Zn Batteries Research Articles

High mass loading potassium ion stabilized manganese dioxide nanowire forests for rechargeable Zn batteries

Manganese dioxide (MnO2) represents an ideal cathode material for rechargeable aqueous Zn batteries due to its high theoretical capacity (308 mAh g−1), suitable potential (1.4 V vs. Zn2+/Zn), natural abundance, and negligible toxicity. However, the capacity and rate capability of MnO2 deteriorate significantly in thick electrodes owing to its low electrical and ionic conductivities. Herein, we report the design of high mass loading potassium ion stabilized α-MnO2 (K0.133MnO2) nanowire forests on carbon cloth through a seed-assisted hydrothermal method for Zn batteries. The vertically aligned K0.133MnO2 nanowire forests with uninterrupted charge transport afford a high area capacity of 3.54 mAh cm−2 and a capacity retention of 79.2% over 1000 cycles in aqueous electrolyte. Moreover, the high area capacity and cyclability can be readily transferred to quasi-solid-state devices.

Ethanol as Solvent Additives with Competitive Effect for High-Stable Aqueous Zinc Batteries.

Aqueous zinc-ion batteries are emerging as promising sustainable energy-storage devices. However, their cyclic stability is still a great challenge due to the inevitable parasitic reaction and dendrite growth induced by water. Herein, a cosolvent strategy based on competitive effect is proposed to address the aforementioned challenges. Ethanol with a higher Gutmann donor number demonstrates lower polarity and better wettability on the Zn surface compared with water, which endows ethanol with the ability of minimizing water activity by weakening H bonds and preferentially adsorbing on the Zn electrode. The above competitive advantages synergistically contribute to inhibiting the decomposition of free water and dendrite growth. Besides, an organic-inorganic hybrid solid-electrolyte interphase layer is in situ built based on ethanol additives, where organic matrix suppresses water corrosion while inorganic fillers promote fast Zn2+ diffusion. Consequently, the electrolyte with ethanol additives boosts a high reversibility of Zn deposition, long-term durability, as well as superior Zn2+ diffusibility in both Zn half-cells (Zn||Cu and Zn||Zn batteries) and Zn full cells (Zn||PTCDA and Zn||VO2 batteries). This work sheds light on a universal strategy to design a high-reversible and dendrite-free Zn anode for stable aqueous batteries.

Design Principle of Insulating Surface Protective Layers for Metallic Zn Anodes: A Case Study of ZrO2

AbstractAqueous Zn batteries, which use metallic Zn as anodes, have gained significant attention due to their affordability and high safety standards. However, these Zn anodes are plagued by issues such as Zn dendritic growth and side reactions, including corrosion and hydrogen evolution. One straightforward yet effective approach to mitigate these issues is to apply protective coatings to the Zn anodes to enhance their reversibility. It is generally believed that these protective layers should have a high affinity for Zn. Contrarily, this study proposes that non‐conductive coatings should form a strong binding with H+ ions while maintaining a weaker interaction with Zn2+ ions, thereby ensuring a higher selectivity for H+ over Zn2+. This concept is illustrated using zirconium dioxide (ZrO2), an ionic conductor that meets these criteria and effectively curbs side reactions and dendritic growth of Zn. Remarkably, Zn anodes coated with ZrO2 layer demonstrate a lifespan exceeding 6000 h at 1 mA cm−2 and 1 mAh cm−2, significantly outperforming uncoated ones, which last <200 h. This discovery introduces a novel design principle for insulating surface coatings, potentially applicable not only for Zn but also for other metal anodes.

Scalable and economical production of oxygen deficient vanadium oxide with tunable vacancies concentration for bendable zinc ion batteries

Although vanadium oxides have high theoretical capacity and low cost, their practical application in aqueous zinc ion batteries (AZIBs) is bottlenecked by sluggish diffusion kinetics and capacity decline. Herein, the oxygen-deficient V2O5-x·nH2O (defined as VOd) with tunable oxygen vacancy concentration has been obtained via an economic and scalable method. The introduction of oxygen vacancies not only provides extra sites for Zn2+ storage, but also reduces the electrostatic barrier for Zn2+ intercalation, resulting in enhanced capacity and cycling stability. As a result, VOd cathode with proper amount of oxygen defect exhibits a high capacity of 415 mAh g−1 and energy density of 294 Wh kg−1 at 0.2 A g−1, estimating a roughly chemical costs of $64/kWH for VOd cathode. Besides, the VOd exhibits excellent stability at 20 A g−1 with average capacity decay of 0.004 % per cycle for 5000 cycles. Moreover, the bendable quasi-solid VOd//Zn battery maintains stable capacity of 200 mAh g−1 at 2 A g−1 even when repeatedly bending to straight angles. Therefore, the economical production of VOd cathode and construction of bendable quasi-solid battery provides a feasible way to boost the construction of efficient flexible energy storage devices and broadened application of AZIBs.

