High Coulombic Efficiency Research Articles

Molecular Design of Imino Anion Acceptors Enables Long‐Life Fluoride Ion Batteries

AbstractAnion acceptors (AAs) enable to dissolve metal fluoride salts and achieve reversible fluorination and defluorination in fluoride ion batteries (FIBs). However, most reported strategies only focus on boron‐ and alcohol‐based AAs with strong Lewis acidity and excessive hydrogen bond (HB) strength, which often leads to the uncontrollable mass loss of active materials and the inferior reduction stability of electrolyte. Although amino and imine groups possess preferable anti‐reductive property, their HB strengths are apparently too weak to dissociate fluoride salts. Here a novel strategy is proposed for molecular structure design toward imino AAs by introducing double bonds and pyridine‐N into the five‐membered‐ring of pyrrolidine. Therein the conjugation effect, inductive effect, and α effect are synergistically utilized to enhance the Lewis acidity of imino group. Theoretical calculations and experiments prove that 1,2,4‐triazole AA retains the reduction stability in the maximum extent while increasing the HB strength of imino group. Based on this imino AA, the electrolyte achieves an unprecedented wide electrochemical stability window (5.5 V), enabling highly reversible cycling of fluorination and defluorination for CuF2||Pb full cells (>300 cycles) with a Cu+‐mediated two‐step redox mechanism, for PbF2‐Pb||PbF2‐Pb symmetric cells (1600 h) with low overpotential, and for PbF2||Pb asymmetric cells with high coulombic efficiency.

Room-Temperature CsPbI3-Quantum-Dot Reinforced Solid-State Li-Polymer Battery.

A novel polymer electrolyte based on CsPbI3 quantum dots (QDs) reinforced polyacrylonitrile (PAN), named as PIL, is exploited to address the low room-temperature (RT) ion conductivity and poor interfacial compatibility of polymer solid-state electrolytes. After optimizing the content of CsPbI3 QDs, RT ion conductivity of PIL largely increased from 0.077 to 0.56 mS cm-1, and its Li-ion transference number ( ) from 0.20 to 0.63. It is revealed that the synergistic enhancement of Li-ion transport and interface stability is realized by CsPbI3 QDs through Lewis acid-base interaction, ordered polarization of PAN, and interface chemical regulation. These two effects guarantee the robust solid-electrolyte interface (SEI) in PIL-based solid-state batteries. Consequently, PIL electrolyte enables solid-state Li-metal batteries to deliver extraordinary RT cycling performance as verified by excellent cycling stability (>2000h at 0.1mA cm-2) of Li|PIL|Li symmetric batteries. Moreover, Li|PIL|LFP (LFP is LiFePO4) and Li|PIL|NCM811(NCM811 is Li(Ni0.8Co0.1Mn0.1)O2) batteries maintain capacity retention of 81.2% and 77.9%, respectively, after 600 cycles at 0.5 C, as well as good rate-capability and very high Coulombic efficiency at RT.

Tailoring a High Loading Atomic Zinc with Weak Binding to Sodium Toward High-Energy Sodium Metal Batteries.

Single-atom materials provide a platform to precisely regulate the electrochemical redox behavior of electrode materials with atomic level. Here, a multifield-regulated sintering route is reported to rapidly prepare single-atom zinc with a very high loading mass of 24.7 wt.% by significantly improved diffusion kinetics and stronger charge transfer between zinc and nitrogen atoms. X-ray absorption near edge structure (XANES) spectra for Zn K-edges during the charge and discharge process verify the stable single-atom zinc structure and the reversible slight reduction and oxidation of Zn sites, which is much different from the previous report of the alloying reaction process. This result suggests atomic Zn acts as an active sites through weak binding with sodium to regulate the Na ion fluxes. Finally, Cu foil coated with a ≈2µm layer of such material exhibits a high Coulombic efficiency of ≈99.99% up to 1700 cycles at 1mAhcm-2. An ultra-low overpotential of 3mV and an unprecedented life span of over 3200h in a symmetrical cell is achieved. Due to the very thin coating layer, anode-free sodium battery fabricated by Na3V2(PO4)3 cathode displays a prominent energy density of 320WhKg-1, demonstrating strong potential in practical application.

Realizing an Energy-Dense Potassium Metal Battery at -40 °C via an Integrated Anode-Free and Dual-Ion Strategy.

