Stable Zinc Research Articles

Three-dimensional mixed-valence polyoxovanadates@polyaniline architecture towards high-performance rechargeable aqueous zinc-ion batteries cathode

Aqueous zinc ion batteries (AZIBs) are toward promising candidates of energy storage systems for their low cost, high safety and eco-friendliness, whereas the sluggish reaction kinetics and unstable internal structure of cathode materials greatly limited the practical application of AZIBs. Herein, we employ the three-dimensional mixed-valance polyoxovanadates [Co3(H2O)12][VIV10VV8O42(SO4)]·24H2O (CoVO) coated with polyaniline (PANI) as stable zinc ion storage material (denoted as CoVO@PANI). The 3D highly porous CoVO framework constructs multidimensional interconnected Zn2+ migration channels, and the high conductivity of PANI facilitates the formation of oxygen defects during in-situ polymerization process and inhibits the polyoxovanadates dissolution. Density functional theory calculation reveals that PANI significantly regulates the electronic property of the CoVO host, further promoting the electron/ion transfer kinetics and thus contributing to high-effciency Zn2+ storage performance. As expected, the optimized as-fabricated CoVO@PANI60 cathode exhibits a high reversible capacity of 456.8 mAh g−1 at 0.1 A g−1 and long-term cyclability with capacity retention of 90.4 % after 1500 cycles at 10 A g−1.

A Water‐Insoluble Yttrium‐Based Complex as Dual‐Ionic Electrolyte Additive for Stable Aqueous Zinc Metal Batteries

AbstractAqueous batteries employing Zinc metal anodes (ZMAs) are considered to be promising next‐generation energy storage systems. However, the severe interfacial side reactions and dendrite growth restrict the practical application of ZMAs in aqueous electrolytes. Herein, a water‐insoluble dual‐ionic electrolyte additive of yttrium 2,4,5‐trifluorophenylacetate (YTFPAA) is developed to stabilize the aqueous ZMAs. Notably, the ethanol‐solvated TFPAA− can capture H+ and thus buffer the decreased electrolyte pH caused by the hydrolysis of Y3+. Furthermore, the ethanol‐solvated TFPAA− can dynamically adsorb onto the surface of ZMAs through a reversible oxidation‐reduction reaction, effectively suppressing the interfacial side reactions by forming a water‐poor interface, and enhancing the reversibility of Zn2+ deposition/stripping by redistributing the Zn2+ flux. These favorable effects of TFPAA− combined with the dynamic electrostatic shielding effect of Y3+ ultimately enable uniform and dense Zn2+ deposition. As a result, the Zn/Zn cells assembled with 0.25YTFPAA electrolyte exhibit an impressive cycle life of 2100 h at 0.5 mA cm−2–0.25 mAh cm−2. More importantly, the assembled V2O5/Zn full cell shows an ultra‐long cycle life of up to 18000 cycles at 5.0 A g−1. This work highlights the rational design of multifunctional ionic additives for stabilizing aqueous ZMAs.

A highly stable zinc anode protected by a corrosion inhibitor for seawater-based zinc-ion batteries

The island-based energy storage is of urgent need for the grid construction combined with renewable energy for offshore operation. The direct use of seawater as a substitute of deionized water shows its great promise for aqueous zinc-ion batteries in such a specific situation. However, the metal corrosion, dendrite growth, and hydrogen evolution stand out in the harsh seawater environment. To address these challenges, we proposed a corrosion inhibitor that was effective in the field of metal anti-corrosion, 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTCA), to inhibit anode corrosion caused by Cl– and active H2O molecules by forming a stable solid electrolyte interphase (SEI) film in the seawater-based electrolyte. Besides, PBTCA can chelate with other cations present in seawater, such as Ca2+ and Mg2+, thereby preventing the aggregation and precipitation of sparingly soluble species. Under a current density of 5 mA cm−2, the seawater-based zinc-ion battery exhibited an exceptional cycle life exceeding 2000 h and maintained a Coulombic efficiency of over 99.6% after 2000 cycles. Additionally, the performance of the Zn||ZVO full battery was significantly enhanced with the addition of PBTCA. This study provides a simple, low-cost, and efficient approach for making the seawater-based zinc-ion batteries useable.

