Dendritic Growth Research Articles

Spatiotemporal prediction of solidified dendrites based on convolutional long-short-term neural network

The formation and growth of dendrites during the solidification of metals are critical factors influencing material properties. Accurate prediction of dendritic growth morphology and evolution is of great significance for materials science research and industrial applications. Traditional simulation methods, such as the phase-field method, provide high-precision results but are computationally expensive and time-consuming. Recently, with the advancement of deep learning technology, data-driven approaches have shown great potential in materials science. This paper proposes the use of Convolutional Long-Short-Term Memory Network (ConvLSTM) to capture spatiotemporal dependencies for predicting the spatiotemporal evolution of dendritic solidification in materials. By training on historical data of dendritic growth, the ConvLSTM neural network model predicts the future growth morphology of the dendritic microstructure during solidification. The model accurately forecasts the future morphology and appearance of the microstructure. Case studies were conducted using a generated dataset of dendritic solidification simulations, and the results demonstrate that the ConvLSTM model effectively captures the complex dynamic characteristics of dendritic growth and provides high-precision prediction results. This offers new insights for material design and optimization.

Study on the enhancement of flexible zinc-air battery performance with polyethylene glycol and nano SiO2 composite hydrogel

Flexible zinc-air batteries have garnered significant attention due to their high energy density, low cost, and environmental friendliness. However, issues such as poor cycle life and anode dendrite growth severely hinder their practical application. This study introduces polyethylene glycol (PEG) as a pore-forming agent and incorporates nano SiO2 into a polyacrylamide/carboxymethyl cellulose (PAM/CMC) composite hydrogel, resulting in a PAM/CMC/PEG/SiO2 (PCPS) composite hydrogel. Phase analysis and electrochemical characterization of PCPS were conducted. The hydrogel electrolyte formed in an alkaline KI environment, when assembled into a battery, achieved a capacity of 494.6 mAh/g and maintained a low potential range of 0.36 V for over 40 h, with an energy efficiency of 86.3 % for the first 60 cycles. To address the issue of dendrite growth in alkaline environments, this study also explores the performance of PCPS composite hydrogel in near-neutral environments.

Revealing the Effects of Pressure on the SDAS and Columnar Dendrite Growth Rate in 30Cr15Mo1N Ingot by Phase Field Method

Revealing the Effects of Pressure on the SDAS and Columnar Dendrite Growth Rate in 30Cr15Mo1N Ingot by Phase Field Method

Coupling Solvation Structure Regulation and Interface Engineering via Reverse Micelle Strategy Toward Highly Stable Zn Metal Anode

AbstractThe stability of aqueous Z inc (Zn) ion energy storage devices is significantly compromised by the instability at the electrode/electrolyte interface, which can result in the growth of Zn dendrites, self‐corrosion, and various other side reactions. Regulating the Zn‐ion （Zn2+) solvation structure through electrolyte additives has been proved to be effective strategy in stabilizing the Zn anode, but the influence of free water on the solvation structure is often lacking in‐depth exploration. Herein, the piperazine‐N,N‐bis(2‐hydroxypropanesulfonic acid) sodium salt (POPSO‐Na) is presented as a multifunctional electrolyte additive, which enhances the stability of the Zn anode by modulating the deposition and stripping environment of Zn2⁺ and limiting the presence of free water in the electrolyte during cycling. Theoretical calculation and experimental results demonstrate that the POPSO‐Na additive can not only replace the structural water around Zn2+ to destroy the original solvation sheath, but also form reverse micelle interface structure to hinder the proton transition and constrain the free water in the electrolyte. Thus, the Zn||Zn battery utilizing the ZnSO4+POPSO‐Na electrolyte exhibits an impressive cycle life of 1600 h at a current density of 1 mA cm−2, achieving an average Coulomb efficiency (CE) of ≈100%, which is significantly better than that observed with the ZnSO4 electrolyte. Moreover, the Zn||Cu battery with ZnSO4+POPSO‐Na electrolyte achieves high stability even after cycling for over 2000 h.

Crystallographic Reorientation Induced by Gradient Solid-Electrolyte Interphase for Highly Stable Zinc Anode.