Activation and degradation mechanisms of α-V2O5 cathode materials in Zn-ion battery

Vanadium oxides with high specific capacity have been widely used as cathode materials for aqueous Zn-ion batteries. However, the interactions between the aqueous electrolytes and Vanadium oxides are still unclear. In particular, the intercalation of proton and water which can play a critical role in the degradation process is less well understood. Moreover, the mechanism for the capacity increase during the electrochemical cycling, known as the activation process, is still under debate. In this study, we systematically investigated the α-V2O5||Zn battery system with state-of-the-art characterization tools and electrochemical testing techniques to reveal the activation and degradation processes. It is discovered that the activation can be mainly attributed to the intercalation of protons and water in the first 100 cycles, which destabilizes the overall structural integrity, leading to capacity degradation afterward. It is also revealed that two main cathode electrolyte interface (CEI) components can be formed on the cathode surface, namely Zn3(V2O7)(OH)2·2H2O and Znm(CF3SO3)n(OH)2m-n·nH2O. The formation of Zn3(V2O7)(OH)2·2H2O-based CEI component is irreversible, while Znm(CF3SO3)n(OH)2m-n·nH2O-based CEI component can be reversibly cycled. Different structure-stabilizing charge/discharge protocols are proposed accordingly, which could leverage the structural integrity with thorough phase transition in the activation stage to enhance the cycling performance of the V-based cathodes. We hope to spur further interest in the fundamental understanding of the cathode materials in Zn-ion batteries.

Two-dimensional copper vanadate intercalated vanadium carbide MXene nanoplates as a high-performance cathode for aqueous Zn-ion batteries

Cathode materials play a crucial role in the energy-storage performances of zinc ion battery (ZIB). In this paper, the two-dimensional vanadium carbide MXene (V2C-MXene) nanoplates intercalated by Cu3V2O7(OH)2·2 H2O (CuVO) are synthesized. The intercalation of CuVO in the interlayers of V2C-MXene overcomes self-aggregation of CuVO and improves its structural stability. Meanwhile, the enlarged interlayer spacing of highly conductive V2C-MXene upgrades the electron transfer within the composite. As the cathode electrode of ZIB, the CuVO intercalated V2C-MXene (CuVO@V2C-MXene) battery shows capacity as high as 551.8 mAh g−1 when discharged at 0.5 A g−1. The capacity retention rate reaches 91.8% after 3000 cycles at high current density of 6.0 A g−1. As a comparison, the CuVO//Zn battery has capacity only 193.3 mAh g−1 at 0.5 A g−1, with the capacity retention of just 43.1% after 3000 cycles at 6.0 A g−1. Simultaneously, the CuVO@V2C-MXene//Zn illustrates greatly improved rate capability compared with CuVO//Zn. The CuVO@V2C-MXene composite nanoplates in this work show promise in fabrication of high capacity metal ion batteries.

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.

Revealing the role of calcium ion intercalation of hydrated vanadium oxides for aqueous zinc-ion batteries

Exploring suitable high-capacity V2O5-based cathode materials is essential for the rapid advancement of aqueous zinc ion batteries (ZIBs). However, the typical problem of slow Zn2+ diffusion kinetics has severely limited the feasibility of such materials. In this work, unique hydrated vanadates (CaVO, BaVO) were obtained by intercalation of Ca2+ or Ba2+ into hydrated vanadium pentoxide. In the CaVO//Zn and BaVO//Zn batteries systems, the former delivered up to a 489.8 mAh g−1 discharge specific capacity at 0.1 A g−1. Moreover, the remarkable energy density of 370.07 Wh kg−1 and favorable cycling stability yard outperform BaVO, pure V2O5, and many reported cathodes of similar ionic intercalation compounds. In addition, pseudocapacitance analysis, galvanostatic intermittent titration (GITT) tests, and Trasatti analysis revealed the high capacitance contribution and Zn2+ diffusion coefficient of CaVO, while an in-depth investigation based on EIS elucidated the reasons for the better electrochemical performance of CaVO. Notably, ex-situ XRD, XPS, and TEM tests further demonstrated the Zn2+ insertion/extraction and Zn-storage mechanism that occurred during the cycle in the CaVO//Zn battery system. This work provides new insights into the intercalation of similar divalent cations in vanadium oxides and offers new solutions for designing cathodes for high-capacity aqueous ZIBs.

