Efficient Charge Storage in Zinc–Iodine Batteries based on Pre-Embedded Iodine-Ions with Reduced Electrochemical Reaction Barrier and Suppression of Polyiodide Self-Shuttle Effect

Aqueous zinc Iodine batteries are considered as a promising energy storage system due to their high energy/power density, and safety. However, polyiodide shuttling leads to severe active mass loss, which results in lower Coulombic efficiency and limits the cyclic life. Herein, a novel structure-limiting strategy to pre-embed iodide ions into Prussian blue (PBI) is proposed. The DFT calculations and electrochemical characterization reveal that the formation of Ferrum Iodine bond reduces the electrochemical reaction energy barrier of subsequent iodide-ions at the pre-embedding sites, improves the I⁻ oxidation reaction kinetic process, and suppresses the polyiodide self-shuttle. The PBI//Zn batteries exhibit a low Tafel slope (155 mV dec⁻¹). Moreover, UV–vis spectroscopy confirms that the proposed strategy suppresses the polyiodide self-shuttle. As a result, the PBI//Zn battery achieves high iodide utilization and Coulomb efficiency (242 mAh g⁻¹ at 0.2 A g⁻¹, CEs ≈ 100%), as well as high multiplicity performance of 197.2 mAh g⁻¹ even at 10 A g⁻¹(82% of initial capacity). The PBI//Zn battery also renders excellent cyclic stability with a capacity retention of 94% at 4 A g⁻¹ after 1500 cycles. The device exhibits a high energy density of 142 W h kg⁻¹ at a power density of 5538 W kg⁻¹.     

Toward Shuttle-Free Zn–I2 Battery: Anchoring and Catalyzing Iodine Conversion by High-Density P-Doping Sites in Carbon Host

Zn–iodine (I₂) battery, as a promising energy storage device, especially under high I₂ loading, is harassed by the shuttle effect of the soluble polyiodide intermediates. Herein, the bifunctional role of 2D carbon nanosponge with rich P-dopant (4.2 at%) and large specific surface area (1966 m² g⁻¹) in anchoring I₂/I_x⁻ (x = 1, 3 or 5) and catalyzing their mutual conversion is reported. Both experiment and computational results reveal the transfer of electrons from the P-doped site to iodine species, showing strong interfacial interaction. When being used as a host, it possesses high specific capture capacity for I₂ (3.34 g_iodine g⁻¹ or 1.6 mg_iodine m⁻²) and I_x⁻ (6.12 g_triiodide g⁻¹ or 3.1 mg_triiodide m⁻²), which thus effectively suppresses the shuttle effect, supported by in situ UV–vis and Raman spectra. In addition to the strong interfacial interaction that favors iodine conversion, the P-doped sites can also catalyze the conversion of I₅⁻ to I₂, which is the rate-determining step. Consequently, Zn–I₂ batteries under a high I₂ content (70 wt%) deliver high specific capacity (220.3 mAh g⁻¹), superior Coulombic efficiency (>99%), and low self-discharge rate; moreover, they can also operate steadily at 2 A g⁻¹ with ignorable capacity decay for 10 000 cycles.     

Advanced Zinc–Iodine Batteries with Ultrahigh Capacity and Superior Rate Performance Based on Reduced Graphene Oxide and Water-in-Salt Electrolyte

Aqueous rechargeable zinc–iodine batteries have received increasing attention in the field of portable electronics due to their high safety, low-cost, and great electrochemical performance. However, the insulated nature of iodine and the unrestricted shuttle effect of soluble triiodide seriously limit the lifespan and Coulombic efficiency (CE) of the batteries. Herein, a high-performance zinc–iodine energy storage system based on the hydrothermal reduced graphene oxide (rGO) and a high concentration zinc chloride water-in-salt electrolyte are promoted. The 3D microporous structures and outstanding electrical conductivity of rGO make it an excellent host for iodine, while the water-in-salt electrolyte effectively suppresses the shuttle effect of triiodide and improves the CE of the system. As a result, an ultra-high I₂ mass loading of 25.33 mg cm⁻² (loading ratio of 71.69 wt.%) is realized during the continuous charging/discharging process. The batteries deliver a high capacity of 6.5 mAh cm⁻² at 2 mA cm⁻² with a much-improved CE of 95% and a prominent rate performance with capacity of 1 mAh cm⁻² at 80 mA cm⁻². A stable long-term cycling performance is also achieved with capacity retention of 2 mAh cm⁻² after 2000 cycles at 50 mA cm⁻².     