Oriented zinc (Zn) electrodeposition is critical for the long-term performance of aqueous Zn metal batteries. However, the intricate interfacial reactions between the Zn anode and electrolytes hinder a comprehensive understanding of Zn metal deposition. Here, the reaction pathways of Zn deposition and report the preferential formation of Zn single-crystalline nuclei followed by dense Zn(002) deposition is elucidated, which is induced by a gradient solid-electrolyte interphase (SEI). The gradient SEI composed of abundant B-O and C species facilitates faster Zn2+ nucleation rate and smaller nucleus size, promoting the formation of Zn single-crystalline nuclei. Additionally, the homogeneity and mechanical stability of SEI ensure the crystallographic reorientation of Zn anodes from Zn(101) to (002) planes, efficiently inhibiting dendrite growth and metal corrosion during the Zn2+ stripping/plating process. These advantages significantly enhance the stability of the Zn anode, as demonstrated by the prolonged cycling lifespan of symmetric Zn batteries and exceptional reversibility (>99.5%) over 5000 cycles in Zn//Cu asymmetric batteries. Notably, this strategy also enables the stable operation of anode-free Zn//I2 batteries with a long lifespan of 3000 cycles. This work advances the understanding of Zn electrochemical behaviors, encompassing Zn nucleation, growth, and Zn2+ stripping/plating.

Nucleophilic Sn Seeding and Interface Engineering for Highly Stable Sodium Metal Batteries.

Sodium metal is a promising anode material for energy storage beyond lithium-ion batteries due to its abundance and low cost. However, the uncontrolled growth of dendrites and associated safety concerns have limited the practical application of sodium metal batteries (SMBs). By embedding nucleophilic tin seeds in a free-standing carbon film (FSF), here, an effective solution is developed to stabilize the sodium metal anode. The highly conductive and porous carbon matrix, intimately embedded with abundant Sn seeds (C@Sn), enables remarkably uniform sodium plating, and provides long-term stability for SMBs. Mechanistic studies confirm the formation of an Na─Sn alloy on interface which helps to lower the nucleation barrier for sodium plating. Hence, symmetric sodium cells equipped with C@Sn FSFs can sustain uninterrupted sodium plating and stripping for almost 2600h at a high areal capacity of 4mAhcm-2, achieving an average Coulombic efficiency (CE) of 99.88%. In addition, full cells prepared with commercial Na3V2(PO4)3 cathode and C@Sn-FSFs anode deliver remarkable cycling (90mAhg-1 beyond 1300 cycles at 1C) and excellent rate performance. This ingenious strategy of embedding Sn particles within a carbon matrix offers an overall compelling solution to enhance the longevity of sodium anodes.

Tailoring the Lithium Deposition on Cu Substrate by a Functionalized‐polysiloxane Layer

Owing to the high theoretical capacity of 3860 mAh·g‐1 and low redox potential, lithium metal is the best candidate for the development of next generation high‐energy density lithium‐ion batteries. However, notorious lithium dendrites growth and the poor compatibility of liquid electrolyte hinder the commercialization of lithium metal batteries. In this work, an anode‐less system was used to understand the change in lithium deposition on Cu current collector after the additional functionalized‐polysiloxane (PE) layer. The PE structure consists of lithiophobic and lithiophilic side chains which facilitate the uniform lithium deposition on Cu substrate. This evidence was collected by scanning electron microscopy (SEM) after the cycling test of half‐cell configuration and the lithium deposition with different current densities. The reversibility was improved by 5% compared with the bare Cu. In addition, the potential polarization was lowered after the addition of PE layer on bare Cu. Thus, the higher cycle stability (40%) and more stable coulombic efficiency are observed on the PE@Cu||NCM83 cell compared with the bare‐Cu||NCM83 during the cycle test.

Constructing Dual Schottky Junctions for High‐Performance Zinc Anode

AbstractAqueous zinc ion batteries provide new solutions for achieving environmentally friendly and safe energy storage devices. Unfortunately, the further application is hampered by the growth of zinc dendrites caused by uneven zinc deposition, hydrogen evolution and other side interfacial reactions at the zinc anode. Herein, a multifunctional Bi‐Bi2O3 hybrid artificial interface layer is constructed on the surface of the zinc anode using an in situ conversion reaction. Among them, the Bi‐Bi2O3 Schottky structure not only significantly accelerates the migration of Zn2+ through its built‐in electric field, but also effectively improves the hydrogen evolution barrier (ΔGH*), thereby suppressing side reactions. Moreover, the Schottky contact formed between the interface layer and the metal zinc interface also regulates the electronic distribution state on the zinc surface and optimizes the deposition process of Zn2+, ensuring a more uniform and orderly zinc deposition process. Based on the synergistic effect of dual Schottky junctions, symmetric batteries achieve stable cycling for 2000 h under the conditions of 1.0 mA cm−2 and 1.0 mAh cm−2. The full cell assembled with α‐MnO2 as the cathode maintains capacity of 112.7 mAh g−1 after 1000 cycles at 1 A g−1 with a capacity retention rate of 84%.

