A Safe Organic/Inorganic Composite Anode for Sodium-Ion Batteries

Sodium-ion batteries (SIBs), based on hard carbon anodes and Na⁺-intercalation compound cathodes, have gained significant attention. Nonetheless, hard carbon anodes involve the storage of Na⁺ at a low potential, typically below 0.1 V (vs Na/Na⁺), which increases the risk of dendritic Na growth on the anode surface during overcharging. Herein, a safe organic/inorganic composite anode containing tetrasodium 3,4,9,10-perylenetetracarboxylate (Na₄PTC) and Metallic bismuth (Bi) with a weight ratio of 7:2, which exhibits an average potential of 0.7 V (vs Na⁺/Na) and a capacity of 150 mAh g⁻¹ is proposed. The electrode reaction involves a reversible coordination reaction within the organic host and alloying reactions within the metallic Bi component. Importantly, the organic component efficiently buffers the volume changes in Bi during the alloying reaction, while the metallic Bi enhances the electronic conductivity of the organic material. As a result, this composite anode shows high cycle stability and rate performance, even under high mass loadings ranging from 10 to 50 mg cm⁻². Furthermore, it is demonstrated that the Na-ion full cell, consisting of the composite anode and the Na₃V₂O₂(PO₄)₂F cathode, exhibits minimal capacity degradation over 100 cycles while maintaining a high areal capacity of 1.1 mA cm⁻².     

Carboxyl-Dominant Oxygen Rich Carbon for Improved Sodium Ion Storage: Synergistic Enhancement of Adsorption and Intercalation Mechanisms

Oxygen-containing groups in carbon materials have been shown to affect the carbon anode performance of sodium ion batteries; however, precise identification of the correlation between specific oxygen specie and Na⁺ storage behavior still remains challenging as various oxygen groups coexist in the carbon framework. Herein, a postengineering method via a mechanochemistry process is developed to achieve accurate doping of (20.12 at%) carboxyl groups in a carbon framework. The constructed carbon anode delivers all-round improvements in Na⁺ storage properties in terms of a large reversible capacity (382 mAg⁻¹ at 30 mA g⁻¹), an excellent rate capability (153 mAg⁻¹ at 2 A g⁻¹) as well as good cycling stability (141 mAg⁻¹ after 2000 cycles at 1.5 A g⁻¹). Control experiments, kinetic analysis, density functional theory calculations, and operando measurements collectively demonstrate that carboxyl groups not only act as active sites for Na⁺ capacitive adsorption through suitable electrostatic interactions, but also gradually expand d-spacing by inducing a repulsive force between carbon layers with Na⁺ preadsorbed, and hence facilitate diffusion-controlled Na⁺ insertion process. This work provides a new insight in the rational tunning of oxygen-containing groups in carbon for boosting reversible Na⁺ storage through a synergy of adsorption and intercalation processes.     

Achieving a Quasi-Solid-State Conversion of Polysulfides via Building High Efficiency Heterostructure for Room Temperature Na–S Batteries

The practical application of room temperature sodium–sulfur (RT Na–S) batteries are prevented by the sulfur insulation, the severe shuttling effect of high-order sodium polysulfides (Na₂S_n, 4 ≤ n ≤ 8), and the sluggish reaction kinetics. Therefore, designing an ideal host material to suppress the polysulfides shuttle process and accelerate the redox reactions of soluble NaPSs to Na₂S₂/Na₂S is of paramount importance for RT Na–S batteries. Here, a quasi-solid-state transformation of NaPSs is realized by building high efficiency MoC-W₂C heterostructure in freestanding multichannel carbon nanofibers via electrospinning and calcination methods (MoC-W₂C-MCNFs). The multichannel carbon nanofibers are interlinked micro-mesoporous structures that can accommodate volume change of electrode materials and confine the entire redox process of NaPSs (restraining the polysulfides shuttle process). Meanwhile, the MoC-W₂C heterostructure with abundant heterointerfaces can facilitate electron/ion transport and accelerate conversion of NaPSs. Consequently, the S/MoC-W₂C-MCNFs cathode delivers a high capacity of 640 mAh g⁻¹ after 500 cycles at 0.2 A g⁻¹ and an excellent reversible performance of 200 mAh g⁻¹ after ultralong 3500 cycles at 4 A g⁻¹. What's more, the heterostructure catalytic mechanism (a quasi-solid-state transformation) is proposed and confirmed in carbonate electrolyte by combining experimentally and theoretically.     