Potassium (K)-based batteries hold great promise for cryogenic applications owing to the small Stokes radius and weak Lewis acidity of K+. Nevertheless, energy-dense (>200 W h kg-1cathode+anode) K batteries under subzero conditions have seldom been reported. Here, an over 400 W h kg-1cathode+anode K battery is realized at -40 °C via an anode-free and dual-ion strategy, surpassing these state-of-the-art K batteries and even most Li/Na batteries at low temperatures (LTs). By introduction of a strongly associating salt as an additive to this anode-free K battery, an anion-derived solid electrolyte interphase can be established for a highly reversible, zero-excess K plating/stripping behavior on a bare current collector. Meanwhile, a binary solvent is rationally designed for lowering the cation desolvation energy barrier, which ensures comparably facile cation and desolvation-free anion kinetics in this dual-ion structure even at LTs. Consequently, the K||Al half-cell delivers a high Coulombic efficiency of 99.98% at -40 °C. By pairing with a high-energy cathode, a proof-of-concept anode-free K dual-ion battery (N/P = 0) is fabricated, delivering a record-high energy density of 407 W h kg-1cathode+anode with stable cycling of 183 cycles (80% capacity retention) at -40 °C. This work paves a way toward energy-dense batteries at extreme scenarios.

Monofluorinated acetal electrolyte for high-performance lithium metal batteries

High degree of fluorination for ether electrolytes has resulted in improved cycling stability of lithium metal batteries due to stable solid electrolyte interphase (SEI) formation and good oxidative stability. However, the sluggish ion transport and environmental concerns of high fluorination degree drive the need to develop less fluorinated structures. Here, we depart from the traditional ether backbone and introduce bis(2-fluoroethoxy)methane (F2DEM), featuring monofluorination of the acetal backbone. High coulombic efficiency and stable long-term cycling in Li||Cu half cells can be achieved with F2DEM even under fast Li metal plating conditions. The performance of F2DEM is further compared with diethoxymethane (DEM) and 2-[2-(2,2-difluoroethoxy)ethoxy]-1,1,1-trifluoroethane (F5DEE). A significantly lower overpotential is observed with F2DEM, which improves energy efficiency and enables its application in high-rate conditions. Comparative studies of F2DEM with DEM and F5DEE in anode-free lithium iron phosphate (LiFePO4) LFP pouch cells and high-loading LFP coin cells further show improved capacity retention of F2DEM electrolyte, demonstrating its practical applicability. More importantly, we also extensively investigate the underlying mechanism for the superior performance of F2DEM through various techniques, including X-ray photoelectron spectroscopy, scanning electron microscopy, cryogenic electron microscopy, focused ion beam, electrochemical impedance spectroscopy, and titration gas chromatography. Overall, F2DEM facilitates improved Li deposition morphology with reduced amount of dead Li. This enables F2DEM to show superior performance, especially under higher charging and slower discharging rate conditions.

Riveting Nucleation Enabled Long Cycling Life Calcium Metal Anodes.

Calcium metal batteries with high capacity and low cost are promising alternatives to Li-ion batteries for large-scale energy storage. However, its development is crucially impeded by the irreversible Ca metal anode, which is highly associated with uncontrollable Ca plating/stripping. Here, we report a new riveting strategy to regulate the nucleation and growth of a Ca metal anode in the 3D structure of a carbon nanotube film (CNF) by introducing in situ-formed Na metal mediators. Na metal mediators are found to first deposit in the CNF substrate prior to Ca nucleation and subsequently induce dense and uniform Ca plating due to their thermodynamically favorable kinetics. Therefore, even at a high current density of 10mA cm-2 and a high capacity of 5 mAh cm-2, it realizes the uniform nucleation and growth of dendrite-free Ca metal. Moreover, an unprecedented cycling life of over 800 cycles is also achieved for Ca metal batteries with a high coulombic efficiency above 98.4%. This work demonstrates the significance of a riveting strategy to enable the superior performance of Ca metal batteries by regulating the plating/stripping behaviors of Ca metal anodes and paves a new way for the development of Ca metal batteries.

