Zn Anode Research Articles

Stable zinc anode solid electrolyte interphase via inner Helmholtz plane engineering

The inner Helmholtz plane and thus derived solid-electrolyte interphase (SEI) are crucial interfacial structure to determine the electrochemical stability of Zn-ion battery (ZIB). In this work, we demonstrate that introducing β-cyclodextrins (CD) as anion-receptors into Zn(OTf)2 aqueous electrolyte could significantly optimize the Zn anode SEI structure for achieving stable ZIB. Specifically, β-CD with macrocyclic structure holds appropriate cavity size and charge distribution to encase OTf- anions at the Zn metal surface to form β-CD@OTf- dominated inner Helmholtz structure. Meanwhile, the electrochemically triggered β-CD@OTf- decomposition could in situ convert to the organic-inorganic hybrid SEI (ZnF2/ZnCO3/ZnS‒(C-O-C/*CF/*CF3)), which could efficiently hinder the Zn dendrite growth with maintain the proper SEI mechanical strength stability to guarantee the long-term stability. The thus-derived Zn | |Zn pouch cell (21 cm2 size) with β-CD-containing electrolyte exhibits a cumulative capacity of 6450 mAh−2 cm−2 at conditions of 10 mAh cm−2 high areal capacity. This work gives insights for reaching stable ZIB via electrolyte additive triggered SEI structure regulation.

Artificial aluminum-doped SiO2 aerogel coating layer regulating zinc ions flow for highly reversible dendrite-free zinc anodes

As a sustainable, safe, and cost-effective alternative to conventional lithium-ion batteries, aqueous rechargeable zinc-metal-based batteries have attracted significant attention in large-scale energy storage. However, their practical application is hindered by zinc anode degradation, primarily dendrite growth and corrosion, which compromise battery performance and lifespan. Herein, we present an aluminum-doped silica (Al-SiO2) aerogel coating layer to address these issues. The aluminum-doped silica aerogel coating layer offers improved hydrophilicity and zinc ion adsorption capabilities because of its porous structure, high surface area, and functional groups. By facilitating uniform zinc ion deposition and providing a physical barrier against corrosion, the Al-SiO2 aerogel coating layer significantly mitigates dendrite formation and extends the electrochemical stability and operational lifespan of aqueous rechargeable zinc-metal-based batteries. Symmetric cell tests reveal that zinc anodes coated with Al-SiO2 can achieve stable cycling over 3000 h, indicating exceptional reversibility and rate performance, much better than that of the bare Zn anode. Furthermore, the Al-SiO2 aerogel-coated zinc anode coupled with MnO2 cathode forms a stable rechargeable full battery. This work contributes to the body of knowledge on advanced materials for energy storage, highlighting the potential of aerogel coatings as a scalable and effective solution for improving the performance and durability of zinc metal anode for aqueous rechargeable zinc-metal-based batteries.

Hydrophobic, zincophilic and conductive SEI protective layer stabilizes metallic Zn anode under high current densities

The uncontrollable growth of Zn dendrites and adverse side reactions significantly hinder the application of metallic Zn anodes in aqueous batteries. Herein, nitrogen-doped carbon skeleton/ZnO nanocrystalline are grown in-situ within carbon hollow dodecahedrons (denoted as CZCHD) through the controlled pyrolysis of zeolitic imidazole framework-8 dodecahedrons coated with polydopamine. The solid electrolyte interface layer constructed by CZCHD suppresses hydrogen evolution and corrosion reactions, reduces nucleation barrier, improves Zn deposition kinetics, accelerates desolvation and transport of Zn2+ ions, and regulates Zn deposition behavior. When tested in symmetric cells, CZCHD@Zn anodes afford exceptional plating/stripping stability at 5 mA cm−2/1 mAh cm−2 (2681 h), 10 mA cm−2/10 mAh cm−2 (780 h), and 20 mA cm−2/20 mAh cm−2 (240 h). In asymmetric cells, CZCHD@Cu exhibits average Coulombic efficiency of 99.5 % over 500 cycles. Morphological and structural evolution analyses demonstrate the preferential horizontal flaky Zn deposition beneath the CZCHD protective layer, with no Zn dendrites observed on the surface. Furthermore, when coupled with MnVO cathodes, the assembled full cells display stable cycling performance at 2 and 5 A/g. The stable, reversible, efficient, dendrite-free Zn deposition is attributed to the synergistic effects of high hydrophobicity, strong zincophilicity and high electrical conductivity of CZCHD, which is confirmed by contact angle measurements, theoretical calculations based on density functional theory, and electrochemical impedance spectroscopy.