Sodium Sulfide Cathodes Superseding Hard Carbon Pre‐sodiation for the Production and Operation of Sodium–Sulfur Batteries at Room Temperature

This study demonstrates for the first time a room temperature sodium–sulfur (RT Na–S) full cell assembled based on a pristine hard carbon (HC) anode combined with a nanostructured Na₂S/C cathode. The development of cells without the demanding, time‐consuming and costly pre‐sodiation of the HC anode is essential for the realization of practically relevant RT Na–S prototype batteries. New approaches for Na₂S/C cathode fabrication employing carbothermal reduction of Na₂SO₄ at varying temperatures (660 to 1060 °C) are presented. Initial evaluation of the resulting cathodes in a dedicated cell setup reveals 36 stable cycles and a capacity of 740 mAh g_S^?1, which correlates to ≈85% of the maximum value known from literature on Na₂S‐based cells. The Na₂S/C cathode with the highest capacity utilization is implemented into a full cell concept applying a pristine HC anode. Various full cell electrolyte compositions with fluoroethylene carbonate (FEC) additive have been combined with a special charging procedure during the first cycle supporting in situ solid electrolyte interphase (SEI) formation on the HC anode to obtain increased cycling stability and cathode utilization. The best performing cell setup has delivered a total of 350 mAh g_S^?1, representing the first functional full cell based on a Na₂S/C cathode and a pristine HC anode today.     

A High-Capacity and High-Voltage Aqueous Zn-Polymer Battery with Self-Charging Function

Organic electrodes in aqueous batteries rely on electrochemical redox reactions for charge and discharge. The organic cathode at a discharged state can be spontaneously oxidized when exposed to air, which facilitates the development of air-charging batteries. However, polymer cathodes in aqueous rechargeable Zn-ion batteries (ARZIBs) generally show low discharge median voltage below 1 V. Herein, a new polymer cathode is reported that is prepared by electrodepositing poly(4-hydroxydiphenylamine, HDPA) onto mesoporous activated carbon and shows a relatively high discharge voltage plateau at ≈1.1 V when coupled with a Zn anode. Its self-charging performances at different conditions are investigated. Also, a high areal capacity of 3.8 mAh cm⁻² of the cathode is achieved. The poly(4-HDPA) contains both amino and carbonyl groups, and the carbonyl group is found to be fully responsible for redox reaction. Further investigation suggests that both Zn²⁺ and H⁺ in the ZnSO₄ electrolyte participate in the charge storage process, and the H⁺ plays a dominant role. The air-charging mechanism of this polymer cathode is elucidated both experimentally and theoretically. To demonstrate the practical applications, prototypes of box-shaped battery pack are air-charged to either drive a mini electric fan or light up LEDs.     

Soft Carbon as Anode for High‐Performance Sodium‐Based Dual Ion Full Battery

Sodium‐based dual ion full batteries (NDIBs) are reported with soft carbon as anode and graphite as cathode for the first time. The NDIBs operate at high discharge voltage plateau of 3.58 V, with superior discharge capacity of 103 mA h g^?1, excellent rate performance, and long‐term cycling stability over 800 cycles with capacity retention of 81.8%. The mechanism of Na⁺ and PF₆^? insertion/desertion during the charging/discharging processes is proposed and discussed in detail, with the support of various spectroscopies.     

Steel Anti-Corrosion Strategy Enables Long-Cycle Zn Anode

The progress of aqueous zinc batteries (AZBs) is limited by the poor cycling life due to Zn anode instability, including dendrite growth, surface corrosion, and passivation. Inspired by the anti-corrosion strategy of steel industry, a compounding corrosion inhibitor (CCI) is employed as the electrolyte additive for Zn metal anode protection. It is shown that CCI can spontaneously generate a uniform and ≈30 nm thick solid-electrolyte interphase (SEI) layer on Zn anode with a strong adhesion via Zn O bonding. This SEI layer efficiently prohibits water corrosion and guides homogeneous Zn deposition without obvious dendrite formation. This enables reversible Zn deposition and dissolution for over 1100 h under the condition of 1 mA cm⁻² and 1 mAh cm⁻² in symmetric cells. The Zn-MnO₂ full cells with CCI-modified electrolyte deliver an ultralow capacity decay rate (0.013% per cycle) at 0.5 A g⁻¹ over 1000 cycles. Such an innovative strategy paves a low-cost way to achieve AZBs with long lifespan.     