Preparation, characterization, and anticancer evaluation of polydatin conjugated with zinc MOF and encapsulated by liponiosomes as a potential nanotool-induce apoptosis

Tumor is a serious worldwide issue that ranks as the second cause of mortality, regardless of the region's status. It is treated with a variety of techniques, including chemotherapy, radiotherapy, and surgery, however, there are drawbacks, such as adverse medication reactions. The investigation of stable and effective zinc metal-organic frameworks (ZMOFs) for medicinal applications has received increasing attention. Herein, we report the fabrication of our work has promised a drug delivery system (DDS) by polydatin (PD)-loaded ZMOF (PD-ZMOF) and encapsulated into liponiosomes (LNs) to form (PD-ZMOF@LNs) for increased drug targeting to tumor cells. The obtained compounds were characterized using XRD, SEM, TEM, FTIR, TGA, BET, PDI, zeta seizer, and zeta potentials (ZP) analysis. A computational approach based on Monte Carlo simulation was adopted to elucidate the PD loading mechanism into the ZMOF. Both ZMOF and PD-ZMOF@LNs showed no significant weight loss up to approximately 551⁰C, indicating their high thermal stability and the final weight decrease due to the full degradation of the ZMOF framework at that point. TEM images of ZMOF and PD-ZMOF@LNs NPs demonstrated a spherical-like and needle-like particles with an average diameter of 17.6 nm and 27.3 nm (*P < 0.05), respectively. The hydrodynamic size analyzer displayed an average particle size of 194.4 nm, with ZP of +23 mV. The encapsulation efficiency (EE), loading capacity (LC), drug release (DR), and drug-release kinetics of PD and PD-ZMOF@LNs were evaluated, and the results showed that PD was EE into ZMOF up to 91.27 ± 0.83 % (*P < 0.05). To understand the procedure of PD release at pH 6.9, four kinetic models were examined to identify which model best fit the obtained release data, and the Zero-order model demonstrated excellent release fitness with R2 = 0.9953. Anticancer activity of optimized free PD, ZMOF, and PD-ZMOF@LNs was evaluated in MCF-7 cells utilizing cell viability and flow-cytometric assays. Our samples demonstrate anti-tumor activity against MCF-7 cells with inhibitory concentrations (IC50) at 105 ± 1.5 µg/mL for PD-ZMOF@LNs. The surviving fraction and plating efficiency colony formation potential for PD-ZMOF@LNs were 32 % and 23 %, respectively (*P < 0.05). Flow cytometry analysis indicated that PD-ZMOF@LNs induced apoptosis in 77.39 % of MCF-7 cells.

Bi-Functional Electrolyte Additive Leading to a Highly Reversible and Stable Zinc Anode.

A stable stripping/plating process of the zinc anode is extremely critical for the practical application of aqueous zinc metal batteries. However, obstacles, including parasitic reactions and dendrite growth, notoriously deteriorate the stability and reversibility of zinc anode. Herein, Methyl l-α-aspartyl-l-phenylalaninate (Aspartame) is proposed as an effective additive in the ZnSO4 system to realize high stability and reversibility. Aspartame molecule with rich polar functional groups successfully participates in the solvation sheath of Zn2+ to suppress water-induced side reactions. The self-driven adsorption of Aspartame on zinc anode improves uniform deposition with a dose of 10mm. These synergetic functions endow the zinc anode with a significantly long cycling lifespan of 4500h. The cell coupled with a vanadium-based cathode also exhibited a high-capacity retention of 71.8% after 1000 cycles, outperforming the additive-free counterparts.