Multidimensional core-shell nanocomposite of iron oxide-carbon tube and graphene nanosheet: A lithium-ion battery anode with enhanced performance through structural optimization

A novel multidimensional composite of 1D iron oxide (Fe3O4)-carbon tube and 2D graphene nanosheet (GNS) was demonstrated to be used as the anode material for lithium-ion batteries (LIBs). Fe3O4-carbon tube-GNS manifested a unique core–shell composite structure, where the Fe3O4 nanoparticles were embedded in the carbon tube with the GNS. The material characterization confirmed that the Fe3O4 nanoparticles were embedded in the highly graphitized carbon tube with the dispersed GNS. Fe3O4-carbon tube-GNS exhibited a high porosity (surface area: 62.3 m2/g, pore volume: 0.112 m3/g). It also exhibited an excellent electrochemical performance with a high reversible capacity (900 mAh/g at 1 A/g), a high coulombic efficiency (∼100 % for 100 cycles), and good rate capability (491 mAh/g at 5 A/g). The excellent electrochemical performance of our composite is attributed to the suppressed/accommodated volume expansion of Fe3O4 and formation of a stable solid electrolyte interphase (SEI) layer during lithiation/delithiation caused by unique multidimensional composite structure of Fe3O4-carbon tube-GNS with a continuous transport path for electrons and Li+. In addition, such the enhanced lithium storage of our composite is confirmed with the kinetic characterization at various scan rates by analyzing their storage and capacitive contributions.

A bismuth oxide-modified copper host achieving bubble-free and stable potassium metal batteries.

Due to the minimal electrochemical oxidation-reduction potential, the potassium (K) metal anode has emerged as a focal in K-ion batteries. However, the reactivity of the K metal anode leads to significant side reactions, particularly gas evolution. Mitigating gas generation from K metal anodes has been a persistent challenge in the field. In this study, we propose a dual protective layer design through pre-treatment of the K metal anode, employing a Bi2O3 modification layer alongside a stable solid electrolyte interface (SEI) formed during the initial charge-discharge cycle, which significantly suppresses gas evolution. Furthermore, we observe that the Bi2O3 modification layer enhances K nucleation due to its strong potassiophilicity when incorporated into the substrate material. The resultant SEI, consisting of dual inorganic layers of Bi-F and K-F formed through the Bi2O3 modification, effectively mitigates side reactions and gas generation while inhibiting dendrite growth. Utilizing a Cu@BO@K host, we achieve a nucleation overpotential as low as 40 mV, with a stability of 1900 h in a Cu@BO@K‖Cu@BO@K cell and a high average Coulombic efficiency of 99.2% in a Cu@BO@K‖Cu cell at 0.5 mA cm-2/0.5 mA h cm-2. Additionally, Cu@BO@K‖PTCDA also presents a high reversible capacity of 114 mA g-1 at 100 mA g-1 after 200 cycles. We believe that this work presents a viable pathway for mitigating side reactions in K metal anodes.

Solid-Liquid-Solid Growth of Doped Silicon Nanowires for High-Performance Lithium-Ion Battery Anode

Silicon nanowires (SiNWs) have great potential in electronic devices, sensors, energy storage, and conversion devices. Despite various ways to synthesize SiNWs, however, the growth of SiNWs directly from stable, abundant, sustainable silica sources has yet to be achieved. Herein, we report a modified alumino-reduction process of the silica to produce tin (Sn)-doped SiNWs that can be initiated at low temperature (250 °C) based on a solid-liquid-solid growth mechanism in analogy to the well-known vapor-liquid-solid (VLS). In this growth process, the reduced silicon atoms migrate freely in the molten salt and alloy with pre-reduced Sn. The supersaturation of silicon in the Sn-Si alloy leads to the precipitation of single-crystal SiNWs. The prepared SiNWs are of excellent crystallinity and doped with high non-equilibrium concentration (~3.0at.%) of Sn. This process with the solid-liquid-solid mechanism can also be extended to produce other group IV elements-based nanowires such as germanium. In addition, the prepared Sn-doped SiNWs as the anode material in lithium-ion batteries exhibit excellent performance with a high initial Coulombic efficiency of 85.4%, and a substantial reversible capacity of 1133 mAh g-1 even after 500 cycles at 4Ag-1. By utilizing the solid-liquid-solid mechanism, this modified alumino-reduction process offers a novel route for synthesizing doped SiNWs, holding promise for diverse applications.

Spatially confined transition metals boost high initial coulombic efficiency in alloy anodes.