Single‐Anion Conductive Solid‐State Electrolytes with Hierarchical Ionic Highways for Flexible Zinc‐Air Battery

AbstractFlexible zinc‐air batteries are leading power sources for next‐generation smart wearable electronics. However, flexible zinc‐air batteries suffer from the highly‐corrosive safety risk and limited lifespan due to the absence of reliable solid‐state electrolytes (SSEs). Herein, a single‐anion conductive SSE with high‐safety is constructed by incorporating a highly amorphous dual‐cation ionomer into a robust hybrid matrix of functional carbon nanotubes and polyacrylamide polymer. The as‐fabricated SSE obtains dual‐penetrating ionomer‐polymer networks and hierarchical ionic highways, which contribute to mechanical robustness with 1200 % stretchability, decent water uptake and retention, and superhigh ion conductivity of 245 mS ⋅ cm−1 and good Zn anode reversibility. Remarkably, the flexible solid‐state zinc‐air batteries delivers a high specific capacity of 764 mAh ⋅ g−1 and peak power density of 152 mW ⋅ cm−2 as well as sustains excellent cycling stability for 1050 cycles (350 hours). This work offers a new paradigm of OH− conductors and broadens the definition and scope of OH− conductors.

Single-Anion Conductive Solid-State Electrolytes with Hierarchical Ionic Highways for Flexible Zinc-Air Battery.

Flexible zinc-air batteries are leading power sources for next-generation smart wearable electronics. However, flexible zinc-air batteries suffer from the highly-corrosive safety risk and limited lifespan due to the absence of reliable solid-state electrolytes (SSEs). Herein, a single-anion conductive SSE with high-safety is constructed by incorporating a highly amorphous dual-cation ionomer into a robust hybrid matrix of functional carbon nanotubes and polyacrylamide polymer. The as-fabricated SSE obtains dual-penetrating ionomer-polymer networks and hierarchical ionic highways, which contribute to mechanical robustness with 1200 % stretchability, decent water uptake and retention, and superhigh ion conductivity of 245 mS ⋅ cm-1 and good Zn anode reversibility. Remarkably, the flexible solid-state zinc-air batteries delivers a high specific capacity of 764 mAh ⋅ g-1 and peak power density of 152 mW ⋅ cm-2 as well as sustains excellent cycling stability for 1050 cycles (350 hours). This work offers a new paradigm of OH- conductors and broadens the definition and scope of OH- conductors.

Tailoring Oxygen‐Depleted and Unitary Ti3C2Tx Surface Terminals by Molten Salt Electrochemical Etching Enables Dendrite‐Free Stable Zn Metal Anode

AbstractTwo‐dimensional Ti3C2Tx MXene materials, with metal‐like conductivities and versatile terminals, have been considered to be promising surface modification materials for Zn‐metal‐based aqueous batteries (ZABs). However, the oxygen‐rich and hybridized terminations caused by conventional methods limit their advantages in inhibiting zinc dendrite growth and reducing corrosion‐related side reactions. Herein, −O‐depleted, −Cl‐terminated Ti3C2Tx was precisely fabricated by the molten salt electrochemical etching of Ti3AlC2, and controlled in situ terminal replacement from −Cl to unitary −S or −Se was achieved. The as‐prepared −O‐depleted and unitary‐terminal Ti3C2Tx as Zn anode coatings provided excellent hydrophobicity and enriched zinc‐ionophilic sites, facilitating Zn2+ horizontal transport for homogeneous deposition and effectively suppressing water‐induced side reactions. The as‐assembled Ti3C2Sx@Zn symmetric cell achieved a cycle life of up to 4200 h at a current density and areal capacity of 2 mA cm−2 and 1 mAh cm−2, respectively, with an impressive cumulative capacity of up to 7.25 Ah cm−2 at 5 mA cm−2//2 mAh cm−2. These findings provide an effective electrochemical strategy for tailoring −O‐depleted and unitary Ti3C2Tx surface terminals and advancing the understanding of the role of specific Ti3C2Tx surface chemistry in regulating the plating/stripping behaviors of metal ions.