Constructing zinc-tin alloy interface for highly stable alkaline zinc anode

Aqueous alkaline zinc batteries have received widespread attention owing to its higher electrode potential and faster reaction kinetics compared to in mild aqueous electrolyte. However, Zn metal anode in alkaline electrolyte usually suffers more severe corrosion, passivation, and hydrogen evolution reaction. Herein, an interface chemical regulation strategy employs to in-situ construct a Zn-Sn alloy layer during cycling. The K2[Sn(OH)6] has been introduced into the electrolyte as the deposition overpotential of Zn and Sn in alkaline electrolyte is approximate leading to their simultaneously plating. The Zn-Sn alloy layer not only prevents Zn anode corrosion and suppresses the dendrite growth but also promotes the reaction kinetics. Therefore, the Zn||Zn cell exhibits a long life of 400 h in alkaline electrolyte about 20 times of that in without K2[Sn(OH)6] electrolyte. Moreover, the N-NCP@PQx||Zn full cell displays a superior cycle performance of 4000 cycles with 93% capacity retention at 2 A/g.

Low-Cost Aqueous Electrolyte with MBA Additives for Uniform and Stable Zinc Deposition.

Aqueous zinc ion batteries (AZIBs) are attracting increasing research interest due to their intrinsic safety, low cost, and scalability. However, the issues including hydrogen evolution, interface corrosion, and zinc dendrites at anodes have seriously limited the development of aqueous zinc ion batteries. Here, N,N-methylenebis(acrylamide) (MBA) additives with -CONH- groups are introduced to form hydrogen bonds with water and suppress H2O activity, inhibiting the occurrence of hydrogen evolution and corrosion reactions at the interface. In situ optical microscopy demonstrates that the MBA additive promotes the uniform deposition of Zn2+ and then suppresses the dendrite growth on the zinc anode. Therefore, Zn//Ti asymmetric batteries demonstrate a high plating/stripping efficiency of 99.5%, while Zn//Zn symmetric batteries display an excellent cycle stability for more than 1000 h. The Zn//MnO2 full cells exhibit remarkable cycling stability for 700 cycles in aqueous electrolytes with MBA additives. The additive engineering via MBA achieved the dendrite-free Zn anodes and stable full batteries, which is favorable for advanced AZIBs in practical applications.

Designing carboxymethyl cellulose based hydrogel electrolyte membranes enhanced by inorganic nanoparticle toward stable zinc anode

Aqueous zinc metal batteries have garnered substantial attention ascribing to affordability, intrinsic safety, and environmental benignity. Nevertheless, zinc metal batteries yet are challenged with potential service life issues resulted from dendrites and side reaction. In this paper, a strategy of nanoparticles doped hydrogel is proposed for constructing carboxymethyl cellulose/graphite oxide hybrid hydrogel electrolyte membranes with exceptional ionic conductivity, anti-swelling property, and simultaneously addressing the dendrites and parasitic reaction. The pivotal functions of the carboxymethyl cellulose/graphite oxide hydrogel electrolyte in mitigating hydrogen evolution and fostering accelerated Zn deposition have been elucidated based on principles of thermodynamic and reaction kinetic. The carboxymethyl cellulose/graphite oxide hydrogel electrolyte endows exceptional cycling longevity (800 h at 1 mA cm−2/1 mAh·cm−2) for Zn||Zn battery, as well as high Coulombic efficiency for Zn||Cu battery (averagely 99.14% within 439 cycles at 1 mA cm−2/1 mAh·cm−2). The assembled Zn||NH4V4O10 battery delivers a high reversible specific capacity of 328.5 mAh·g−1 at 0.1 A g−1. Moreover, the device of Zn||NH4V4O10 pouch battery remains operational under severe conditions like bending and cutting. This work provides valuable reference in developing inorganic nanoparticle hybrid hydrogel electrolyte for realizing high-performance zinc metal batteries.

Harnessing Ion-Dipole Interactions for Water-Lean Solvation Chemistry: Achieving High-Stability Zn Anodes in Aqueous Zinc-Ion Batteries.