Lithium‐Pretreated Hard Carbon as High‐Performance Sodium‐Ion Battery Anodes

Hard carbon (HC) is the state‐of‐the‐art anode material for sodium‐ion batteries (SIBs). However, its performance has been plagued by the limited initial Coulombic efficiency (ICE) and mediocre rate performance. Here, experimental and theoretical studies are combined to demonstrate the application of lithium‐pretreated HC (LPHC) as high‐performance anode materials for SIBs by manipulating the solid electrolyte interphase in tetraglyme (TEGDME)‐based electrolyte. The LPHC in TEGDME can 1) deliver > 92% ICE and ≈220 mAh g^?1 specific capacity, twice of the capacity (≈100 mAh g^?1) in carbonate electrolyte; 2) achieve > 85% capacity retention over 1000 cycles at 1000 mA g^?1 current density (4 C rate, 1 C = 250 mA g^?1) with a specific capacity of ≈150 mAh g^?1, ≈15 times of the capacity (10 mAh g^?1) in carbonate. The full cell of Na₃V₂(PO₄)₃‐LPHC in TEGDME demonstrated close to theoretical specific capacity of ≈98 mAh g^?1 based on Na₃V₂(PO₄)₃ cathode, ≈2.5 times of the value (≈40 mAh g^?1) with nontreated HC. This work provides new perception on the anode development for SIBs.     

An Iodine-Chemisorption Binder for High-Loading and Shuttle-Free Zn–Iodine Batteries

Aqueous zinc–iodine (Zn–I₂) batteries have attracted considerable research interest as an alternative energy storage system due to their high specific capacity, intrinsic safety, and low cost. However, the notorious shuttle effect of soluble polyiodides causes severe capacity loss and poor electrochemical reversibility, restricting their practical usage. Herein, this study reports a bifunctional binder (polyacrylonitrile copolymer, as known as LA133) with strong iodine-chemisorption capability for aqueous Zn–I₂ batteries to suppress polyiodide shuttling. From both calculation and experimental data, this study reveals that the amide and carboxyl groups in LA133 binder can strongly bond to polyiodides, significantly immobilizing them at cathode side. As a result, fewer byproducts, slower hydrogen evolution, and lesser Zn dendrite in the Zn–I₂ battery are observed. Consequently, the battery shows high specific capacity (202.8 mAh g⁻¹) with high iodine utilization efficiency (96.1%), and long cycling lifespan (2700 cycles). At the high mass loading of 7.82 mg cm⁻², the battery can still retain 83.3% of its initial capacity after 1000 cycles. The specific capacity based on total cathode slurry mass reaches 71.2 mAh g⁻¹, higher than most of the recent works. The strategy opens a new avenue to address the shuttling challenge of Zn–I₂ batteries through bifunctional binder.     

Inducing the Preferential Growth of Zn (002) Plane for Long Cycle Aqueous Zn-Ion Batteries

Uncontrolled growth of Zn dendrites is the main reason for the short-circuit failure of aqueous Zn-ion batteries. Using electrolyte additives to manipulate the crystal growth is one of the most convenient strategies to mitigate the dendrite issue. However, most additives would be unstable during cycling due to the structural reconstruction of the deposition layer. Herein, it is proposed to use 1-butyl-3-methylimidazolium cation (BMIm⁺ ion) as an electrolyte additive, which could steadily induce the preferential growth of (002) plane and inhibit the formation of Zn dendrites. Specifically, BMIm⁺ ion will be preferentially adsorbed on (100) and (101) planes of Zn anodes, forcing Zn²⁺ ion to deposit on the (002) plane, thus inducing the preferential growth of the (002) plane and forming a flat and compact deposition layer. As a result, the Zn anode cycles for 1000 h at10 mA cm⁻² and 10 mAh cm⁻² as well as a high Coulombic efficiency of 99.8%. Meanwhile, the NH₄V₄O₁₀||Zn pouch cell can operate stably for 240 cycles at 0.4 A g⁻¹. The BMIm⁺ ion additive keeps a stable effect on the structural reconstruction of the Zn anode during the prolonged cycling.     