The Interaction Between Fluorinated Additives and Imidazolyl Ionic Liquid Electrolytes in Lithium Metal Batteries: A First‐Principles Study

ABSTRACTThis investigation employs first‐principles calculations to explore the interaction between imidazolium ionic liquids (ILs) and fluoride additives on lithium metal surface. Our focus lies in the comprehensive analysis of three distinct categories of fluorinated additives, each differing in their degree of fluorination. The computations reveal that fluorination plays a significant role in determining both the ionic conductivity and the formation of the solid–electrolyte interphase (SEI) film. Specifically, heightened fluorination enhances the oxidative stability of the system but diminishes the strength of solvent binding, resulting in the formation of larger salt/anion clusters and a decrease in ionic conductivity. Conversely, increased fluorination facilitates the interaction between fluorinated additives and the lithium metal surface, thereby aiding in the formation of a stable SEI film characterized by an abundance of inorganic LiF components. This is important as it serves to suppress dendrite growth and mitigate interface side reactions. Considering the combined influences of ionic conductivity and film formation, 1FP is suggested as the optimal candidate for pyridine‐based additive systems, with FEC preferred for cyclic ester‐based additive systems and BC for chain ester‐based additive systems. This study provides theoretical references for the design of ionic liquid‐fluorinated additive electrolyte systems that can protect the lithium metal anode.

An Ultrahigh-Modulus Hydrogel Electrolyte for Dendrite-Free Zinc Ion Batteries.

Quasi-solid-state aqueous zinc ion batteries suffer from anodic zinc dendrite growth during plating/stripping processes, impeding their commercial application. The inhibition of zinc dendrites by high-modulus electrolytes has been proven to be effective. However, hydrogel electrolytes are difficult to achieve high modulus owing to their inherent high water contents. This work reports a hydrogel electrolyte with ultrahigh modulus that can overcome the growth stress of zinc dendrites through mechanical suppression effect. By combining wet-annealing, solvent-exchange, and salting-out processes and tuning the hydrophobic and crystalline domains, a hydrogel electrolyte is obtained with substantial water content (≈70%), high modulus (198.5MPa), high toughness (274.3MJ m-3), and high zinc-ion conductivity (28.9 mS cm-1), which significantly outperforms the previously reported poly(vinyl alcohol)-based hydrogels. As a result, the hydrogel electrolyte exhibits excellent dendrite-suppression effect and achieves stable performance in Zn||Zn symmetric batteries (1800h of cycle life at 1mA cm-2). Moreover, the Zn||V2O5 pouch batteries display excellent cycling life and operate stably even under extreme conditions, such as large bending angle (180°) and automotive crushing. This work provides a promising approach for designing mechanically reliable hydrogel electrolytes for advanced aqueous zinc ion batteries.

Gradient Distribution of Zincophilic Sites for Stable Aqueous Zinc-Based Flow Batteries with High Capacity.

Current collectors, as reaction sites, play a crucial role ininfluencing various electrochemical performances in emerging cost-effective zinc-based flow batteries (Zn-based FBs). 3D carbon felts (CF) are commonly used but lack effectiveness in improving Zn metal plating/stripping. Here, a current collector with gravity-induced gradient copper nanoparticles (CF-G-Cu NPs) is developed, integrating gradient conductivity and zincophilicity to regulate Zn deposition and suppress side reactions. The CF-G-Cu NPs electrode modulates Zn nucleation and growth via the zincophilic Cu/CuZn5 alloy has been confirmed by density functional theory (DFT) calculations. Finite element simulation demonstrates the gradient internal structure effectively optimizes the local electric/current field distribution to regulate the Zn2+ flux, improving bottom-up plating behavior for Zn metal and mitigating top-surface dendrite growth. As a result, Zn-based asymmetrical FBs with CF-G-Cu NPs electrodes achieve an areal capacity of 30 mAhcm-2 over 640h with Coulombic efficiency of 99.5% at 40mAcm-2. The integrated Zn-Iodide FBs exhibit a competitive long-term lifespan of 2910h (5800 cycles) with low energy efficiency decay of 0.062% per cycle and high cumulative capacity of 112800 mAhcm-2 at a high current density of 100mAcm-2. This gradient distribution strategy offers a simple mode for developing Zn-based FB systems.