The reversibility and stability of aqueous zinc-ion batteries (AZIBs) are largely limited by water-induced interfacial parasitic reactions. Here, dimethyl(3,3-difluoro-2-oxoheptyl)phosphonate (DP) is introduced to tailor primary solvation sheath and inner-Helmholtz configurations for robust zinc anode. Informed by theoretical guidance on solvation process, DP with high permanent dipole moments can effectively substitute the coordination of H2O with charge carriers through relatively strong ion-dipolar interactions, resulting in a water-lean environment of solvated Zn2+. Thus, interfacial side reactions can be suppressed through a shielding effect. Meanwhile, lone-pair electrons of oxygen and fluorinated features of DP also reinforce the interfacial affinity of metallic zinc, associated with exclusion of neighboring water to facilitate reversible zinc planarized deposition. Thus, these merits endow the Zn anode with a high-stability performance exceeds 3800 hours at 0.5 mA cm-2 and 0.5 mAh cm-2 for Zn||Zn batteries and a high average Coulombic efficiency of 99.8 % at 4 mA cm-2 and 1 mAh cm-2 for Zn||Cu batteries. Benefiting from the stable zinc anode, the Zn||NH4V4O10 cell maintains 80.3 % of initial discharge capacity after 3000 cycles at 5 A g-1 and exhibits a high retention rate of 99.4 % against to the initial capacity during the self-discharge characterizations.

Hydrophobic and zincophilic organic hierarchical nano-membranes with ordered molecular packing for stable zinc metal anodes

Rechargeable aqueous Zn metal batteries hold significant potentials as one of the next-generation energy-storage devices due to their low cost and high safety. However, the uncontrollable dendrite growth and low efficiency in plating/stripping of Zn anodes hinder the commercial application of aqueous Zn-ion batteries (AZIBs). Herein, inspired by hydrophobic lotus, a multifunctional organic hierarchical nano-membrane serving as an artificial protective layer is constructed through the gas-liquid interface method, using self-assembled organic nanosheets (NOS). The organic nano-membrane exhibits ordered molecular packing, accompanied by uniform distribution of zincophilic carbonyl (CO) groups on the Zn metal surface. These groups function as active sites, homogenizing Zn2+ flux and accelerating Zn2+ deposition. Simultaneously, the hydrophobic membrane isolates active water, thereby restraining side reactions, effectively suppressing corrosion and extremely inhibiting dendrite growth. Consequently, NOS@Zn anode exhibits stable cycling over 2400 h and an average coulombic efficiency (CE) of 99.69 % (600 cycles) at 1 mA cm−2. Furthermore, NOS@Zn||CNT-MnO2 full cell presents remarkable capacity retention, approximately 5 times higher than that of Zn||CNT-MnO2 after 3000 cycles at 2 A g−1. This work develops an innovative organic interface modification material paving the way for dendrite-free Zn metal anodes and advancing the practical application of large-scale Zn-based energy storage systems.

CARACTÉRISATION ET ÉVALUATION IN VITRO DE L’ACTIVITÉ ANTIBACTÉRIENNE DE NANOPARTICULES D’OXYDE DE ZINC PRÉPARÉES À BASE DE L’EXTRAIT AQUEUX DES FEUILLES DE CHROMOLAENA ODORATA (L.) R. M. KING &amp; H. ROBINSON (ASTERACEAE)

In the present study, zinc oxide nanoparticles were prepared using the aqueous extract of the leaves of Chromolaena odorata. These biosynthesized nanocrystals were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray energy dispersive spectroscopy (EDS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). XRD results on the prepared powder confirmed the presence of ZnO, with an estimated mean size of 24 nm. The SEM and TEM images indicated that the synthesized nanoparticles were spherical in shape with good particle dispersion. FTIR spectroscopy also confirmed the presence of ZnO in the synthesized powder through to the presence of the band localized between 800-500 cm-1, which is characteristic of the (Zn−O) bonds in zinc oxide. The antimicrobial activity of the prepared nanopowders against the bacterial strains E. coli and S. aureus demonstrated significant inhibitory effects. These inhibitory effects were more pronounced on E. coli than on S. aureus with maximum inhibition zones of 16 and 14 mm, respectively. It appears that this method can be used for the rapid and environmentally-friendly biosynthesis of stable zinc oxide nanoparticles having antimicrobial properties.

