Suppress Dendrite Growth Research Articles

Unraveling the Role and Impact of Alumina on the Nucleation and Reversibility of β‐LiAl in Aluminum Anode Based Lithium‐Ion Batteries

AbstractAluminum, due to its high abundance, very attractive theoretical capacity, low cost, low (de−) lithiation potential, light weight, and effective suppression of dendrite growth, is considered as a promising anode candidate for lithium‐ion batteries (LIBs). However, its practical application is hindered due to multiple detrimental challenges, including the formation of an amorphous surface oxide layer, pulverization, and insufficient lithium diffusion kinetics in the α‐phase. These outstanding intrinsic challenges need to be addressed to facilitate the commercial production of Al‐based batteries. The native passivation layer, Al2O3, plays a critical role in the nucleation and reversibility of lithiating aluminum and is thoroughly investigated in this study using high precision electrochemical micro calorimetry. The enthalpy of crystallization of β‐LiAl is found to be 40.5 kJ mol−1, which is in a strong agreement with the value obtained by calculation using Nernst equation (40.04 kJ mol−1). Surface treatment of the active material by the addition of 25 nm of alumina increases the nucleation energy barrier by 83 % over the native oxide layer. After the initial nucleation, the added alumina does not negatively impact the reversibility at 0.1 C rate, suggesting the removal of alumina is not necessary for improving the cyclability of aluminum anode based lithium‐ion batteries. Moreover, the coulombic efficiencies are also found to be slightly higher in the alumina treated samples compared to the untreated ones.

Amorphous High‐Entropy Alloy Interphase for Stable Lithium Metal Batteries

AbstractThe unstable anode/electrolyte interphase induces severe lithium dendrite growth hindering the practical application of lithium metal batteries. The lithium alloy interphase presents a promising strategy for regulating Li+ plating/stripping behavior. However, binary or ternary alloys are insufficient to address various challenges in lithium metal batteries and the high temperature required for alloy preparation hampers their direct applications on lithium metal surfaces. In this study, a high‐entropy alloy (HEA) interphase is developed on lithium metal surfaces via room‐temperature magnetron sputtering, showcasing multifunctional advantages in regulating Li+ plating/stripping behavior. The cocktail effect of the (HEA) facilitated the formation of a homogeneous amorphous interphase with abundant lithiophilic sites and magnetic properties, promoting uniform Li+ nucleation and deposition. Furthermore, the high mechanical strength and corrosion resistance of HEA provided physicochemical stability for the lithium anode interphase, consistently suppressing dendrite growth. Consequently, lithium metal anodes with HEA interphases exhibited robust cycling performance lasting over 4000 h at 2 mA cm−2. The LFP full battery demonstrated high‐capacity retention of 90% with an average Coulombic efficiency of 99.7%. Thus, the HEA interphases on lithium metal surfaces offer controllable regulation of Li+ deposition behavior through high‐entropy manipulation, opening novel strategies for stable lithium metal batteries.

Rational design of hybrid electrolyte for all-solid-state lithium battery based on investigation of lithium-ion transport mechanism

Lithium all-solid-state batteries (ASSBs) are a promising technology for achieving high energy density, long cycle life, and safe rechargeable battery systems. Among these, Li ASSBs using solid polymer electrolytes (SPEs) have gained attention owing to their processability, lightweight nature, flexibility, and favorable electrode contacts. However, SPEs have low ionic conductivity, low Li+ transference number, and lack mechanical strength, limiting cell performance. Therefore, the present study focuses on the development of hybrid polymer electrolytes (HPEs) by incorporating Li1+xAlxTi2-x(PO4)3 (LATP) of Li/Na superionic conductor-type materials into SPEs. The HPEs with LATP 10 wt% exhibited significant improvements with an ionic conductivity of 7.23 × 10−4 S cm−1 at 45 °C and a Li+ transference number of 0.61. Density functional theory calculations supported the enhanced Li-ion migration through the polymer-LATP interface achieved by the optimized LATP content. The addition of LATP particles enhanced the mechanical strength of the electrolytes, effectively suppressing dendrite growth, resulting in a 66.65 % capacity retention after 320 cycles, highlighting the crucial role of high-performance HPEs in advanced ASSBs. By addressing the limitations of SPEs, HPEs offer promising opportunities to unlock the full potential of solid-state battery technologies for various energy storage systems.

Amorphous FeSnOx Nanosheets with Hierarchical Vacancies for Room-Temperature Sodium-Sulfur Batteries.