Carbonate Ester-Based Electrolyte Enabling Rechargeable Zn Battery to Achieve High Voltage and High Zn Utilization.

Owing to the high H2O activity, the aqueous electrolyte in the Zn battery exhibits a narrow electrochemical window and inevitable hydrogen evolution reaction, limiting the anode utilization ratio and performance at high voltage. Carbonate ester, the well-developed electrolyte solvent in Li-ion batteries, exhibits aprotic properties and high anodic stability. However, its use in Zn metal batteries is limited due to the low solubility of Zn salts in carbonate esters. Herein, we propose a carbonate ester-based electrolyte (EC:DMC:EMC = 1:1:1 wt %), which contains a new Zn salt (Zn(BHFip)2) characterized by low cost, easy synthesis, and excellent aprotic solvent solubility. The BHFip- anion assists in forming Zn2+ conductive SEI on the anode and decomposes at high voltage to generate a protective CEI layer on the cathode. The Zn//Zn symmetric cell using such electrolyte achieves a remarkable Zn utilization ratio of 91% for 125 h, which has rarely been reported before. Furthermore, the Zn//LiMn2O4 full cell with an average operation voltage of 1.7 V demonstrates reliable cycling for 135 cycles with an N/P ratio of 1:1. In addition, the Zn//LiNi0.5Mn1.5O4 full cell exhibits a high discharge median voltage exceeding 2.2 V for 280 cycles, with the high voltage plateau (above 2 V) constituting 82% of the total capacity.

Boosting the reversibility of Zn anodes via synergistic cation–anion interface adsorption with addition of multifunctional potassium polyacrylate

Rechargeable aqueous Zn batteries have the edge in resource reserve, cost, energy and conversion efficiency due to the inherent features of metal Zn anodes. However, the application of Zn-based batteries is being seriously hindered by Zn dendrites and water-induced side-reactions. Here, potassium polyacrylate (K-PAM) is proposed as the electrolyte additive to form a synergistic cation–anion interface on Zn surface. The carboxyl anions and K+ cations are preferentially adsorbed on the Zn surface due to the intrinsic surfactant characteristics, which could homogenize Zn plating and suppress parasitic reactions. The synergistic regulation of K-PAM additive endows the ZnZn symmetric cells with excellent cyclic durability of 1250 h at 1 mA cm−2, which is significantly better than the polyacrylic acid additive only with carboxyl anions. Moreover, trace K-PAM addition into traditional ZnSO4 electrolyte endows the ZnCu batteries with a considerable average Coulombic efficiency of 99.2 %. Additionally, higher capacity retention and excellent cycling stability of ZnVO2 cells further mark K-PAM as a potentially impressive aqueous electrolyte additive for high-performance Zn-based batteries. This work will provide a promising method for the synergistic regulation with cations and anions of electrolyte additives to improve the stability and reversibility of Zn anodes.

A self-regulated interface enabled by trivalent gadolinium ions toward highly reversible zinc metal anodes