Sulfur Mismatch Substitution in Layered Double Hydroxides as Efficient Oxygen Electrocatalysts for Flexible Zinc–Air Batteries

Although layered double hydroxides (LDHs) are extensively investigated for oxygen electrocatalysis, their development is hampered by their limited active sites and sluggish reaction kinetics. Here, sulfur mismatch substitution of NiFe–LDH (S–LDH) is demonstrated, which are in-situ deposited on nitrogen-doped graphene (S–LDH/NG). This atomic-level sulfur incorporation leads to the construction of the tailored topological microstructure and the modulated electronic structure for the improved catalytic activity and durability of bifunctional electrocatalysts. The combined computational and experimental results clarify that the electron transfer between the sulfur anion and Fe³⁺ generates the high-valence Fe⁴⁺ species, while the mismatch substitution of the sulfur anion induces the metallic conductivity, an increased carrier density, and the reduced reaction barrier. Consequently, the as-fabricated Zn–air battery achieves a high power density of 165 mW cm^-2, a large energy density of 772 Wh kg_Zn^-1 at 5 mA cm^-2, and long cycle stability for 120 h, demonstrating its real-life operation.     

Separation Effect of Graphene Sheets with N,O Codoping and Molybdenum Clusters for Reversible Lithium–Iodine Batteries

Lithium–iodine (Li–I₂) batteries with ideal discharge potential plateau and abundant iodine resources have attracted considerable attention. However, the poor electrical conductivity of iodine with high solubility in organic electrolytes, and the Li dendrite issue have severely limited the practical application of Li–I₂ batteries. Herein, this work demonstrates that the bifunctionalization of polypropylene (PP) separator with molybdenum clusters on N, O codoped graphene nanosheets (Mo-rGO@PP) is efficient to promote the reversible redox reactions of polyiodides to suppress the shuttle effect, and enhance the Li affinity for the uniform Li plating/stripping. Typically, the Li symmetric battery assembled with Mo-rGO@PP separator exhibits an ultralong lifespan of >2000 h with a low overpotential of <25 mV at 10 mA cm⁻². With such a separation effect to effectively suppress the polyiodide shuttle and dendrite growth, the Li–I₂ battery delivers a long cycle life of over 6000 cycles with a reversible capacity of 170 mAh g⁻¹ at 10 C. With deep insights into the ion flux and redox regulation, this work demonstrates the promising advances via the separation effect for developing high-performance redox batteries.     

Electrospinning Synthesis of Self-Standing Cobalt/Nanocarbon Hybrid Membrane for Long-Life Rechargeable Zinc–Air Batteries

Integrating high-efficiency oxygen electrocatalyst directly into air electrodes is vital for zinc–air batteries to achieve higher electrochemical performance. Herein, a self-standing membrane composed of hierarchical cobalt/nanocarbon nanofibers is fabricated by the electrospinning technique. This hybrid membrane can be directly employed as the bifunctional air electrode in zinc–air batteries and can achieve a high peak power density of 304 mW cm⁻² with a long service life of 1500 h at 5 mA cm⁻². Its assembled solid-state zinc–air battery also delivers a promising power density of 176 mW cm⁻² with decent flexibility. The impressive rechargeable battery performance would be attributed to the self-standing membrane architecture integrated by oxygen electrocatalysts with abundant cobalt–nitrogen–carbon active species in the hierarchical electrode. This study may provide effective electrospinning solutions in integrating efficient electrocatalyst and electrode for energy storage and conversion technologies.     

Challenges and Solutions for Lithium–Sulfur Batteries with Lean Electrolyte

Lithium–sulfur (Li–S) batteries have high theoretical energy density and are regarded as next-generation batteries. However, their practical energy density is much lower than the theoretical value. In previous studies, the increase of the areal capacity of the cathode and the decrease of the negative/positive ratio can be well achieved, yet the energy density shows no corresponding increase. The main reason is the difficulty in decreasing electrolyte dosage because lean electrolyte inevitably causes the deterioration of reaction kinetics and sulfur utilization. Thus, the electrolyte/active material ratio in the reported works is usually higher than 10 µL mg⁻¹, much higher than that in Li-ion batteries (usually lower than ≈0.3 µL mg⁻¹ for cathode). Although many works have focused on this topic, a systematic discussion is still rare. This review systematically discusses the key challenges and solutions for assembling high-performance lean-electrolyte Li–S batteries. First, the key challenges arising from lean-electrolyte conditions are discussed in detail. Then, the approaches and the recent progress to reduce electrolyte usage, including optimization of electrode porosity and ion conduction, the introduction of electrocatalysis, exploration of new active materials, electrolyte regulation, and Li metal protection are reviewed. Finally, future research directions in lean-electrolyte Li–S batteries are proposed.     