Room-temperature sodium-sulfur (RT Na-S) batteries, noted for their low material costs and high energy density, are emerging as a promising alternative to lithium-ion batteries (LIBs) in various applications including power grids and standalone renewable energy systems. These batteries are commonly assembled with glass fiber membranes, which face significant challenges like the dissolution of polysulfides, sluggish sulfur conversion kinetics, and the growth of Na dendrites. Here, we develop an amorphous two-dimensional (2D) iron tin oxide (A-FeSnOx) nanosheet with hierarchical vacancies, including abundant oxygen vacancies (Ovs) and nano-sized perforations, that can be assembled into a multifunctional layer overlaying commercial separators for RT Na-S batteries. The Ovs offer strong adsorption and abundant catalytic sites for polysulfides, while the defect concentration is finely tuned to elucidate the polysulfides conversion mechanisms. The nano-sized perforations aid in regulating Na ions transport, resulting in uniform Na deposition. Moreover, the strategic addition of trace amounts of Ti3C2 (MXene) forms an amorphous/crystalline (A/C) interface that significantly improves the mechanical properties of the separator and suppresses dendrite growth. As a result, the task-specific layer achieves ultra-light (~0.1 mg cm-2), ultra-thin (~200 nm), and ultra-robust (modulus=4.9 GPa) characteristics. Consequently, the RT Na-S battery maintained a high capacity of 610.3 mAh g-1 and an average Coulombic efficiency of 99.9 % after 400 cycles at 0.5 C.

Amorphous FeSnOx Nanosheets with Hierarchical Vacancies for Room‐Temperature Sodium‐Sulfur Batteries

AbstractRoom‐temperature sodium‐sulfur (RT Na−S) batteries, noted for their low material costs and high energy density, are emerging as a promising alternative to lithium‐ion batteries (LIBs) in various applications including power grids and standalone renewable energy systems. These batteries are commonly assembled with glass fiber membranes, which face significant challenges like the dissolution of polysulfides, sluggish sulfur conversion kinetics, and the growth of Na dendrites. Here, we develop an amorphous two‐dimensional (2D) iron tin oxide (A‐FeSnOx) nanosheet with hierarchical vacancies, including abundant oxygen vacancies (Ovs) and nano‐sized perforations, that can be assembled into a multifunctional layer overlaying commercial separators for RT Na−S batteries. The Ovs offer strong adsorption and abundant catalytic sites for polysulfides, while the defect concentration is finely tuned to elucidate the polysulfides conversion mechanisms. The nano‐sized perforations aid in regulating Na ions transport, resulting in uniform Na deposition. Moreover, the strategic addition of trace amounts of Ti3C2 (MXene) forms an amorphous/crystalline (A/C) interface that significantly improves the mechanical properties of the separator and suppresses dendrite growth. As a result, the task‐specific layer achieves ultra‐light (~0.1 mg cm−2), ultra‐thin (~200 nm), and ultra‐robust (modulus=4.9 GPa) characteristics. Consequently, the RT Na−S battery maintained a high capacity of 610.3 mAh g−1 and an average Coulombic efficiency of 99.9 % after 400 cycles at 0.5 C.

Effects of solid electrolyte particle size and silver-carbon interlayer on lithium deposition in all-solid-state lithium-metal batteries

All-solid-state batteries with lithium-metal anodes are expected to exhibit high performance. For practical application, the growth of lithium dendrites must be suppressed. One method to suppress dendrite growth is to insert a carbon interlayer at the interface between the anode and solid electrolyte (SE). Dendrite growth is related to the anode interface properties and depends on the SE particle size used in the SE layer. Appropriate control of the SE particle size used at the anode interface can improve battery performance. In this study, the effects of SE particle size and carbon interlayer type on lithium-metal deposition morphology are investigated by X-ray CT measurement. The results show that dendrite growth is suppressed when the small-particle SE is used owing to the smaller pores between the SE layer and carbon interlayer. In addition, by controlling the SE particle size distribution using a double SE layer, both high ionic conductivity and dendrite suppression can be achieved. Furthermore, dendrite growth can be suppressed using a silver particle-added carbon interlayer, even with the large-particle SE where dendrites are prone to grow more easily.