Alloy-type materials hold significant promise as high energy density anodes for lithium-ion batteries. However, the initial coulombic efficiency (ICE) is significantly hindered by the poor reversibility of the conversion reaction and volume expansion. Here, the NiO/SnO2 multilayers with a hybrid interface of alloy and transition metal oxides are proposed to generate Ni nanoparticles within confined layers, catalyzing Li2O decomposition and suppressing the coarsening of Sn or Li2O particles. Supported by density functional theory (DFT) calculations and revealed by operando magnetometry, the spatially confined, well maintained Ni active sites lower the energy barrier for Li-O bond rupture and enhance the migration dynamics of Li+. The enhanced reaction kinetics lead to achievement of an impressive ICE of 92.3% and a large capacity of 1247 mA h g-1 with 97% retention after 800 cycles. Furthermore, the NiO/SnO2 anode exhibits excellent electrochemical performances in both Na/K-ion batteries. Notably, when constructed with the same framework, SiO2 also delivers significantly improved lithium storage properties with ultra-high ICEs. This work paves the way for advanced designs of alloy-type anodes that satisfy both ICE and overall electrochemical performance.

Storage Stability of pre-lithiation agent Li6CoO4: Exposed to components of dry air and moist gases

Pre-lithiation is a critical technology in the field of lithium-ion batteries (LIBs). The unfavorable storage conditions of the pre-lithiation agent Li6CoO4 (LCO) lead to harmful surface reactions, resulting in poor electrochemical performance and limiting its practical application. In this work, we have synthesized LCO with high initial charge capacity (826.5 mAh g-1) and low coulombic efficiency (6.5%). Ex-situ XRD reveals the structural evolution of the LCO material during the first charge and the O2 evolution was measured by differential electrochemical mass spectrometry (DEMS), and the de-lithiation mechanism of LCO was proposed. On the other hand, the formation of non-active LiOH and Li2CO3 impurities on the surface of the material under different storage conditions was revealed by Raman spectroscopy. According to the results of LCO materials stored in different air components, it can be found that moisture and CO2 are the key factors causing the degradation of LCO materials, and LCO materials in dry environment or protective atmosphere have good storage stability.

Enhancing battery longevity by regulating the solvation chemistry of organic iodide

For rechargeable zinc‐iodine batteries, the low electrical conductivity of iodine and the easy dissolution of polyiodide in the electrolyte need to be carefully managed to ensure efficient operation. Herein, we introduce an organic iodized salt, formamidinium iodide (CH5N2I), to modulate the solvation structure of iodide ion, aimed to improve the reaction kinetics of iodine for reversible redox conversion. The participation of formamidinium ion (FA+) into solvation structure leads to the formation of the favorable FAIZn(H2O)42+ complex, facilitating easier desolvation for redox conversion with iodine. Consequently, the inhibited formation of soluble polyiodide efficiently suppresses self‐discharging and improves reversible redox conversion. Specifically, the fabricated battery demonstrates extraordinary cycling stability, with 90.1% capacity retention after 10,000 cycles and high coulombic efficiency of 99.6%. These results provide inspiring principles to develop organohalide materials for high‐performance rechargeable batteries through the solvation modification and interface regulation strategies.

Enhancing battery longevity by regulating the solvation chemistry of organic iodide.

For rechargeable zinc-iodine batteries, the low electrical conductivity of iodine and the easy dissolution of polyiodide in the electrolyte need to be carefully managed to ensure efficient operation. Herein, we introduce an organic iodized salt, formamidinium iodide (CH5N2I), to modulate the solvation structure of iodide ion, aimed to improve the reaction kinetics of iodine for reversible redox conversion. The participation of formamidinium ion (FA+) into solvation structure leads to the formation of the favorable FAIZn(H2O)4 2+ complex, facilitating easier desolvation for redox conversion with iodine. Consequently, the inhibited formation of soluble polyiodide efficiently suppresses self-discharging and improves reversible redox conversion. Specifically, the fabricated battery demonstrates extraordinary cycling stability, with 90.1 % capacity retention after 10,000 cycles and high coulombic efficiency of 99.6 %. These results provide inspiring principles to develop organohalide materials for high-performance rechargeable batteries through the solvation modification and interface regulation strategies.

Enhancing Stability and 6C Fast Charging in µSi||LiNi0.8Co0.1Mn0.1O2 Lithium-Ion Batteries Using Conductive Binders With Multiple Hydrogen Bonds.