Aqueous zinc-ion batteries (AZIBs) have become an ideal candidate for large-scale energy storage systems owing to their inherent safety and highly competitive capacity. However, severe dendrite growth and side reactions on the surface of zinc metal anodes lead to quick performance deterioration, seriously impeding the commercialization of AZIBs. In this work, a self-regulated zinc metal/electrolyte interface is constructed to solve these problems by incorporating the trivalent Gd3+ additive with a lower effective reduction potential into the aqueous ZnSO4 electrolyte. It is revealed that the inert Gd3+ ions preferentially adsorb on the active sites of the zinc anode, and the induced electrostatic shielding layer is beneficial to uniform Zn deposition. Meanwhile, the adsorbed Gd3+ ions act as a buffer interface to lower the direct contact of the zinc anode with water molecules, thereby suppressing the interfacial parasitic reaction. These features endow the Zn//Zn battery using 0.2 M Gd3+ ions with 2940 h of cycling life at 5 mA cm−2 and a cumulative plating capacity (CPC) of 6.2 Ah cm−2 at 40 mA cm−2. When assembling with a MnO2 cathode, the full cell using the modified electrolyte exhibits a high capacity of 268.9 mAh/g at 0.2 A/g, as well as improved rate capability and cycle stability. The results suggest the great potential of a rare earth ion additive in reinforcing Zn metal anodes for developing practical AZIBs.

Separator pore size induced oriented Zn deposition

Aqueous zinc batteries (AZBs) are promising alternatives to lead-acid batteries for large-scale energy storage. In this work, we developed a TiO2-grafted polyethylene (TiO2-PE) separator for AZBs with excellent hydrophilicity. The TiO2-PE separator demonstrates the thinnest thickness of 9 μm, significantly decreasing the inactive mass of the entire battery comparing with the commercial glass fiber separator (260 μm). We further prove that the separator pore size can modulate the Zn deposition morphology. The (002)-orientated Zn deposition is induced when the pore size is smaller than the crystal critical length. Therefore, the 0.2 μm pores in TiO2-PE induce a (002)-orientated Zn deposition, while the 2 μm pores in glass fiber lead to a randomly oriented growth of Zn metal. This work highlights the opportunities in the pore size-modulated deposition/dissolution process in Zn and other metal batteries.

Two Birds with One Stone: Green Solvent Enabled High‐Stability and Durable Zn Anode in Both Non‐Aqueous and Aqueous Electrolytes

AbstractRechargeable zinc batteries are promising choices for eco‐friendly, safe and cost‐effective energy storage solutions. However, their commercial adoption faces challenges such as low Coulombic efficiency (CE) and poor reversibility of Zn anodes. To address these issues, a new green electrolyte based on N,N'‐Dimethylpropyleneurea (DMPU) has been developed, affording a robust, dendrite‐free Zn anode with over 5000 h of cycle stability and a high average CE of 98.49%. Zn anode in DMPU‐electrolyte significantly outperforms aqueous electrolyte with 67 times longer cycle life, demonstrating excellent anode stability. Moreover, ultra‐stable Zn anode in DMPU‐electrolyte cycled for over 10 000 cycles at 1.0 mA cm−2 showcases excellent reversibility. The Dimethylpropyleneurea‐triflate anion generated solid electrolyte interphase enables homogeneous and rapid Zn2+‐diffusion at the electrode interface, leading to a structured hexagonal Zn deposit. Furthermore, as electrolyte additive, DMPU significantly stabilizes Zn anode at severe conditions (5.0 and 10.0 mA cm−2) along with remarkable enhancement in CE (99.12%). This study offers valuable insights into the development of hybrid and organic electrolytes to advance Zn battery technology.

Synergistic Engineering of Carbon Nanotubes Threaded NiSe2/Co3Se4 Quantum Dots with Rich Se Vacancies for High‐Rate Nickel–Zinc Batteries

AbstractLimited by sluggish reaction kinetics, insufficient electrode utilization and severe volume deformation, designing nickel‐based materials with high capacity and rate capability is still a challenge. Herein, a carbon nanotubes threaded NiSe2/Co3Se4 quantum dots embedded in carbon nanospheres with rich Se vacancies both in NiSe2 and Co3Se4 is elaborately designed via MOF template method. The formation mechanism of the Se vacancies is elucidated for the first time, which is ascribed to the release of gas during the decomposition of organic ligand inhibits the ordered arrangement of atoms. The CNT‐V‐NiCoSe possesses many significant superiorities, such as sufficiently exposed active sites, high electrode utilization, favorable charge‐carrier migration, and relaxed structure deformation. Consequently, the CNT‐V‐NiCoSe electrode shows top‐level specific capacity (384 mAh g−1 at 1 A g−1), ultrahigh rate capability (209 mAh g−1 at 150 A g−1) and remarkable cycling durability. The CNT‐V‐NiCoSe//Zn battery achieves maximum energy density of 615.6 Wh kg−1 and maximum power density of 81.7 kW kg−1. Density functional theory calculations elucidate the Se vacancies improve the density of states at Fermi level, facilitates internal charge transfer, and enhances OH− adsorption ability. This study provides guidance for the preparation of high‐performance electrode materials with rich vacancies by template method.