Anti-corrosive and carbonyl-rich interlayer enables highly reversible zinc anode

Aqueous zinc ion batteries (AZIBs) are considered as highly promising candidates for large-scale energy storage due to their exceptional safety profile, environmental sustainability, and cost-effectiveness. However, the progress of AZIBs is impeded by several challenges including the formation of zinc dendrites, self-corrosion issues, and hydrogen evolution. Herein, we demonstrate the in-situ fabrication of a hydrophobic and carbonyl-rich zinc phthalate (ZCHO) solid electrolyte interphase (SEI) layer on the zinc foil through a facile liquid deposition method. The incorporation of carbonyls into the ZCHO layer enhances ion migration dynamics by attracting Zn2+, while also promoting preferential deposition onto the (002) surface, effectively mitigating water-induced corrosion and hydrogen evolution, likewise reducing charge transfer resistance. These inherent advantages contribute to a homogeneous distribution of Zn2+ concentration on the zinc anode surface, thereby suppressing dendrite growth. The results demonstrate that the symmetric battery exhibits an impressive cycle life of over 2300 h under a current density of 1 mA cm−2, with an areal capacity of 0.5 mAh cm−2. Additionally, it demonstrates stable cycling for more than 700 h at 5 mA cm−2, 0.25 mAh cm−2. Furthermore, when assembled with NH4V4O10, the full battery delivers a specific capacity of 222.9 mAh g−1 after undergoing 1000 cycles under a current density of 5 A g−1 while maintaining a capacity retention rate of 86.26 %. This study presents a novel and facile approach to advance research on high-performance AZIBs.

Isomeric dichloropyrazine of dual-function additives: Synergistic enhancement of lithium anode protection and sulfur redox kinetics in lithium–sulfur batteries

Lithium-sulfur batteries (LSBs) currently face challenges such as low sulfur utilization, inadequate cycling stability, and unstable lithium anode interfaces. In this study, dichloropyrazines (DCPs) are introduced as dual-functional additives into electrolyte and 2,5-DCP exhibits the most promising performance enhancement. This superiority can be attributed to its strong redox activity, lower molecular orbital energy gap, and more negative relative binding energy compared to the other DCP isomers. Specifically, DCPs demonstrate their dual functionality by promoting the formation of a stable organic-inorganic hybrid solid electrolyte interface (SEI) rich in LiCl on lithium anodes. This ensures uniform lithium deposition and suppresses dendrite growth. At sulfur cathodes, density functional theory (DFT) calculations confirm that DCPs facilitate lithium polysulfides (LiPSs) conversion kinetics through Li–N bond formation. LSBs with 2,5-DCP exhibit excellent stability at a 1C rate and retain 86.6 % capacity after 800 cycles. This study demonstrates DCPs' potential as effective dual-functional electrolyte additives in designing high-performance LSBs.

Anion trapping-coupling strategy driven asymmetric nonflammable gel electrolyte for high performance sodium batteries

Gel polymer electrolytes, promising electrolyte candidates for advanced sodium metal batteries (SMBs), suffer from the great challenges of combustion risk and inferior interfacial stability caused by poor mechanical properties and low Na+ selectivity. Herein, we proposed a rational anion trapping-coupling strategy to build a mechanically robust asymmetric nonflammable composite gel electrolyte (AS-NFCGE) by introducing in-situ coupled boron nitride nanosheets (BNNs) on glass fiber matrix embedded with synchronous polymerized flame-retardant polymer. Theoretical calculations, finite-element simulations, and experimental tests prove that the high coupling BNNs with anion trapping effect constructed asymmetric structure can significantly accelerate selective Na+ migration kinetics, enhance mechanical properties of AS-NFCGE and endow a similar single-ion conducting behavior to homogenize ion-distribution at the anode side, thus improving interfacial stability and suppressing dendrite growth to achieve ultra-stable SMBs. Specifically, the AS-NFGE delivers high ionic conductivity and Na+ transference number (0.73) together with excellent flam-retardant. Consequently, the dendrite-free Na/Na symmetric cell exhibits considerable cycling life for over 3000 h at 0.1 mA cm−2 with low overvoltage. Applications of the AS-NFCGE in SMBs further demonstrate the excellent electrochemical performances, and no thermal runaway and no electrolyte leakage occur for pouch cells using AS-NFCGE. This strategy provides new insight into the development of safe and high-energy SMBs and the beyond.

Water-Capture Filter Paper Separator Realizing Ambient Li-Air Battery.