TiO2-Induced Conversion Reaction Eliminating Li2CO3 and Pores/Voids Inside Garnet Electrolyte for Lithium–Metal Batteries

Garnet Li₇La₃Zr₂O₁₂ (LLZO) is regarded as a promising solid electrolyte due to its high Li⁺ conductivity and excellent chemical stability, but suffers from grain boundary resistance and porous structure which restrict its practical applications in lithium–metal batteries. Herein, a novel and highly efficient TiO₂-induced conversion strategy is proposed to generate Li ion-conductive Li_0.5La_0.5TiO₃, which can simultaneously eliminate the pre-existing pores/voids and contamination Li₂CO₃. The Li/LLZTO-5TiO₂/Li symmetric cell exhibits a high critical current density of 1.1 mA cm⁻² at 25°C, and the long-term lithium cycling stability of over 1500 h at 0.1 mA cm⁻². More importantly, the excellent performance of LLZTO-5TiO₂ electrolyte is verified by LiCoO₂/LiFePO₄ coupled full cells. For example, The LiCoO₂ coupled full cell exhibits a significant discharge rate capacity of 108 mAh g⁻¹ at 0.1 C, and a discharge capacity retention rate of 91.23% even after 150 cycles of charge and discharge. COMSOL Multiphysics and density functional theory calculation reveal that LLZTO-5TiO₂ electrolyte has a strong lithium affinity and uniform Li ions distribution, which can improve the cycle stability of Li–metal batteries by preventing dendrite growth.     

A Multifunctional Catalytic Interlayer for Propelling Solid–Solid Conversion Kinetics of Li2S2 to Li2S in Lithium–Sulfur Batteries

The theoretically high-energy-density lithium–sulfur batteries (LSBs) are seriously limited by the disadvantages including the shuttle effect of soluble lithium polysulfides (LiPSs) and the sluggish sulfur redox kinetics, especially for the most difficult solid–solid conversion of Li₂S₂ to Li₂S. Herein, a multifunctional catalytic interlayer to improve the performance of LSBs is tried to introduce, in which Fe_1–xS/Fe₃C nanoparticles are embedded in the N/S dual-doped carbon network (NSC) composed by nanosheets and nanotubes (the final product is named as FeSC@NSC). The well-designed 3D NSC network endows the interlayer with a satisfactory LiPSs capture-catalytic ability, thus ensuring fast redox reaction kinetics and suppressing LiPSs shuttling. The density functional theory calculations disclose the catalytic mechanisms that FeSC@NSC greatly improves the liquid–solid (LiPSs to Li₂S₂) conversion and unexpectedly the solid–solid (Li₂S₂ to Li₂S) one. As a result, the LSBs based on the FeSC@NSC interlayer can achieve a high specific capacity of 1118 mAh g⁻¹ at a current density of 0.2 C, and a relatively stable capacity of 415 mAh g⁻¹ at a large current density of 2.0 C after 700 cycles as well as superior rate performance.     

Chemical Polishing of CdTe and CdZnTe in Iodine–Methanol Etching Solutions

Iodine-containing polishing etchants were tested on CdTe and Cd_1−x Zn _x Te surfaces with different orientations. The nature of the chemical dissolution of CdTe with (111)A, (111)B, (110), and (100) orientations in the I₂–methanol solution was studied. It was established that this dissolution is diffusion controlled. Study of the chemical composition and structure of the (211)B Cd_1−x Zn _x Te surfaces etched under different conditions was carried out. X-ray photoelectron spectroscopy (XPS) measurements showed that a stoichiometric surface was achieved after short heating of the etched surface in vacuum. Reflection high-energy electron diffraction (RHEED) measurements reveal a high-quality single-crystalline surface layer in samples etched with iodine–methanol solutions as compared with bromine–methanol treatment.     