Oligopeptide‐Induced Multifunctional Interface Layer with Protonated Hydrophobic Behavior and Strong Affinity for Highly Stable Zinc Anode

AbstractZinc‐ion batteries (ZIBs) have attracted wide attention due to their low redox potential, high capacity, and intrinsic safety. However, key issues such as zinc dendrite growth, corrosion, and passivation on zinc anode detrimentally affect the electrochemical performance. Herein, as proof of a concept of oligopeptide, glutathione with functional groups including –NH2 and −SH is introduced as an electrolyte additive to construct a multifunctional electrode–electrolyte interface layer on the zinc anode. A protonated amino group (NH3+) is formed, which prevents the adsorption of water molecules on the Zn anode, building a hydrophobic interface layer and thus attenuating corrosion. Moreover, the strong interaction between the −SH and the zinc allows glutathione molecules to be tightly anchored to the electrode surface, constructing a robust interface layer. Consequently, a long cycling life of nearly 3000 h at 1 mA cm−2 for the Zn||Zn symmetric battery is achieved, and a stable cycling life of 1600 h is demonstrated at 3 mA cm−2. Furthermore, Zn||activated carbon (AC) hybrid capacitor with the glutathione‐containing electrolyte runs stably for nearly 28 000 cycles at 5 A g−1, among the best results of reported Zn hybrid capacitors.

Blocking the passivation reaction via localized acidification and cation selective interface towards highly stable zinc anode

The variations of pH triggers either the formation of zinc sulfate hydroxide (ZSH) or the hydrogen evolution reaction (HER), leading to unsatisfactory zinc anode efficiency. In order to establish a balanced approach that suppresses the HER while creating an acidic environment to eliminate ZSH formation, this study introduces an environmentally friendly chelating additive, tetrasodium iminodisuccinate (IDS), into the ZnSO4 electrolyte. This additive serves to generate a localized acidic environment and a cation-selective surface barrier. The preferentially adsorbed IDS anions create a water-poor interface and engage in synergistic regulation of cation and anion via electrostatic effects, promoting smooth Zn deposition and reducing by-product formation. Additionally, IDS can strongly interact with Zn2+ and adapt to pH variations, thereby providing a stable environment that mitigates side reactions. Unlike sacrificial additives, IDS demonstrates stability under test conditions, resulting in a truly reversible and stable electrolyte system. The implementation of this multifunctional additive results in a prolonged lifespan of metallic Zn, reaching 2548 h, and a promoted coulombic efficiency of 99.5 %. Furthermore, the improved stability of Zn anodes is observed in Zn//LiFePO4 cells, exhibiting the capacity retention of 97.0 % over 800 cycles. This strategy opens up a new pathway for enhancing the stability and reversibility of Zn anodes.

Stable Zinc Electrode Reaction Enabled by Combined Cationic and Anionic Electrolyte Additives for Non-Flow Aqueous Zn─Br2 Batteries.

Aqueous zinc-bromine batteries hold immense promise for large-scale energy storage systems due to their inherent safety and high energy density. However, achieving a reliable zinc metal electrode reaction is challenging because zinc metal in the aqueous electrolyte inevitably leads to dendrite growth and related side reactions, resulting in rapid capacity fading. Here, it is reported that combined cationic and anionic additives in the electrolytes using CeCl3 can simultaneously address the multiple chronic issues of the zinc metal electrode. Trivalent Ce3+ forms an electrostatic shielding layer to prevent Zn2+ from concentrating at zinc metal protrusions, while the high electron-donating nature of Cl- mitigates H2O decomposition on the zinc metal surface by reducing the interaction between Zn2+ and H2O. These combined cationic and anionic effects significantly enhance the reversibility of the zinc metal reaction, allowing the non-flow aqueous Zn─Br2 full-cell to reliably cycle with exceptionally high capacity (>400mAh after 5000 cycles) even in a large-scale battery configuration of 15×15cm2.

Activating the Intrinsic Zincophilicity of PAM Hydrogel to Stabilize the Metal-Electrolyte Dynamic Interface for Stable and Long-Life Zinc Metal Batteries.