Lithium-air battery (LAB) is regarded as one of the most promising energy storage systems. However, the challenges arising from the lithium metal anode have significantly impeded the progress of LAB development. In this study, cellulose-based filter paper (FP) is utilized as a separator for ambient Li-air batteries to suppress dendrite growth and prevent H2O crossover. Thermogravimetric analysis and molecular spectrum reveal that FP enables ambient Li-air battery operation due to its surface functional groups derived from cellulose. The oxygen-enriched surface of cellulose not only enhances ion conductivity but also captures water and confines solvent molecules, thereby mitigating anode corrosion and side reactions. Compared with commercial glassfiber (GF) separator, this cellulose-based FP separator is cheaper, renewable, and environmentally friendly. Moreover, it requires less electrolyte while achieving prolonged and stable cycle life under real air environment conditions. This work presents a novel approach to realizing practical Li-air batteries by capturing water on the separator's surface. It also provides insights into the exploration and design of separators for enabling practical Li-air batteries toward their commercialization.

Extension of Aqueous Zinc Battery Life Using a Robust and Hydrophilic Polymer Separator

AbstractThe use of zinc (Zn) metal as an anode in aqueous batteries offers an eco‐friendly and cost‐effective energy storage solution. However, Zn dendrite formation severely restricts the cycle life of the battery toward practical application. Herein, a commercially hydrophilic polytetrafluoroethylene (PTFE) membrane is demonstrated as a separator to significantly extend the cycle life of the Zn metal anode. In contrast with the conventional fragile glass fiber separator, a wetted PTFE separator exhibited high mechanical strength (stress of 34.3 MPa at 41.4% strain) and favorable hydrophilicity, which both efficiently suppress dendrite growth. The uniform and robust pore structures are proven to facilitate a homogeneous Zn2+ ion flux and a high transfer number of Zn2+ (0.81), which has guaranteed reversible Zn plating/stripping. As a proof of concept, the PTFE separator extended the cycle life considerably to over 3000 h and promoted a Zn plating/stripping efficiency of 99.5% in the unmodified 2 m ZnSO4 aqueous electrolyte. This advancement underscores the significant potential of the PTFE separator for enhancement of the cycling durability of aqueous zinc‐ion batteries (AZIBs).

Constructing Highly Stable Zinc Metal Anodes via Induced Zn(002) Growth.

The nonuniform electric field at the surface of a zinc (Zn) anode, coupled with water-induced parasitic reactions, exacerbates the growth of Zn dendrites, presenting a significant impediment to large-scale energy storage in aqueous Zn-ion batteries. One of the most convenient strategies for mitigating dendrite-related issues involves controlling crystal growth through electrolyte additives. Herein, we present thiamine hydrochloride (THC) as an electrolyte additive capable of effectively stabilizing the preferential deposition of the Zn(002) plane. First-principles calculations reveal that THC tends to adsorb on Zn(100) and Zn(101) planes and is capable of inducing the deposition of Zn ion onto the (002) plane and the preferential growth of the (002) plane, resulting in a flat and compact deposition layer. A THC additive not only effectively suppresses dendrite growth but also prevents the generation of side reactions and hydrogen evolution reaction. Consequently, the Zn||Zn symmetric battery exhibits long-term cycling stability of over 3000 h at 1 mA cm-2/1 mAh cm-2 and 1000 h at 10 mA cm-2/10 mAh cm-2. Furthermore, the NH4V4O10||Zn full battery also displays excellent cycling stability and a high reversible capacity of 210 mAh g-1 after 1000 cycles at 1 A g-1, highlighting a significant potential for practical applications.

In Situ Forming Na─Sn Alloy/Na2S Interface Layer for Ultrastable Solid State Sodium Batteries

AbstractThe poor interfacial compatibility between sodium superionic conductor (NASICON) electrolyte and metallic sodium anode will lead to severe dendrite penetration, impeding the application of NASICON electrolytes for solid state sodium batteries. Herein, a homogeneous SnS2 coating layer is sputtered on the surface of Na3.4Zn0.1Zr1.9Si2.2P0.8O12 electrolyte to in situ construct a kinetically stable Na─Sn alloy/Na2S interlayer, possessing superior Na affinity, low diffusion barrier, and electronic insulating character to suppress dendrite growth, which is confirmed by experiments and density‐functional theory calculations. Benefiting from the Na─Sn alloy/Na2S interphase, the critical current density of Na3.4Zn0.1Zr1.9Si2.2P0.8O12 increases from 2.4 to 9.4 mA cm−2. In addition, the obtained Na3V2(PO4)3/Na3.4Zn0.1Zr1.9Si2.2P0.8O12@SnS2/Na solid state batteries exhibit a high initial reversible discharge capacity of 115.1 mAh g−1 at 0.1 °C with an initial Coulombic efficiency of 93.6%, and a capacity retention rate of 88.1% after 1000 cycles at 1 C.