Water-Soluble Cross-Linking Functional Binder for Low-Cost and High-Performance Lithium–Sulfur Batteries

Binders play an important role in battery systems. The lithium–sulfur (Li–S) batteries have poor cycling performance owing to large volume alteration of sulfur and shuttle effect. Herein, a novel water-soluble functional binder (named GN-BA) is prepared by the cross-linking effect between gelatin and boric acid. The excellent binder can effectively maintain the integrated electrode stable, buffer the volume changes, prevent active materials exfoliation from current collectors, and anchor polysulfides by chemical bonding. Sulfur electrodes in this binder also exhibit a loosely stacked porous structure, which is advantageous to the electrolyte permeation and fast ion diffusion. X-ray photoelectron spectroscopy, ultraviolet-visible spectroscopy, and density functional theory calculations further verified that the binder can anchor polysulfides by forming B O Li, C O Li, and C N Li chemical bonds. At 0.5 C, a high initial capacity of 980 mA h g⁻¹ can be obtained, which is higher than those sulfur cathodes with traditional poly(vinylidene fluoride) binder. When the sulfur loading is up to 5.0 mg cm⁻², a high areal specific capacity of 5.7 mA h cm⁻² and excellent cycling stability are achieved. This study proposes an economical and environmentally friendly strategy for the construction of advanced binders and promotes the practical application of high-energy Li–S batteries.     

Nanofluid Electrolyte with Fumed Al2O3 Additive Strengthening Zincophilic and Stable Surface of Zinc Anode toward Flexible Zinc–Nickel Batteries

Flexible zinc–nickel batteries (FZNBs) have been considered as a promising power supply for wearable electronics due to the intrinsic safety, high operating voltage and superior rate performance. However, the serious self-corrosion of zinc and the redistribution of dissolved [Zn(OH)₄]²⁻ on the electrode surface limit the electrochemical performance of FZNBs. Herein, the nanofluid electrolyte with fumed Al₂O₃ additive is introduced into FZNBs and a protective layer is formed due to the adsorption of Al₂O₃ on the electrodeposited zinc anode. The protective layer strengthens the zincophilicity of the anode and homogenizes the deposition of [Zn(OH)₄]²⁻, avoiding the dendrite formation and the shape change of electrode. Meanwhile, by suppressing the [Zn(OH)₄]²⁻ diffusion from the anode surface to the bulk electrolyte, the interface stabilization is effectively promoted, thereby improving zinc utilization rate and inhibiting the corrosion. Hence, the FZNBs assembled with Al₂O₃-nanofluid electrolyte and electrodeposited zinc anode demonstrates superior energy density of 210 Wh L⁻¹ with a stable cycling of 575 h. Furthermore, FZNBs modified with Al₂O₃-nanofluid electrolyte have a promising future in the field of wearable and portable electronics.     

Harvesting Air and Light Energy via “All-in-One” Polymer Cathodes for High-Capacity,Self-Chargeable,and Multimode-Switching Zinc Batteries

Aqueous rechargeable Zinc (Zn)–polymer batteries are promising alternatives to prevalent Li-ion cells in terms of cost, safety, and rate capability but they suffer from limited specific capacity in addition to poor environmental adaptability. Herein, air and light are successfully utilized from external environments in single near-neutral two-electrode Zn batteries to enable remarkably improved electrochemical performance, fast self-charging, and switchable multimode-operation from Zn–polymer to Zn–air cells. This system is enabled by a well-designed polyaniline-nanorod-array based “all-in-one” cathode combining reversible redox capability, oxygen reduction activity, and photothermal-responsiveness. The initiative design allows perfect integration of multiple energy harvesting from ambient “air” and light, energy conversion, and storage in one single cathode. Thus, it can act as an efficient light-assisted electrically-rechargeable Zn–polymer cell featuring the highest specific capacity of 430.0 mAh g⁻¹ among all existing polymer cathodes. Without external power sources, it can be self-charged to deliver a high discharging capacity of 363.1 mAh g⁻¹ by concurrently harvesting chemical energy from air and light energy for only 20 min. It can also switch to a light-responsive Zn–air battery mode to surmount the output capacity limit of Zn–polymer battery mode for continued electricity supply.     