Artificial Hydrophilic Organic and Dendrite-Suppressed Inorganic Hybrid Solid Electrolyte Interface Layer for Highly Stable Zinc Anodes.

Aqueous zinc-ion batteries (AZIBs) have gained significant attentions for their inherent safety and cost-effectiveness. However, challenges, such as dendrite growth and anodic corrosion at the Zn anode, hinder their commercial viability. In this paper, an organic-inorganic coating layer (Nafion-TiO2) was introduced to protect the Zn anode and electrolyte interface. Briefly, Nafion effectively shields against the corrosion from water molecules through the hydrophobic wall of -CF3 and guided zinc deposition from the -SO3 functional group, while TiO2 particles with a higher Young's modulus (151 GPa vs 120 GPa from Zn metal) suppress the zinc dendrite formation. As a result, with the protection of Nafion-TiO2, the symmetrical Zn∥Zn battery shows an improved cycle life of 1,750 h at 0.5 mA cm-2, and the full cell based on Zn∥MnO2 shows a long cycle life over 1,500 cycles at 1 A g-1. Our research offers a novel approach for protecting zinc metal anodes, potentially applicable to other metal anodes such as those in lithium and sodium batteries.

A Multifaceted Competitive Zn–Cu Battery Unleashed by Optimizing Charge Protocols

AbstractRechargeable alkaline Zn–Cu batteries show great potential for energy storage systems due to their high capacity, cost‐effectiveness, and environmental‐friendliness. However, restricted by the severe dissolution upon charging, rapid capacity decline occurs throughout the cycle. Herein, the charging protocol is adjusted to bypass the dissolution stage of high‐valent states, thereby preserving the optimal reaction section of Zn–Cu batteries and greatly improving cycling stability. Additionally, a self‐activation process in the initial stage led to the spontaneous transformation of the original electroplated Cu particles on nickel foam from 10 to 4 mm, enhancing both conductivity and mass transfer, ultimately increasing the utilization of active materials. The battery achieved a discharge capacity of 349.5 mAh g−1, an ultra‐flat charge–discharge voltage platform, over 92% energy efficiency, a low cost of only $43.25 per kWh, and an exceptionally stable cyclic performance with no noticeable decay over 400 cycles. These 5D improvements position the Cu electrode as a robust candidate for the positive electrode material in the next generation of commercial Zn batteries.

Bimetal-Initiated Concerted Zn Regulation Enabling Highly Stable Aqueous Zn-Ion Batteries

Aqueous zinc ion batteries are highly sought after for the next generation of sustainable energy storage systems. However, their development is significantly impeded by the presence of undesired zinc dendrites, which greatly reduce their cycle life. It is well-received that surface passivation by introducing foreign metals represents a compelling measure to enhance the stability of Zn anodes. Nevertheless, the vast potential of effecting concerted interplay between multiple metal elements for enhanced overall performance in Zn ion batteries remains elusive, due to the overwhelming challenge in creating uniform textures from hetero-units and understanding the mechanism underlying the synergistic performance gain. In this work, an innovative bimetallic overlaying strategy is proposed that renders possible the synergy between AgZn3 and CuZn5 in effecting uniform Zn deposition in a laterally confined and compact manner. The seeded growth of Zn on the bimetal-modulated interface effectively reduces the nucleation potential barrier, yielding a low nucleation overpotential (25 mV). In full cell testing with a commercial MnO2 applied as the cathode, superb cycling stability, surpassing the results reported in previous works, is achieved. The cell delivers an outstanding remaining capacity of 215 mA h g−1 after 300 cycles with almost no capacity degradation observed. The simple and highly efficient bimetal design, which synergizes the strengths of distinct metals, has the potential to drive innovations in the development of multicomponent aqueous Zn batteries with exceptional performance.

Dynamically Ion-Coordinated Bipolar Organodichalcogenide Cathodes Enabling High-Energy and Durable Aqueous Zn Batteries.