Micro-sized silicon (µSi) anodes are an attractive alternative to graphite for high-energy lithium-ion batteries (LIBs) due to their low cost and high specific capacity. However, they suffer from severe volume expansion during lithiation, leading to fast capacity decay and poor rate capability. Herein, a new hybrid binder featuring a cross-linked conductive network and multiple hydrogen bonds for µSi anodes with high areal capacity is reported. This binder demonstrates multi-scale synergistic effects, including robust binder-derived solid electrolyte interphase, multiple networks to mitigate electrode pulverization and efficient ion/electron transfer pathways. As a result, the µSi anodes exhibit long-term cyclability and exceptional rate performance, achieving a high specific capacity of 1481.3 mAh g-1 at 12 A g-1 and maintaining 960.5 mAh g-1 at 20 A g-1. When paired with the LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode, the µSi||NCM811 full cell delivers an impressive capacity of 145.8 mAh g-1 under fast 6C charging conditions, along with high Coulombic efficiency during cycling. This research presents an effective strategy for enabling fast charging and stable cycling in high-energy µSi-based LIBs.

Impact of Metal Oxide Nanoparticles on SEI and on Sodium Deposition - Dissolution

Abstract Sodium metal batteries (SMBs) are emerging as a next-generation rechargeable technology due to sodium’s abundance, cost-effectiveness, and high theoretical specific capacity. However, challenges such as uneven sodium plating, dendrite formation, and low coulombic efficiency (CE) limit their performance. This study explores the impact of various additives to carbonate based electrolyte, including metal oxide nanoparticles (Al2O3, TiO2) and vinylene carbonate (VC), on the electrochemical behavior of SMBs, focusing on sodium deposition morphology, solid electrolyte interphase (SEI) composition, and capacity losses. The VC additive contributed to a thicker SEI, characterized by an inorganic-rich inner layer and polymer-rich outer layer, resulting in the highest CE across current rates. In contrast, Al2O3 samples demonstrated intermediate performance, with NaOH on the SEI surface and reduced polymer content compared to VC. Additionally, we show that capacity losses from isolated “dead” sodium represent the largest contributor to total capacity losses, with cells containing VC and 1% Al2O3 exhibiting the lowest total capacity losses. Moreover, the study demonstrates the uneven distribution of sodium deposition on the aluminum CC, especially its tendency to favor regions with lower fluorine concentration in the SEI. The findings from this study are important for optimizing SMB design, stability, and cycling efficiency.

Suppressing Zinc Metal Corrosion by an Effective and Durable Corrosion Inhibitor for Stable Aqueous Zinc Batteries

AbstractThe development of aqueous zinc‐ion batteries (AZIBs) for large‐scale industrial applications is substantially constrained by the persistent issue of zinc anode corrosion. This study introduces fucoidan (FCD), a corrosion inhibitor, to effectively mitigate the corrosion‐related challenges in zinc metal anodes. FCD forms a robust, covalently bonded layer on the zinc surface at a low concentration of 25 mm through interactions between the lone pairs on its polar atoms and the d orbitals of zinc. This layer is ultrathin, which does not deteriorate ion transfer but effectively shields the zinc from corrosive electrolytes and promotes uniform zinc deposition, resulting in suppressed corrosion, passivation, and dendrite formation. Consequently, the Zn||Zn cells exhibit excellent reversibility, stably operating for 2700 h at 1 mA cm−2 under 1 mAh cm−2 and 400 h at 10 mA cm−2 under 10 mAh cm−2. Furthermore, a large‐sized Zn||I2 pouch cell with a high iodine loading of 2 g and a discharge capacity of ≈300 mAh is demonstrated, which shows minimal capacity degradation—<3% after 300 cycles—and maintains a high Coulombic efficiency of ≈99.5%. The corrosion inhibition strategy proposed in this study provides crucial insights for enhancing the durability and practicability of AZIBs.

Towards Highly Stable Sn2+ Electrolyte for Aqueous Tin Batteries Using Hydroquinone Antioxidant.

Sn redox chemistry in aqueous acidic electrolyte was characterized with high reversibility and kinetics, which is considered as competitive anode material for aqueous batteries. Unfortunately, divalent Sn2+ is unstable in aqueous electrolyte. It was revealed that Sn2+ is easy to be oxidized to tetravalent Sn4+ by dissolved oxygen and then forms precipitate through hydrolysis process, leading to serious performance decay. Here, hydroquinone (HQ) was employed as antioxidant to prevent Sn2+ oxidation. With addition of HQ, Sn2+ electrolyte can maintain transparent and colorless after long-time exposure under air atmosphere, while large amounts of sediment were observed in the electrolyte without HQ. Moreover, HQ can adsorb on electrode surface to regulate Sn deposition and suppress Sn dendrite formation. With the difunctional HQ additive, Sn anode shows a stable cycling performance more than 1500 cycles with a high average coulombic efficiency (CE) of 99.9%. And the organic||Sn cell shows high cycling stability for 10,000 cycles with 71% capacity retention. The hydroquinone antioxidant strategy provides a facile and cost-effective way to develop highly stable Sn2+-based electrolyte.