Cobalt(II)-Centered Fluorinated Phthalocyanine-Sulfur SNAr Chemistry for Robust Lithium–Sulfur Batteries with Superior Conversion Kinetics

Due to the exceptional theoretical energy density and low cost of elemental sulfur, lithium–sulfur (Li–S) batteries are spotlighted as promising post-lithium-ion batteries. Despite these advantages, the performance of Li–S batteries would need to be improved further for their wide dissemination in practical applications. Here, cobalt(II)-centered fluorinated phthalocyanine, namely, F-Co(II)Pc, is reported as a multi-functional component for sulfur cathodes with the following benefits: 1) enhanced conversion kinetics as a result of the catalytic effect of the cobalt(II) center, 2) efficient sulfur linkage via the fluorine functionality, which undergoes a nucleophilic aromatic substitution (S_NAr) reaction, 3) suppression of the shuttling issue by the nitrogen atoms because of their strong affinity with polysulfides, and 4) the necessary aromaticity to engage in π–π interaction with reduced graphene oxide for electrical conductivity. The resulting electrode has promising electrochemical properties, such as sustainable cycling for 700 cycles and robust operation with a sulfur loading of 12 mg_sulfur cm⁻², unveiling the promising nature of phthalocyanine and its related molecular families for advanced Li–S batteries.     

Effects of Fluorinated Diluents in Localized High-Concentration Electrolytes for Lithium–Oxygen Batteries

A stable electrolyte is critical for practical application of lithium–oxygen batteries (LOBs). Although the ionic conductivity and electrochemical stability of the electrolytes have been extensively investigated before, their oxygen solubility, viscosity, volatility, and the stability against singlet oxygen (¹O₂) still need to be comprehensively investigated to provide a full picture of the electrolytes, especially for an open system such as LOBs. Herein, a systematic investigation is reported on the localized high-concentration electrolytes (LHCEs) using different fluorinated diluents in comparison with those of conventional electrolytes. The physical properties and activation energies for reactions with singlet oxygen (¹O₂) of these electrolytes are calculated by density functional theory. The electrochemical performances of LOBs using these electrolytes are compared. This study reveals that the correlation between the stability of the electrolytes and their physical and electrochemical properties depends strongly on the diluents in LHCEs. Therefore, it shines light on the rational design of new electrolytes for LOBs.     

Poly(2,5-Dihydroxy-1,4-Benzoquinonyl Sulfide) As an Efficient Cathode for High-Performance Aqueous Zinc–Organic Batteries

Aqueous rechargeable zinc-ion batteries (ZIBs) have attracted considerable attention as a promising candidate for low-cost and high-safety electrochemical energy storage. However, the advancement of ZIBs is strongly hindered by the sluggish ionic diffusion and structural instability of inorganic metal oxide cathode materials during the Zn²⁺ insertion/extraction. To address these issues, a new organic host material, poly(2,5-dihydroxy-1,4-benzoquinonyl sulfide) (PDBS), has been designed and applied for zinc ion storage due to its elastic structural factors (tunable space and soft lattice). The aqueous Zn-organic batteries based on the PDBS cathode show outstanding cycling stability and rate capability. The coordination moieties (O and S) display the strong electron donor character during the discharging process and can act as the coordination arms to host Zn²⁺. Also, under the electrochemical environment, the malleable polymer structure of PDBS permits the rotation and bending of polymer chains to facilitate the insertion/extraction of Zn²⁺, manifesting the superiority and uniqueness of organic electrode materials in the polyvalent cation storage. Finally, quasi-solid-state batteries based on aqueous gel electrolyte demonstrate highly stable capacity under different bending conditions.     

Hybrid Liquid–Solid Composite Electrolytes for Sulfide-Based Solid-State Batteries: Advantages and Limitation

All-solid-state batteries (SSBs) represent one of the most promising avenues for surpassing the energy density limitations of conventional lithium-ion batteries. However, the unstable interfacial contact between the solid-state electrolyte and the electrode poses a critical challenge for practical applications. To tackle this issue, a hybrid system incorporating both liquid electrolytes (LEs) and sulfide solid-state electrolytes may serve as a viable alternative. In this hybrid system, the LE facilitates the in situ formation of a solid electrolyte interphase layer, thereby enhancing the physical interface contact. Consequently, the electrochemical lifetime of the hybrid all-SSBs is significantly improved, as evidenced by the stable lithium plating behavior observed through analytical techniques such as in situ X-ray imaging. Nonetheless, the hybrid system exhibits clear limitations, and several issues that need to be addressed for its practical implementation are identified. In conclusion, potential solutions that could be employed to overcome these challenges are proposed.     