Constructing High‐Performance Zn‐Iodine Batteries with CuI‐PVP Composite Layer Coated Zn Anodes

AbstractAqueous zinc‐iodine (Zn‐I2) batteries featuring abundant raw materials, inherent safety, excellent cost competitiveness and environmental benignity have been identified as one kind of important electrochemical energy storage devices. However, these batteries always suffer from inferior electrochemical performance, because of dendrite growth and corrosion/passivation of the anodes. Herein, a copper iodide‐polyvinylpyrrolidone (CuI‐PVP) composite layer is proposed to suppress the parasitic reactions and protect the Zn anodes. In this layer, the CuI can spontaneously react with metallic Zn and convert into Cu and Cu5Zn8 (2CuI+Zn→2Cu+ZnI2; 5Cu+8Zn→Cu5Zn8). The highly zincophilic Cu and Cu5Zn8, as heterogeneous seeds, can guide the uniform Zn nucleation and deposition, while alleviating corrosion of the Zn anodes. At the same time, the iodide species releasing from the composite layer can be oxidized and deposited on the cathodes, contributing additional capacity. As a result, the symmetric cell prepared with the CuI‐PVP@Zn anodes demonstrates a long cycling lifetime of 1400 hours at 1 mA cm−2 and 1 mAh cm−2. Under an even higher current density of 5 mA cm−2, the CuI‐PVP@Zn cell can still stably work for more than 660 hours. The practical application of this CuI‐PVP@Zn electrode has been further demonstrated in Zn‐I2 full batteries, which achieve 60 % higher specific capacity than the untreated ones (251.4 vs. 157.1 mAh g−1 after 2800 cycles).

Multifunctional Nanocomposite Polymer‐integrated Ca‐doped CeO2 Electrolyte for Robust and High‐rate All‐solid‐state Sodium‐ion Batteries

AbstractDue to the seamless interfaces between solid polymer electrolytes (SPEs) and electrode materials, SPEs‐based all‐solid‐state sodium‐ion batteries (ASSSIBs) are considered promising energy storage systems. However, the sluggish Na+ transport and uncontrollable Na dendrite propagation still hinder the practical application of SPEs‐based ASSSIBs. Herein, Ca‐doped CeO2 (Ca−CeO2) nanotube framework is synthesized and integrated with poly (ethylene oxide) methyl ether acrylate‐perfluoropolyether copolymer (PEOA‐PFPE), resulting in multifunctional solid nanocomposite electrolytes (namely SNEs, i.e., PEOA‐PFPE/Ca−CeO2). Our investigations demonstrate that the fluorous effect incurred by the fluorine‐containing PEOA‐PFPE and the oxygen vacancy effect induced by the Ca−CeO2 framework could synergistically promote the dissociation of sodium salt, ultimately enhancing the Na+ mobility in SNEs. Besides, the resultant SNEs construct rapid Na+ transport channels and homogenize the Na deposition in SNEs/Na interface, which effectively prevents the Na dendrite growth. Furthermore, the assembled carbon‐coated sodium vanadium phosphate (NVP@C)||PEOA‐PFPE/Ca−CeO2||Na coin cell delivers impressive rate capability of 97.9 mAh g−1 at 2 C and outstanding cycling stability with capacity retention of 84.3 % after 300 cycles at 1 C. This work illustrates that constructing multifunctional SNEs via incorporating functional inorganic frameworks into fluorine‐containing SPEs could be a promising strategy for the commercialization of robust and high‐performance ASSSIBs.

Advanced Eutectogel Electrolyte for High‐Performance and Wide‐Temperature Flexible Zinc‐Air Batteries

AbstractDespite ongoing challenges, achieving further breakthroughs in the development of gel polymer electrolytes with a wide temperature range, excellent liquid retention capability and enhanced anode compatibility in flexible zinc‐air batteries (FZABs) remains a significant objective. This study presents a significant advancement in the development of choline chloride/ethylene glycol‐polyvinyl alcohol (ChCl/EG‐PVA) eutectogel electrolyte, tailored for high‐performance operation across a wide temperature range. Systematic in‐situ and ex‐situ characterizations and theoretical simulations confirm the formation of robust hydrogen bonding and denser polymer cross‐linked networks within the prepared eutectogel, leading to enhanced liquid retention ability (93.7 % after 96 h exposure to air) and ion transport capacity (ionic conductivity of 171.3 mS cm−1). Additionally, the zincophilicity nature of the choline cation in eutectogel effectively suppresses dendrites growth. The assembled FZAB utilizing this eutectogel electrolyte achieves a peak power density of 109.3 mW cm−2 and a cycle life of 90 h. Notably, the power density of FZAB is maintained as high as 38.2 mW cm−2 at −40 °C and 63.2 mW cm−2 at 50 °C, demonstrating its prominent suitability for applications in extreme temperature conditions. The design of eutectogel provides a novel way to achieve the high‐performance FZAB.