As a potential material to solve rampant dendrites and hydrogen evolution reaction (HER) problem of aqueous zinc metal batteries (AZMB), hydrogel electrolytes usually require additional additives or multi-molecular network strategies to solve existing problems of ionic conductivity, mechanical properties and interface stability. However, the intrinsic zincophilic properties of the gel itself are widely neglected leading to the addition of additional molecules and the complexity of the preparation process. In this work, we innovatively utilize the characteristics of acrylamide's high zincophilic group density, activating the intrinsic zincophilic properties of PAM gel through a simple concentration control strategy which reconstructs a novel zinc-electrolyte interface different from conventional PAM electrolyte. The activated novel gel electrolyte with intrinsic zincophilic properties has high ionic conductivity and effectively suppresses water activity, thereby inhibiting HER corrosion. Meanwhile, it induces uniform deposition of (002) crystal planes, leading to excellent deposition kinetics and long cycle life, thereby ensuring high interfacial stability. Compared with conventional PAM gel electrolytes, the activated zincophilic group-rich hydrogel maintained excellent cycling stability (1 mA/cm2, 1 mAh/cm2) over 2250 hours; The Zn//MnO₂ coin cell using novel zincophilic group -rich hydrogel still retains a high specific capacity of more than 170 mAh/g at 0.5 A/g after 1000 cycles.

Boric acid-induced preferential deposition of (002) plane for highly stable zinc anode

Aqueous zinc-ion batteries (ZIBs) hold significant promise in the future energy storage market. However, the uncontrolled growth of zinc dendrites and the occurrence of side reactions severely constrain the practical deployment of ZIBs. To address these challenges, this study suggests incorporating H3BO3 (HBO) as an electrolyte additive into the ZnSO4 electrolyte, with the aim of inducing preferential growth of the (002) plane. HBO molecules selectively adsorb onto the (100) and (101) planes of zinc, promoting the deposition of Zn2+ ions into the (002) plane and resulting in the formation of a uniformly deposited layer while concurrently inhibiting side reactions. The results demonstrate that ZnǁZn symmetric batteries, with the HBO additive, exhibit stable cycling at high current density, achieving a cycling life of 1100 h at 10 and 10 mAh cm−2 as well as 250 h at 50% depth of discharge. Furthermore, the ZnǁVO2 coin cell demonstrates stable cycling for 1700 cycles at 1 A g−1 and 7000 cycles at 5 A g−1. This study presents a promising case for the commercialization of advanced ZIBs.

Induced Anionic Functional Group Orientation-Assisted Stable Electrode-Electrolyte Interphases for Highly Reversible Zinc Anodes.

Dendrite growth and other side-reaction problems of zinc anodes in aqueous zinc-ion batteries heavily affect their cycling lifespan and Coulombic efficiency, which can be effectively alleviated by the application of polymer-based functional protection layer on the anode. However, the utilization rate of functional groups is difficult to improve without destroying the polymer chain. Here, a simple and well-established strategy is proposed by controlling the orientation of functional groups (─SO3H) to assist the optimization of zinc anodes. Depending on the electrostatic effect, the surface-enriched ─SO3H groups increase the ionic conductivity and homogenize the Zn2+ flux while inhibiting anionic permeation. This approach avoids the destruction of the polymer backbone by over-sulfonation and amplifies the effect of functional groups. Therefore, the modified sulfonated polyether ether ketone (H-SPEEK) coating-optimized zinc anode is capable of longtime stable zinc plating/stripping, and moreover an enhanced cycling steadiness under high current densities is also detected in a series of Zn batteries with different cathode materials, which achieved by the inclusion of H-SPEEK coating without causing any harmful effects on the electrolyte and cathode. This work provides an easy and efficient approach to further optimize the plating/stripping of cations on metal electrodes, and sheds lights on the scale-up of high-performance aqueous zinc-ion battery technology.