In Situ Reconstruction of Electrocatalysts for Lithium–Sulfur Batteries: Progress and Prospects

The current research of Li–S batteries primarily focuses on increasing the catalytic activity of electrocatalysts to inhibit the polysulfide shuttling and enhance the redox kinetics. However, the stability of electrocatalysts is largely neglected, given the premise that they are stable over extended cycles. Notably, the reconstruction of electrocatalysts during the electrochemical reaction process has recently been proposed. Such in situ reconstruction process inevitably leads to varied electrocatalytic behaviors, such as catalytic sites, selectivity, activity, and amounts of catalytic sites. Therefore, a crucial prerequisite for the design of highly effective electrocatalysts for Li–S batteries is an in-depth understanding of the variation of active sites and the influence factors for the in situ reconstruction behaviors, which has not achieved a fundamental understanding and summary. This review comprehensively summarizes the recent advances in understanding the reconstruction behaviors of different electrocatalysts for Li–S batteries during the electrochemical reaction process, mainly including metal nitrides, metal oxides, metal selenides, metal fluorides, metals/alloys, and metal sulfides. Moreover, the unexplored issues and major challenges of understanding the reconstruction chemistry are summarized and prospected. Based on this review, new perspectives are offered into the reconstruction and true active sites of electrocatalysts for Li–S batteries.     

Expediting Stepwise Sulfur Conversion via Spontaneous Built-In Electric Field and Binary Sulfiphilic Effect of Conductive NbB2-MXene Heterostructure in Lithium–Sulfur Batteries

Fabricating metal boride heterostructures and deciphering their interface interaction mechanism on accelerating polysulfide conversion at atomic levels are meaningful yet challenging in lithium–sulfur batteries (LSBs). Herein, novel highly-conductive and binary sulfiphilic NbB₂-MXene heterostructures are elaborately designed with spontaneous built-in electric field (BIEF) via a simple one-step borothermal reduction strategy. Experimental and theoretical results reveal that Nb and B atoms can chemically bond with polysulfides, thereby enriching chemical anchor and catalytic active sites. Meanwhile, the spontaneous BIEF induces interfacial charge redistribution to make more electrons transferred to surface NbB₂ sites, thereby weakening its strong adsorption property yet accelerating polysulfide transfer and electron diffusion on hetero-interface, so providing moderate polysulfide adsorb-ability yet decreasing sulfur-species conversion energy barriers, further boosting the intrinsically catalytic activity of NbB₂-MXene for accelerated bidirectional sulfur conversion. Thus, S/NbB₂-MXene cathode presents high initial capacity of 1310.1 mAh g⁻¹ at 0.1 C, stable long-term lifespan with 500 cycles (0.076% capacity decay per cycle) at 1 C, and large areal capacity of 6.5 mAh cm⁻² (sulfur loading: 7.0 mg cm⁻² in lean electrolyte of 5 µL mg_s⁻¹) at 0.1 C. This work clearly unveils the mechanism of interfacial BIEF and binary sulfiphilic effect on accelerating stepwise sulfur conversion at atomic levels.     

Engineering an Ultrathin and Hydrophobic Composite Zinc Anode with 24 µm Thickness for High-Performance Zn Batteries

The Zn metal anode is subject to uncontrolled dendrites and parasitic reactions, which often require a big thickness of Zn foil, resulting in excess capacity and extremely low utilization. Here, an ultrathin Zn composite anode (24 µm) is developed with a protective hydrophobic layer (covalent (C₂F₄)_n chains and F-doped carbonized ingredient) constructed on Cu foil (denoted as (C₂F₄)_n-C@Cu) as a host by one-step pyrolytic evaporation deposition. The repulsion of (C₂F₄)_n to Zn²⁺ makes the (C₂F₄)_n-C@Cu interface possess enhanced adsorption ability, driving more charge transfer under the layer. With its good hydrophobicity, this layer prevents H₂O from damaging the plated Zn. Combined with the semi-ionic-state fluorine as zincophilic site, the host guides uniform and dense Zn deposition for making ultrathin Zn anode. As a result, the (C₂F₄)_n-C@Cu electrode exhibits high average CE of 99.6% over 3000 cycles at 2 mA cm⁻². Benchmarked against the commercial 20µm-Zn foil, the (C₂F₄)_n-C@Cu@Zn anode achieves enhanced stability (1200 h at 1 mA cm⁻²), only 100 h for the 20µm-Zn foil. When paired with V₂O₅ cathode, the Zn composite anode makes the full cell deliver 88% retention for 2500 cycles.