3D Printed Sodium-Ion Batteries via Ternary Anode Design Affording Hybrid Ion Storage Mechanism

Sodium-ion batteries (SIB), as one of the most appealing grid-scale energy storage devices, have to deal with the trade-off between the capacity output and rate performance. Utilizing 3D-printed (3DP) anode materials with hybrid sodium storage mechanism and elevated mass loading is promising yet poorly explored. Herein, the design of a prototype ternary composite is reported, MoS₂@Bi/N-doped carbon, as a sodium storage candidate to achieve high reversible capacity (604 mAh g⁻¹ at 0.1 A g⁻¹ with an initial output of 709 mAh g⁻¹) and outstanding rate capability (169.6 mAh g⁻¹ at 15 A g⁻¹), outperforming the state-of-the-art reports. This is realized by delicate structural and interfacial engineering of the composite anode, markedly synergizing the conversion-typed MoS₂, alloy-typed Bi, and adsorption-typed N-doped carbon. Theoretical simulations and operando instrumental analysis elaborate the reasons of the boosted electrochemical performance. Encouragingly, a fully 3DP SIB affording an areal mass loading of up to 11.7 mg cm⁻² is demonstrated, retaining a capacity of 114 mAh g⁻¹ at 1.0 A g⁻¹. This work would facilitate the design of 3DP SIB devices with the employment of advanced electrodes harnessing hybrid ion storage features.     

Partially Reduced Holey Graphene Oxide as High Performance Anode for Sodium‐Ion Batteries

The current Na⁺ storage performance of carbon‐based materials is still hindered by the sluggish Na⁺ ion transfer kinetics and low capacity. Graphene and its derivatives have been widely investigated as electrode materials in energy storage and conversion systems. However, as anode materials for sodium‐ion batteries (SIBs), the severe π–π restacking of graphene sheets usually results in compact structure with a small interlayer distance and a long ion transfer distance, thus leading to low capacity and poor rate capability. Herein, partially reduced holey graphene oxide is prepared by simple H₂O₂ treatment and subsequent low temperature reduction of graphene oxide, leading to large interlayer distance (0.434 nm), fast ion transport, and larger Na⁺ storage space. The partially remaining oxygenous groups can also contribute to the capacity by redox reaction. As anode material for SIBs, the optimized electrode delivers high reversible capacity, high rate capability (365 and 131 mAh g^?1 at 0.1 and 10 A g^?1, respectively), and good cycling performance (163 mAh g^?1 after 3000 cycles at a current density of 2 A g^?1), which is among the best reported performances for carbon‐based SIB anodes.     

Elucidation of the Sodium‐Storage Mechanism in Hard Carbons

Hard carbons (HCs) are the most promising candidate anode materials for emerging Na‐ion batteries (NIBs). HCs are composed of misaligned graphene sheets with plentiful nanopores and defects, imparting a complex correlation between its structure and sodium‐storage behavior. The currently debated mechanism of Na⁺‐ion insertion in HCs hinders the development of high‐performance NIBs. In this article, ingenious and reliable strategies are used to elaborate the correlation between the structure and electrochemical performance and further illuminate the sodium‐storage mechanism in HCs. First, filling sulfur into the micropores of HCs can remove the low‐voltage plateau, providing solid evidence for its association with the pore‐filling mechanism. Along with the decreased concentration of defects/heteroatoms at higher treatment temperature, the reduced sloping capacity confirms the adsorption mechanism in the sloping region. Finally, the similar sodium‐insertion behaviors of HCs with ether‐based and ester‐based electrolytes indicate that no Na⁺ ions intercalate between the graphene layers. The determined adsorption‐pore‐filling mechanism encourages the design of more efficient HC anode materials with high capacity for high‐energy NIBs.     

Charge and Discharge Processes and Sodium Storage in Disodium Pyridine‐2,5‐Dicarboxylate Anode—Insights from Experiments and Theory

A combined experimental and computational study of disodium pyridine‐2,5‐dicarboxylate (Na₂PDC) is presented exploring the possibility of using it as a potential anode for organic sodium‐ion batteries. This electrode material can reversibly insert/release two Na cations per formula unit, resulting in high reversible capacity of 270 mA h g^?1 (236 mA h g^?1 after accounting for the contribution from Super P carbon) with excellent cyclability 225 mA h g^?1, with retention of 83% capacity after 100 cycles, and good rate performance with reversible capacity of 138 mA h g^?1 at a 5 C rate. The performance of disodium pyridine dicarboxylate is therefore found to be superior to that of the related and well investigated disodium terephthalate. The material shows two voltage plateaus at about 0.6 V up to Na₂₊₁PDC and then 0.4 V up to full sodiation, Na₂₊₂PDC. The first plateau is attributed to the coordination of inserted Na to nitrogen atoms with bond formation, i.e., a different mechanism from the terephthalate analog. The subsequent plateau is due to coordination to the carboxylic groups.     