A Chemical Sewing Enabled All‐In‐One Control Interface for Robust Zinc Metal Anodes

AbstractDeveloping artificial protective layers is an effective strategy to address the issue of dendrites for aqueous Zn‐metal batteries (ZMBS). However, drawbacks such as rough microscopic morphology, excessive thickness, and single functionality remain, limiting the attainment of a stable zinc anode. Herein, a novel multifunctional organic–inorganic hybrid artificial protective layer is produced by splicing inorganic fragments onto organic materials in situ using a chemical sewing. The protective layer is well‐compatible and also retains the function of organic and inorganic materials, which not only inhibits dendrite production but also alleviates Zn corrosion. The Si─OH bond of the zincophilic group enables planar Zn deposition while forming hydrogen bonds with water, suppressing water activity near the anode and reducing the hydrogen evolution reaction. As expected, the Zn||Zn symmetric cell with a protective layer provides high cycling stability of more than 1960 h at 1 mA cm−2, which is about 28 times higher than that of the symmetric cell assembled without the protective layer. More importantly, a Zn||V2O5 full cell with an ultra‐long lifetime has been achieved with an artificial protective layer. This work provides a potential viable path to achieve long‐lived ZMBS.

A Multifunctional Additive Based on the Cation-Anion Synergistic Effect for Highly Stable Zinc Metal Anodes.

The Zn dendrite and hydrogen evolution reaction have been a "stubborn illness" for the life span of zinc anodes, which significantly hinders the development of aqueous zinc batteries (AZBs). Herein, considering the ingenious molecular structure, a multifunctional additive based on the synergistic regulation of cations and anions at the interface is designed to promote a dendrite-free and stable Zn anode. Theoretical calculations and characterization results verified that the electrostatic shield effect of the cation, the solvation sheath structure, and the bilayer structural solid electrolyte film (SEI) jointly account for the uniform Zn deposition and side reaction suppression. Ultimately, a remarkably high average Coulombic efficiency (CE) of 99.4% is achieved in the Zn||Cu cell for 300 cycles, and a steady charge/discharge cycling over 3000 and 300 h at 1.0 mA cm-2/1.0 mAh cm-2 and 10 mA cm-2/10 mAh cm-2 is obtained in the Zn||Zn cell. Furthermore, the assembled full battery demonstrates a prolonged cycle life of 2000 cycles.

One-stone, two birds: One step regeneration of discarded copper foil in zinc battery for dendrite-free lithium deposition current collector

The ever-growing requirement for electrochemical energy storage has exacerbated the production of spent batteries, and the recycling of valuable battery components has recently received a remarkable attention. Among all battery components, copper foil is widely utilized as a current collector for stable zinc platting and stripping in zinc metal batteries (ZMBs) due to the perfect lattice matching of between metal copper and zinc, which is accompanied by the formation of multiple copper-zinc alloy components during the cycling process. Herein, a novel “two birds with one-stone” strategy through a one simple heat treatment step to revive the discarded copper foil in zinc metal battery is reported to further obtain a lithiophilic current collector (CuxZny-Cu) with multiple copper-zinc alloy components on the surface of the discarded copper foil. Such revived CuxZny-Cu current collector greatly reduces the lithium nucleation overpotential and realizes uniform lithium deposition and further inhibits lithium dendrites growth. The formed multiple CuxZny alloy phases on the surface of discarded copper foil exhibit a low Li nucleation overpotential of only 15 mV at 0.5 mA cm−2 for the first cycle. Moreover, such a CuxZny-Cu current collector could achieve stable cycle for 220 cycles at 0.5 mA cm−2 and 110 cycles at 1 mA cm−2 with a Li plating capacity of 1 mAh cm−2. Theoretical calculations indicate that, compared with pure Cu foil, the formed multiple alloy components of CuZn5, CuZn8, Cu0.61Zn0.39 and CuZn have low adsorption energy of −2.17, −2.55, −2.16 and −2.35 eV with lithium atoms, respectively, which result in reduced lithium nucleation overpotential. The full cell composed of CuxZny alloy current collector with deposition of 5 mAh cm−2 metal Li anode coupled with LiFePO4 (LFP) cathode exhibits a reversible capacity of 125.6 mAh/g after 110 cycles at a current of 0.5 C with capacity retention of 85.1 %. This work proposed a promising strategy to regenerate the discarded copper foil in rechargeable batteries.