β''-Al2O3 protecting layer for stable zinc metal anodes

Aqueous zinc-ion batteries (AZIB) has attracted considerable attention on account of its low cost, high security and environmental friendliness. Nevertheless, the growing dendrites and corrosion reactions on the surface of zinc anode limit the development of AZIB. Herein, β''-Al2O3 with high ion conductivity was firstly employed as an efficient artificial layer for stabilizing the zinc anode. The optimized β''-Al2O3 layer enables homogeneous ion flux and uniform zinc deposition, significantly suppressing dendrite growth and parasitic reactions. Symmetric cells based on this unique protective layer can stably operate for 1600 h under 1 mA cm−2/1 mAh cm−2. Benefiting from the high-performance zinc metal anode, the full cell paired with the NH4V4O10 cathode delivers a high discharge initial capacity of 400 mAh g−1 at 1 A g−1 and good cycling stability. This simple protecting layer provides a new strategy for the modification of zinc metal anode and accelerates the practical application of AZIB.

Ultralong Cycling and Safe Lithium-Sulfur Pouch Cells for Sustainable Energy Storage.

While layered metal oxides remain the dominant cathode materials for the state-of-the-art lithium-ion batteries, conversion-type cathodes such as sulfur present unique opportunities in developing cheaper, safer, and more energy-dense next-generation battery technologies. There has been remarkable progress in advancing the laboratory scale lithium-sulfur (Li-S) coin cells to a high level of performance. However, the relevant strategies cannot be readily translated to practical cell formats such as pouch cells and even battery pack. Here these key technical challenges are addressed by molecular engineering of the Li metal for hydrophobicization, fluorination and thus favorable anode chemistry. The introduced tris(2,4-di-tert-butylphenyl) phosphite (TBP) and tetrabutylammonium fluoride (TBA+F-) as well as cellulose membrane by rolling enables the formation of a functional thin layer that eliminates the vulnerability of Li metal towards the already demanding environment required (1.55% relative humidity) for cell production and gives rise to LiF-rich solid electrolyte interphase (SEI) to suppress dendrite growth. As a result, Li-S pouch cells assembled at a pilot production line survive 400 full charge/discharge cycles with an average Coulombic efficiency of 99.55% and impressive rate performance of 1.5 C. A cell-level energy density of 417Wh kg-1 and power density of 2766W kg-1 are also delivered via multilayer Li-S pouch cell. The Li-S battery pack can even power an unmanned aerial vehicle of 3kg for a fairly long flight time. This work represents a big step forward acceleration in Li-S battery marketization for future energy storage featuring improved safety, sustainability, higher energy density as well as reduced cost.

Artificial LiF‐Rich Interface Enabled by In situ Electrochemical Fluorination for Stable Lithium‐Metal Batteries

AbstractLithium (Li)‐metal batteries are promising next‐generation energy storage systems. One drawback of uncontrollable electrolyte degradation is the ability to form a fragile and nonuniform solid electrolyte interface (SEI). In this study, we propose the use of a fluorinated carbon nanotube (CNT) macrofilm (CMF) on Li metal as a hybrid anode, which can regulate the redox state at the anode/electrolyte interface. Due to the favorable reaction energy between the plated Li and fluorinated CNTs, the metal can be fluorinated directly to a LiF‐rich SEI during the charging process, leading to a high Young's modulus (~2.0 GPa) and fast ionic transfer (~2.59×10−7 S cm−1). The obtained SEI can guide the homogeneous plating/stripping of Li during electrochemical processes while suppressing dendrite growth. In particular, the hybrid of endowed full cells with substantially enhanced cyclability allows for high capacity retention (~99.3 %) and remarkable rate capacity. This work can extend fluorination technology into a platform to control artificial SEI formation in Li‐metal batteries, increasing the stability and long‐term performance of the resulting material.

Accelerated Selective Li+ Transports Assisted by Microcrack-Free Anionic Network Polymer Membranes for Long Cyclable Lithium Metal Batteries.