Revealing Pseudocapacitive Mechanisms of Metal Dichalcogenide SnS2/Graphene‐CNT Aerogels for High‐Energy Na Hybrid Capacitors

SnS₂ nanoplatelet electrodes can offer an exceptionally high pseudocapacitance in an organic Na⁺ ion electrolyte system, but their underlying mechanisms are still largely unexplored, hindering the practical applications of pseudocapacitive SnS₂ anodes in Na‐ion batteries (SIBs) and Na hybrid capacitors (SHCs). Herein, SnS₂ nanoplatelets are grown directly on SnO₂/C composites to synthesize SnS₂/graphene‐carbon nanotube aerogel (SnS₂/GCA) by pressurized sulfidation where the original morphology of carbon framework is preserved. The composite electrode possessing a large surface area delivers a remarkable specific capacity of 600.3 mA h g^?1 at 0.2 A g^?1 and 304.8 mA h g^?1 at an ultrahigh current density of 10 A g^?1 in SIBs. SHCs comprising a SnS₂/GCA composite anode and an activated carbon cathode present exceptional energy densities of 108.3 and 26.9 W h kg^?1 at power densities of 130 and 6053 W kg^?1, respectively. The in situ transmission electron microscopy and the density functional theory calculations reveal that the excellent pseudocapacitance originates from the combination of Na adsorption on the surface/Sn edge of SnS₂ nanoplatelets and ultrafast Na⁺ ion intercalation into the SnS₂ layers.     

Self-Regulating Interfacial Space Charge through Polyanion Repulsion Effect towards Dendrite-Free Polymer Lithium-Metal Batteries

Uncontrolled transport of anions leads to many issues, including concentration polarization, excessive interface side reactions, and space charge-induced lithium dendrites at the anode/electrolyte interface, which severely deteriorates the cycling stability of lithium metal batteries. Herein, an asymmetrical polymer electrolyte modified by a boron-containing single-ion conductor (LiPVAOB), is designed to inhibit the nonuniform aggregation of free anions in the vicinity of the lithium anode through the repulsion effect improving the lithium-ion transference number to 0.63. This LiPVAOB exerts a repulsion interaction with free anions even at a long distance and a selective effect for free anions transport, which diminishes uneven aggregation of free anions at the interface and suppresses space charges-induced lithium dendrites growth. Consequently, the assembled Li||Li cell delivers an ultra-long cycle for over 5400 h. The Li||LiFePO₄ cell exhibits outstanding cycle performance with a capacity retention of 93% over 4500 cycles. In particular, the assembled high-voltage Li||Li_1.2Ni_0.2Mn_0.6O₂ cell (charged to 4.8 V) exhibits good cycle stability with a high specific capacity of 245 mAh g⁻¹. This designed polymer electrolyte provides a promising strategy for regulating ion transport to inhibit space charge-induced lithium dendrite growth for high-performance lithium metal batteries.     

Revealing the Intercalation Mechanisms of Lithium,Sodium, and Potassium in Hard Carbon

Hard carbon is the most promising anode material for sodium‐ion batteries and potassium‐ion batteries owing to its high stability, widespread availability, low‐cost, and excellent performance. Understanding the carrier‐ion storage mechanism is a prerequisite for developing high‐performance electrode materials; however, the underlying ion storage mechanism in hard carbon has been a topic of debate because of its complex structure. Herein, it is demonstrated that the Li⁺‐, Na⁺‐, and K⁺‐ion storage mechanisms in hard carbon are based on the adsorption of ions on the surface of active sites (e.g., defects, edges, and residual heteroatoms) in the sloping voltage region, followed by intercalation into the graphitic layers in the low‐voltage plateau region. At a low current density of 3 mA g^–1, the graphitic layers of hard carbon are unlocked to permit Li⁺‐ion intercalation, resulting in a plateau region in the lithium‐ion batteries. To gain insights into the ion storage mechanism, experimental observations including various ex situ techniques, a constant‐current constant‐voltage method, and diffusivity measurements are correlated with the theoretical estimation of changes in carbon structures and insertion voltages during ion insertion obtained using the density functional theory.     

