn2+ deposition for dendrite -free Zn anodes for aqueous Zn-ion batteries

Aqueous rechargeable Zn-ion batteries (ARZIBs) have attracted much attention owing to their safety, high energy density and environmental friendliness. However, zinc dendrites and corrosive reactions during platting/stripping on the surface of Zn anodes limit the practical applications of ARZIBs. Herein, the hydrophilic and zinophilic ZnCr2O4 interface layer is grown in situ on the surface of Zn metal to stabilize Zn anode. The in-situ grown ZnCr2O4 interface protective layer constrains the 2D diffusion of Zn2+and homogenizes the surface electric field, guiding preferentially horizontal deposition of Zn2+ along the Zn foil surface. In addition, the in situ ZnCr2O4 interface layer possesses strong hydrophilicity and zinophilicity to enable rapid desolvation of Zn(H2O)62+ and improve Zn2+ platting/stripping kinetics for dense Zn deposition without dendrite Zn growth. Consequently, the symmetric cell with ZnCr2O4-protected Zn anode can stably operate more than 1500 h at 1 mA cm−2 with 1 mAh cm−2, while the Cu||ZCO@Zn half-cell presents a high average Coulombic efficiency of over 99.7 % during cycling for more than 100 cycles. In addition, the NH4V4O10||ZCO@Zn full cell exhibits the capacity retention of 83.3 % at 3 A g−1 after 1000 cycles. This investigation provides a feasible strategy to efficiently inhibit zinc dendrites by in-situ constructing hydrophilic-zinophilic artificial protective coating on the surface of Zn anodes.

Zincophilic Metal-Organic-Framework Interface Mitigating Dendrite Growth for Highly Reversible Zinc Metal Batteries.

Aqueous Zn-ion batteries are the ideal candidate for large-scale energy storage systems owing to their high safety and low cost. However, the uncontrolled deposition and parasitic reaction of Zn metal anode hinder their commercial application. Here, the 2D metal-organic-framework (MOF) nanoflakes covered on the surface of Zn are proposed to enable dendrite-free for long lifespan Zn metal batteries. The MOF can facilitate the desolvation process to accelerate reaction kinetic due to its special channel structure. The abundant zincopilicity sites of MOF can realize the homogenous Zn2+ deposition. Consequently, their synergetic effect makes the MOF protected Zn anode good electrochemical performance with a long cycle life of 1400h at 1mA cm-2 and a high depth of discharge of 30 mAh cm-2 (DOD ≈ 54%) continued for over 700h. This work provides a novel strategy for high-performance rechargeable Zn-ion batteries.

Strategies for Optimizing the Zn Anode/Electrolyte Interfaces Toward Stable Zn-Based Batteries.

Aqueous rechargeable Zn-ion batteries (ARZIBs) have attracted extensive attention because of the advantages of high energy density, high safety, and low cost. However, the commercialization of ARZIBs is still challenging, mainly because of the low efficiency of Zn anodes. Several undesirable reactions (e.g., Zn dendrite and byproduct formation) always occur at the Zn anode/electrolyte interfaces, resulting in low Coulombic efficiency and rapid decay of ARZIBs. Motivated by the great interest in addressing these issues, various optimization strategies and related mechanisms have been proposed to stabilize the Zn anode-electrolyte interfaces and enlengthen the cycling lifespan of ARZIBs. Therefore, considering the rapid development of this field, updating the optimization strategies in a timely manner and understanding their protection mechanisms are highly necessary. This review provides a brief overview of the Zn anode/electrolyte interfaces from the fundamentals and challenges of Zn anode chemistry to related optimization strategies and perspectives. Specifically, these strategies are systematically summarized and classified, while several representative works are presented to illustrate the effect and corresponding mechanism in detail. Finally, future challenges and research directions for the Zn anode/electrolyte interfaces are comprehensively clarified, providing guidelines for accurate evaluation of the interfaces and further fostering the development of ARZIBs.

Bi-layered calcium vanadium oxide as a cathode material for wet organic electrolyte-based rechargeable Zn-ion batteries

Zn-ion batteries attract considerable attention as a promising option for large-scale energy storage owing to their many benefits, including safety, high abundance of zinc, low fabrication costs, and ease of handling in air. However, to improve their effectiveness, three key technical challenges must be overcome: low electrolyte performance, metal dendrite formation, and a limited choice of host materials. This study introduces a new cathode material for Zn-ion batteries — double-layered Ca0.26V2O5·H2O — that exhibits outstanding performance in a wet organic electrolyte. The cathode material demonstrates an initial discharge capacity of 268.76 mAh g−1 at a rate of 0.2C and average operating voltage of 0.82 V (vs. Zn2+/Zn) with excellent capacity retention. A reversible Zn intercalation/crystal water extraction reaction is confirmed by conducting elemental and structural analyses, including powder X-ray diffraction. Furthermore, the results of bond valence sum calculations support the formation of a two-dimensional network of Zn-ion conduction pathways along the a-axis and b-axis, illustrating the electrochemical zinc intercalation into the wet organic electrolyte. Overall, this study not only introduces double-layered Ca0.26V2O5·H2O as a new cathode material for Zn-ion batteries but also provides valuable insights into the electrochemical zinc intercalation/crystal water extraction in wet organic electrolytes.

Critical triple roles of sodium iodide in tailoring the solventized structure, anode-electrolyte interface and crystal plane growth to achieve highly reversible zinc anodes for aqueous zinc-ion batteries

Aqueous rechargeable Zn-ion batteries (ARZIBs) are promising for energy storage. However, the Zn dendrite and corrosive reactions on the surface of Zn anode limit the practical uses of ARZIBs. Herein, we present a valid electrolyte additive of NaI, in which I- can modulate the morphology of Zn crystal growth by adsorbing on specific crystal surfaces (002), and guide Zn deposition by inducing a negative charge on the Zn anode. Simultaneously, it enhances the reduction stability of water molecules by participating in the solvation structure of Zn(H2O)62+ by forming ZnI(H2O)5+. At 10 mA cm−2, the assembled Zn symmetrical batteries can run stably over 1,100 h, and the depth of discharge (DOD) can reach 51.3 %. At 1 A g−1, the VO2||Zn full-cell in 2 M ZnCl2 electrolyte with 0.4 M NaI (2 M ZnCl2-0.4 M NaI) maintains of the capacity retention of 75.7 % over 300 cycles. This work offers an insight into inorganic anions as electrolyte additives for achieving stable zinc anodes of ARZIBs.

Fabrication of Zn-doped Co3O4 as cathode material for aqueous rechargeable Zn-ion batteries

The increasing demand for advanced energy-storage systems have led to extensive research on Co3O4//Zn batteries because of their high theoretical capacity, low cost, and environment friendliness. However, the capacity of Co3O4//Zn batteries is decreased by the volume change of Co3O4 cathode in practical application, so its advantages are not fully utilised. To improve the capacity of Co3O4 cathode, a cathode of Zn-doped Co3O4 based on carbon cloth with zeolite imidazole-67 (ZIF-67) precursor in aqueous zinc-ion battery was successfully prepared. The Zn-doped Co3O4 cathode had a uniform arrangement in mild aqueous electrolyte, The battery had a high charge/discharge voltage of 2.2 V, a high specific capacity of 196 mA h/g at 1 A/g, outstanding rate capability, and superior cycle stability of 93.2 % capacity retention over 1000 cycles at 5 A/g. The improvement in electrode material provided a new idea for preparing rechargeable aqueous Zn-ion batteries.