Dual-Substitution Strategy Utilizing Cation Chelation and Assembly Process to Realize Solid Solution Reaction in Layered Oxide Cathode for Na-Ion Batteries.

Na0.67Ni0.33Mn0.67O2 (NNM) is regarded as a promising cathode material for Na-ion batteries (NIBs), but suffers from irreversible phase transformations characterized by multiple voltage plateaus, resulting in poor cycle stability and inferior rate capability. To address these issues, the Na0.67Ni0.18Cu0.10Zn0.05Mn0.67O2 (NNCZM) cathode material is synthesized by a cation chelation and reassembly process, which can promote a more uniform element distribution than that prepared by the solid-state method (S-NNCZM), resulting in better Na+ diffusion kinetics and rate capability. Replacing Ni2+ with a small amount of Zn2+ prevents the P2-O2 phase transformation, while replacing Ni2+ with an appropriate amount of electrochemically active Cu2+ eliminates Na-vacancy ordering and additionally contributes to capacity. Thus, the dual substitution of Cu2+ and Zn2+ for Ni2+ makes the NNCZM electrode synergistically achieve a complete solid solution reaction and better cycling stability. Accordingly, it exhibits a large discharge capacity (110.2 mA h g-1 at 10 mA g-1) with a high initial coulombic efficiency (97.3%), remarkable cycle stability with 84.1% capacity retention over 200 cycles at 200 mA g-1, and excellent rate capability with a discharge capacity of 61.0 mA h g-1 at 2000 mA g-1, significantly outperforming the NNM and S-NNCZM electrodes.

Towards Highly Stable Sn2+ Electrolyte for Aqueous Tin Batteries Using Hydroquinone Antioxidant

Sn redox chemistry in aqueous acidic electrolyte was characterized with high reversibility and kinetics, which is considered as competitive anode material for aqueous batteries. Unfortunately, divalent Sn2+ is unstable in aqueous electrolyte. It was revealed that Sn2+ is easy to be oxidized to tetravalent Sn4+ by dissolved oxygen and then forms precipitate through hydrolysis process, leading to serious performance decay. Here, hydroquinone (HQ) was employed as antioxidant to prevent Sn2+ oxidation. With addition of HQ, Sn2+ electrolyte can maintain transparent and colorless after long‐time exposure under air atmosphere, while large amounts of sediment were observed in the electrolyte without HQ. Moreover, HQ can adsorb on electrode surface to regulate Sn deposition and suppress Sn dendrite formation. With the difunctional HQ additive, Sn anode shows a stable cycling performance more than 1500 cycles with a high average coulombic efficiency (CE) of 99.9%. And the organic||Sn cell shows high cycling stability for 10,000 cycles with 71% capacity retention. The hydroquinone antioxidant strategy provides a facile and cost‐effective way to develop highly stable Sn2+‐based electrolyte.

High-Entropy Electrolytes with High Disordered Solvation Structures for Ultra-Stable Zinc Metal Anodes.

Aqueous zinc-ion batteries (ZIBs) are playing an increasingly important role in the field of energy storage. However, their practical applications are handicapped by severe dendrite formation and side reactions on zinc anodes. Herein, a low-concentration high-entropy (HE) electrolyte strategy is proposed to achieve high reversibility and ultra-durable zinc metal anode. Specifically, this HE electrolyte features multiple anions participating in coordination and highly disordered solvation shells, which would disrupt intrinsic H-bond network between water molecules and suppress interfacial side reactions. Moreover, these diversified weakly solvated structures can lower solvation energy of Zn2+ solvation configurations and enhance zinc ion diffusion kinetics,promoting uniform Zn deposition and electrode interface stability. Consequently, Zn||Zn symmetric cells exhibit over 2,000 hours of cycling stability, and Zn||Cu asymmetric cells achieve high average Coulombic efficiency of 99.9% over 500 cycles. Furthermore, the Zn||PANI full cell with optimized HE-50mM electrolyte delivers a high specific capacity of 110.7 mAh g-1 over 2,000 cycles at 0.5 A g-1 and a capacity retention of 70.4% at 15 A g-1 after 10,000 cycles. Remarkably, even at a low temperature of -20 °C, the Zn||PANI full cells equipped with HE-50mM electrolyte still demonstrate long-term cycling stability over 600 cycles with high-capacity retention of 93.5%.