Stabilizing Multi-Electron NASICON-Na1.5V0.5Nb1.5(PO4)3 Anode via Structural Modulation for Long-Life Sodium-Ion Batteries

Multi-electron NAtrium SuperIonic CONductor (NASICON)-Nb₂(PO₄)₃ (N₀NbP) is an attractive Na-ion battery anode, owing to its low intercalation voltage (1.4 V vs Na⁺/Na⁰) and high capacity (≈150 mAh g⁻¹). However, it suffers from poor capacity retention due to structural degradation. To overcome this issue, extra Na⁺ ions are introduced at the Na(1) sites, via V³⁺ substitution, which can act as stabilizing agents to hold lantern units together during cycling, producing NASICON-Na_1.5V_0.5Nb_1.5(PO₄)₃ (N_1.5VNbP). The N_1.5VNbP anode exhibits reversible capacities of ≈140 mAh g⁻¹ at 1.4 V versus Na⁺/Na⁰ through Nb⁵⁺/Nb⁴⁺/Nb³⁺ and V³⁺/V²⁺ redox activities. The extra Na⁺ ions in the framework forms a complete solid-solution during Na (de)intercalation and enhances sodium diffusivity, in agreement with first-principles calculations. Further, N_1.5VNbP demonstrates extraordinary cycling (89% capacity retention at 5C after 500 cycles) and rate performances (105 mAh g⁻¹ at 5C). Upon pairing the N_1.5VNbP anode with the NASICON-Na₃V₂(PO₄)₃ cathode, the full Na-ion cell delivers a remarkable energy density of 98 Wh kg⁻¹ (based on the mass of anode and cathode) and retains 80% of its capacity at 5C rate over 1000 cycles. The study opens new possibilities for enhancing the electrochemical performance of NASICON anodes via chemical and structural modulations.     

Interrelation Between External Pressure,SEI Structure,and Electrodeposit Morphology in an Anode-Free Lithium Metal Battery

The interrelation is explored between external pressure (0.1, 1, and 10 MPa), solid electrolyte interphase (SEI) structure/morphology, and lithium metal plating/stripping behavior. To simulate anode-free lithium metal batteries (AF-LMBs) analysis is performed on “empty” Cu current collectors in standard carbonate electrolyte. Lower pressure promotes organic-rich SEI and macroscopically heterogeneous, filament-like Li electrodeposits interspersed with pores. Higher pressure promotes inorganic F-rich SEI with more uniform and denser Li film. A “seeding layer” of lithiated pristine graphene (pG@Cu) favors an anion-derived F-rich SEI and promotes uniform metal electrodeposition, enabling extended electrochemical stability at a lower pressure. State-of-the-art electrochemical performance is achieved at 1MPa: pG-enabled half-cell is stable after 300 h (50 cycles) at 1 mA cm⁻² rate −3 mAh cm⁻² capacity (17.5 µm plated/stripped), with cycling Coulombic efficiency (CE) of 99.8%. AF-LMB cells with high mass loading NMC622 cathode (21 mg cm⁻²) undergo 200 cycles with a CE of 99.4% at C/5-charge and C/2-discharge (1C = 178 mAh g⁻¹). Density functional theory (DFT) highlights the differences in the adsorption energy of solvated-Li⁺ onto various crystal planes of Cu (100), (110), and (111), versus lithiated/delithiated (0001) graphene, giving insight regarding the role of support surface energetics in promoting SEI heterogeneity.     

Self-Adaptive Hierarchical Hosts with Switchable Repulsive Shielding for Dendrite-Free Zinc-Ion Batteries

The engineering of anode-electrolyte interphase for highly reversible and dendrite-free Zn plating-stripping continues to pose a significant challenge in the progression of aqueous Zn-ion batteries (AZIBs). In this study, a novel approach is introduced that involves the design of a hierarchical carbon nanotube (CNT)-based host through functionalization with cetyltrimethylammonium cations (CTA⁺). This hierarchical host enables dynamically switchable repulsive shielding to regulate Zn plating. The CNT scaffold, featured with high flexibility and conductivity, facilitates expandable accommodation of continuous Zn plating. Concurrently, the entangled CTA⁺ cations, acting as manipulators to form switchable repulsive shields, dynamically suppress the growth of Zn dendrites, and result in uniform Zn plating within cationic CNT (C-CNT) hosts. The cationic shielding effect is further elucidated through density functional theory calculations. By incorporating the self-adaptive C-CNT host, Zn symmetric cells exhibit an impressively stable cycling lifespan exceeding 6500 h at 1 mA·cm⁻² and achieve a cumulative capacity of 6000 mAh·cm⁻² at 4 mA·cm⁻². Full batteries, by coupling the C-CNT@Zn anode and MnO₂ cathode, demonstrate an 88% capacity retention after 2000 cycles at 2 A·g⁻¹. The design of the self-adaptive C-CNT host offers a promising approach in electrode-electrolyte interphase engineering toward the practical applications of Zn-based energy storage systems.