Polyethylene Glycol-Protected Zinc Microwall Arrays for Stable Zinc Anodes.

Aqueous zinc-ion batteries promise good commercial application prospects due to their environmental benignity and easy assembly under atmospheric conditions, positioning them as a viable alternative to lithium-ion batteries. However, some inherent issues, such as chaotic zinc dendrite growth and inevitable side reactions, challenge the commercialization progress. In this work, we imprint highly ordered zinc microwall arrays to regulate the electric field toward uniform Zn deposition. Afterward, coating a polyethylene glycol protection layer on the zinc microwalls aims to passivate the surface defects that rise unintentionally by mechanical imprinting. Polyethylene glycol can also boost oriented Zn deposition along the (002) plane and inhibit hydrogen gas production, further enhancing the stability of such three-dimensional (3D) hybrid anodes. Compared to the messy electric field near the polyethylene glycol-protected Zn foil, the uniform electric field provided by these 3D hybrid anodes can regulate the Zn deposition behaviors, enabling a longer lifespan and thus certifying the necessity of adding 3D microstructures. Additionally, 3D microstructures can offer a larger surface area than that of the planar Zn foil, providing more reaction sites and higher specific capacity. In this case, the 3D hybrid electrode exhibits a good initial capacity of approximately 120 mA h/g at a current density of 5 A/g and a nice retention of more than 80% after 800 cycles. The proposed scheme paves the way for a long-term stable 3D zinc anode solution with promising application prospects.

Synergistic Long-Term Protection of Inorganic and Polymer Hybrid Coatings for Free-Dendrite Zinc Anodes.

Constructing an artificial solid electrolyte interface protective layer on the surface of the zinc anode is an effective strategy for addressing dendrite growth, passivation, and the hydrogen evolution reaction in aqueous zinc-ion batteries. This study introduces a robust interlayer composed of a polyvinyl butyral matrix decorated with SiO2 particles (PS). Adsorption of water by Si-OH on the surface of SiO2 leads to excellent hydrophilicity and accelerates the desolvation of ions. A highly stable and hydrophilic PS coating enhances ion migration and possesses ultralong protection ability, ensuring uniform ion deposition and a lower nucleation barrier. Anodes protected by the PS coating achieve long-term cycling stability of >4000 h at 2 mA cm-2 in symmetric cells. The assembled PS-Zn//NH4V4O10 full cells exhibit superior electrochemical performance, demonstrating their potential for practical applications in rechargeable zinc batteries.

Advanced Eutectogel Electrolyte for High-Performance and Wide-Temperature Flexible Zinc-Air Batteries.

Despite ongoing challenges, achieving further breakthroughs in the development of gel polymer electrolytes with a wide temperature range, excellent liquid retention capability and enhanced anode compatibility in flexible zinc-air batteries (FZABs) remains a significant objective. This study presents a significant advancement in the development of choline chloride/ethylene glycol-polyvinyl alcohol (ChCl/EG-PVA) eutectogel electrolyte, tailored for high-performance operation across a wide temperature range. Systematic in-situ and ex-situ characterizations and theoretical simulations confirm the formation of robust hydrogen bonding and denser polymer cross-linked networks within the prepared eutectogel, leading to enhanced liquid retention ability (93.7 % after 96 h exposure to air) and ion transport capacity (ionic conductivity of 171.3 mS cm-1). Additionally, the zincophilicity nature of the choline cation in eutectogel effectively suppresses dendrites growth. The assembled FZAB utilizing this eutectogel electrolyte achieves a peak power density of 109.3 mW cm-2 and a cycle life of 90 h. Notably, the power density of FZAB is maintained as high as 38.2 mW cm-2 at -40 °C and 63.2 mW cm-2 at 50 °C, demonstrating its prominent suitability for applications in extreme temperature conditions. The design of eutectogel provides a novel way to achieve the high-performance FZAB.