Rechargeable Li metal batteries have the potential to meet the demands of high-energy density batteries for electric vehicles and grid-energy storage system applications. Achieving this goal, however, requires resolving not only safety concerns and a shortened battery cycle life arising from a combination of undesirable lithium dendrite and solid-electrolyte interphase formations. Here, a series of microcrack-free anionic network polymer membranes formed by a facile one-step click reaction are reported, displaying a high cation conductivity of 3.1 × 10-5 S cm-1 at high temperature, a wide electrochemical stability window up to 5V, a remarkable resistance to dendrite growth, and outstanding non-flammability. These enhanced properties are attributed to the presence of tethered borate anions in microcrack-free membranes, which benefits the acceleration of selective Li+ cations transport as well as suppression of dendrite growth. Ultimately, the microcrack-free anionic network polymer membranes render Li metal batteries a safe and long-cyclable energy storage device at high temperatures with a capacity retention of 92.7% and an average coulombic efficiency of 99.867% at 450 cycles.

Concentration-Driven Interfacial Amorphization toward Highly Stable and High-Rate Zn Metal Batteries.

The interfacial structure holds great promise in suppressing dendrite growth and parasitic reactions of zinc metal in aqueous media. Current advancements prioritize novel component fabrication, yet the local crystal structure significantly impacts the interfacial properties. In addition, there is still a critical need for scalable synthesis methods for expediting the commercialization of aqueous zinc metal batteries (AZMBs). Herein, we propose a scalable concentration-controlled method for realizing crystalline to amorphous transformation of the Zn metal interface with exceptional scalability (>1 m2) and processing consistency (>30 trials). Theoretical and experimental analyses highlight the advantages of amorphous ZnO, which exhibits moderate adsorption energy, strong desolvation ability, and hydrophilicity. Employing the amorphous ZnO-coated zinc metal anode (AZO-Zn) significantly enhances the cycling performance, impressively maintaining 1000 cycles at 100 mA cm-2. The prototype AZO-Zn||MnO2@CNT pouch cell demonstrates a capacity of 15.7 mAh and maintains 91% of its highest capacity over 100 cycles, presenting promising avenues for the future commercialization of AZMBs.

Zn Anode Surviving Extremely Corrosive Polybromide Environment with Alginate-Graphene Oxide Hydrogel Coating.

Zinc-bromine (Zn-Br) redox provides a high energy density and low-cost option for next-generation energy storage systems, and polybromide diffusion remains a major issue leading to Zn anode corrosion, dendrite growth, battery self-discharge and limited electrochemical performance. A dual-functional Alginate-Graphene Oxide (AGO) hydrogel coating is proposed to prevent polybromide corrosion and suppress dendrite growth in Zn-Br batteries through negatively charged carboxyl groups and enhanced mechanical properties. The battery with anode of plain zinc coated with AGO (Zn]AGO) survives a severely corrosive environment with higher polybromide concentration than usual without a membrane, and achieves 80 cycles with 100% Coulombic and 80.65% energy efficiencies, four times compared to plain Zn anode. The promising performance is comparable to typical Zn-Br batteries using physical membranes, and the AGO coating concept can be well adapted to various Zn-Br systems to promote their applications.

Competitive Coordination Structure Regulation in Deep Eutectic Electrolyte for Stable Zinc Batteries.

Rechargeable zinc-based batteries are finding their niche in energy storage applications where cost, safety, scalability matter, yet they are plagued by rapid performance degradation due to the lack of suitable electrolytes to stabilize Zn anode. Herein, we report a competitive coordination structure to form unique quaternary hydrated eutectic electrolyte with ligand-cation-anion cluster. Unraveled by experiment and calculation results, the competing component can enter initial primary coordination shell of Zn2+ ion, partially substituting Lewis basic eutectic ligands and reinforcing cation-anion interaction. The hydration-deficient complexes induced between competing eutectic as hydrogen bond donor-accepter and water also broaden the electrochemical window and confine free water activity. The altered coordination further leads to robust hybrid organic-inorganic enriched solid electrolyte interphase, enabling passivated surface and suppressed dendrite growth. Noticeably, stable Zn plating/stripping for 8000 cycles with high Coulombic efficiencies of 99.6 % and long cycling life of 10000 cycles for Zn-organic batteries are obtained. Even under harsh conditions (small N/P ratio, low temperature), the profits brought by the competitive eutectic electrolyte are still very prominent. This design principle leveraged by eutectic electrolytes with competitive coordination offers a new approach to improve battery performance.