Bipolar organic cathode materials (OCMs) implementing cation/anion storage mechanisms are promising for high-energy aqueous Zn batteries (AZBs). However, conventional organic functional group active sites in OCMs usually fail to sufficiently unlock the high-voltage/capacity merits. Herein, we initially report dynamically ion-coordinated bipolar OCMs as cathodes with chalcogen active sites to solve this issue. Unlike conventional organic functional groups, chalcogens bonded with conjugated group undergo multielectron-involved positive-valence oxidation and negative-valence reduction, affording higher redox potentials and reversible capacities. With phenyl diselenide (PhSe-SePh, PDSe) as a proof of concept, it exhibits a conversion pathway from (PhSe)- to (PhSe-SePh)0 and then to (PhSe)+ as unveiled by characterization and theoretical simulation, where the diselenide bonds are periodically broken and healed, dynamically coordinating with ions (Zn2+ and OTF-). When confined into ordered mesoporous carbon (CMK-3), the dissolution of PDSe intermediates is greatly inhibited to obtain an ultralong lifespan without voltage/capacity compromise. The PDSe/CMK-3 || Zn batteries display high reversibility capacity (621.4 mAh gPDSe -1), distinct discharge plateau (up to 1.4 V), high energy density (578.3 Wh kgPDSe -1), and ultralong lifespan (12 000 cycles) at 10 A g-1, far outperforming conventional bipolar OCMs. This work sheds new light on conversion-type active site engineering for high-voltage/capacity bipolar OCMs towards high-energy AZBs.

Dynamically Ion‐Coordinated Bipolar Organodichalcogenide Cathodes Enabling High‐Energy and Durable Aqueous Zn Batteries

AbstractBipolar organic cathode materials (OCMs) implementing cation/anion storage mechanisms are promising for high‐energy aqueous Zn batteries (AZBs). However, conventional organic functional group active sites in OCMs usually fail to sufficiently unlock the high‐voltage/capacity merits. Herein, we initially report dynamically ion‐coordinated bipolar OCMs as cathodes with chalcogen active sites to solve this issue. Unlike conventional organic functional groups, chalcogens bonded with conjugated group undergo multielectron‐involved positive‐valence oxidation and negative‐valence reduction, affording higher redox potentials and reversible capacities. With phenyl diselenide (PhSe‐SePh, PDSe) as a proof of concept, it exhibits a conversion pathway from (PhSe)− to (PhSe‐SePh)0 and then to (PhSe)+ as unveiled by characterization and theoretical simulation, where the diselenide bonds are periodically broken and healed, dynamically coordinating with ions (Zn2+ and OTF−). When confined into ordered mesoporous carbon (CMK‐3), the dissolution of PDSe intermediates is greatly inhibited to obtain an ultralong lifespan without voltage/capacity compromise. The PDSe/CMK‐3 || Zn batteries display high reversibility capacity (621.4 mAh gPDSe−1), distinct discharge plateau (up to 1.4 V), high energy density (578.3 Wh kgPDSe−1), and ultralong lifespan (12 000 cycles) at 10 A g−1, far outperforming conventional bipolar OCMs. This work sheds new light on conversion‐type active site engineering for high‐voltage/capacity bipolar OCMs towards high‐energy AZBs.

Multifunctional Cellulose Nanocrystals Electrolyte Additive Enable Ultrahigh‐Rate and Dendrite‐Free Zn Anodes for Rechargeable Aqueous Zinc Batteries

AbstractThe design of aqueous zinc (Zn) chemistry energy storage with high rate‐capability and long serving life is a great challenge due to its inhospitable coordination environment and dismal interfacial chemistry. To bridge this big gap, herein, we build a highly reversible aqueous Zn battery by taking advantages of the biomass‐derived cellulose nanocrystals (CNCs) electrolyte additive with unique physical and chemical characteristics simultaneously. The CNCs additive not only serves as fast ion carriers for enhancing Zn2+ transport kinetics but regulates the coordination environment and interface chemistry to form dynamic and self‐repairing protective interphase, resulting in building ultra‐stable Zn anodes under extreme conditions. As a result, the engineered electrolyte system achieves a superior average coulombic efficiency of 97.27 % under 140 mA cm−2, and steady charge–discharge for 982 h under 50 mA cm−2, 50 mAh cm−2, which proposes a universal pathway to challenge aqueous Zn chemistry in green, sustainable, and large‐scale applications.