Diffusion Behavior and Kinetics for the Vapor Phase Infiltration of Trimethylaluminum in Poly(ethylene oxide): An In Situ Quartz Crystal Microgravimetry Study.

Vapor phase infiltration (VPI) facilitates the incorporation of inorganic components into organic polymers, emerging as an effective technique for fabricating organic-inorganic hybrid materials. However, the complexity of diffusion behavior during the VPI process presents challenges in studying diffusion kinetics, particularly for highly reactive precursor-polymer systems such as trimethylaluminum (TMA) and poly(ethylene oxide) (PEO). In this study, we investigate the VPI process of TMA in PEO using in situ quartz crystal microgravimetry (QCM), which enables measurement of diffusion behavior and kinetics with high precision due to its high temporal resolution. Our results indicate that the VPI process consists of two main regions: a rapid diffusion process, corresponding to the initial penetration of the precursor into the film, followed by a slower relaxation process, attributed to the ongoing chemical reaction. The equivalent diffusion coefficient (De) was estimated to be on the order of 10-9 cm2/s and decreased with increasing aluminum content. Using energy application as a proof-of-concept, when optimized, VPI-modified PEO films were successfully utilized as solid polymer electrolytes (SPEs) for lithium metal batteries (LMBs), showcasing superior performance in mitigating lithium dendrite growth. This study offers valuable insights into the VPI process for PEO-TMA systems and provides guidance for optimizing VPI conditions to enhance the performance of advanced materials.

Constructing a Multifunctional SEI Layer Enhancing Kinetics and Stabilizing Zinc Metal Anode

AbstractZn dendrite growth and parasitic reactions at the interface of zinc anode/electrolyte in aqueous zinc batteries severely hinder its lifespan in application. Herein, the zinc anode is effectively stabilized by introducing trace amounts of 4‐aminobutane‐1‐phosphate (ABPA) into the ZnSO4 electrolyte. The ABPA adsorbs onto the surface of zinc anode and then further decomposes to a high conductive organic/inorganic composite in situ SEI layer including amino, partial carbon chain, and zinc phosphate. In the SEI layer, the residual undecomposed carbon chain promotes the desolvation of Zn2+, the amino induces uniform Zn2+ plating and zinc phosphate facilitates the migration of Zn2+. Thus, this in situ SEI layer not only suppresses water‐related side reactions but also enhances the Zn2+ transport kinetics. As a result, Zn||Zn symmetric cell delivers an ultralong cycle life of over 13 000 cycles at 50 mA cm−2 and 1 mAh cm−2. A high average Coulombic efficiency of 99.72% is achieved in over 1000 cycles in Zn||Cu half‐cell. The Zn||I2 full cell delivers a high‐capacity retention of 91.42% after 40,000 cycles. Moreover, a 49 mAh Zn||I2 pouch cell maintains 80.28% capacity retention over 300 cycles and 61.22% after 1000 cycles.

Boosting Dendrite‐Free Zinc Anode with Strongly Polar Functional Group Terminated Hydrogel Electrolyte for High‐Safe Aqueous Zinc‐Ion Batteries

AbstractAqueous zinc‐ion batteries (AZIBs) have become a promising energy storage device due to their low cost and high security. However, the severe dendrite growth and side reactions on metallic zinc (Zn) anode hamper their commercial implementation. Herein, a strongly electronegative trifluoroborate anion (─BF3−) functionalized polyacrylamide hydrogel (PAME) is well‐designed and constructed as the quasi‐solid‐state electrolyte to overcome these obstacles. The PAME chain segments terminated with strongly polar functional groups promote the conversion of water molecules from free water to bound water through the enhanced hydrogen bonding interaction to alleviate the side reactions. Furthermore, the PAME electrolyte featured with hierarchically porous structure and enhanced electrostatic interaction among the ─BF3− groups, and Zn2+ ions homogenizes the high‐flux Zn ion transport and induce the uniform deposition to restrain dendrite growth. Consequently, the assembled Zn‖PAME‖Zn batteries deliver remarkable cycling stability over 1800 h at 1 mA cm−2 and 900 h at 15 mA cm−2. Additionally, the constructed Zn‖PAME‖MnO2 full cells achieve a reversible capacity of 202 mAh g−1 at 2.0 A g−1 with a capacity retention rate of 91.4% over 500 cycles. This work sheds light on constructing the strongly polar hydrogel electrolyte to boost free‐dendrite Zn anodes for long‐lifespan AZIBs.