Tailoring Oxygen-Depleted and Unitary Ti3C2Tx Surface Terminals by Molten Salt Electrochemical Etching Enables Dendrite-Free Stable Zn Metal Anode.

Two-dimensional Ti3C2Tx MXene materials, with metal-like conductivities and versatile terminals, have been considered to be promising surface modification materials for Zn-metal-based aqueous batteries (ZABs). However, the oxygen-rich and hybridized terminations caused by conventional methods limit their advantages in inhibiting zinc dendrite growth and reducing corrosion-related side reactions. Herein, -O-depleted, -Cl-terminated Ti3C2Tx was precisely fabricated by the molten salt electrochemical etching of Ti3AlC2, and controlled in situ terminal replacement from -Cl to unitary -S or -Se was achieved. The as-prepared -O-depleted and unitary-terminal Ti3C2Tx as Zn anode coatings provided excellent hydrophobicity and enriched zinc-ionophilic sites, facilitating Zn2+ horizontal transport for homogeneous deposition and effectively suppressing water-induced side reactions. The as-assembled Ti3C2Sx@Zn symmetric cell achieved a cycle life of up to 4200 h at a current density and areal capacity of 2 mA cm-2 and 1 mAh cm-2, respectively, with an impressive cumulative capacity of up to 7.25 Ah cm-2 at 5 mA cm-2//2 mAh cm-2. These findings provide an effective electrochemical strategy for tailoring -O-depleted and unitary Ti3C2Tx surface terminals and advancing the understanding of the role of specific Ti3C2Tx surface chemistry in regulating the plating/stripping behaviors of metal ions.

A Dual Salt/Dual Solvent Electrolyte Enables Ultrahigh Utilization of Zinc Metal Anode for Aqueous Batteries.

Rechargeable aqueous zincbatteriesare promising in next-generation sustainable energy storage. However, the low zinc (Zn) metal anode reversibility and utilization in aqueous electrolytes due to Zn corrosion and poor Zn2+ deposition kinetics significantly hinder the development of Zn-ion batteries. Here, a dual salt/dual solvent electrolyte composed of Zn(BF4)2/Zn(Ac)2 in water/TEGDME (tetraethylene glycol dimethyl ether) solvents to achieve reversible Zn anode at an ultrahigh depth of discharge (DOD) is developed. An "inner co-salt and outer co-solvent" synergistic effect in this unique dual salt/dual solvent system is revealed. Experimental results and theoretical calculations provide evidence that the ether co-solvent inhibits water activity by forming hydrogen bonding with the water and coordination effects with the proton in the outer Zn2+ solvation structure. Meanwhile, the anion of zinc acetate co-salt enters the inner Zn2+ solvation structure, thereby accelerating the desolvation kinetics. Strikingly, based on the electrolyte design, the zinc anode shows high reversibility at an ultrahigh utilization of 60% DOD with 99.80% Coulombic efficiency and 9.39 mAh cm-2 high capacity. The results far exceed the performance reported in electrolyte design work recently. The work provides fundamental insights into inner co-salt and outer co-solvent synergistic regulation in multifunctional electrolytes for reversible aqueous metal-ion batteries.

Effect of pre-inserted monovalent cations on vanadium-based cathode materials for rechargeable aqueous zinc-ion batteries

Understanding the effect of pre-inserted cations in vanadium-based from a comprehensive perspective plays a vital role in exploring novel cathode materials for Zn-ion storage. In this work, we provide a study of monovalent cations (i.e., Na+, K+, and NH4+) on the Zn2+ storage behaviors of proton-substituted vanadates (i.e., NaVO, KVO, and NH4VO), revealing the intrinsic property (e.g., hydration capacity, bonding strength) of monovalent ions has a significant impact on the amount of pre-inserted cations and crystal water in stacked V–O layers, as well as the morphology of the obtained products, and the structural evolution during the activated process. Due to the enhancement of the ion-diffusion kinetics and stronger capacitance properties from the synergistic effect by pre-inserted Na+ ions and crystal water, the NaVO cathode exhibits superior rate performance and better energy efficiency (60.87 % at 10 A g−1), delivers a high specific capacity of 427.0 mAh g−1 at 0.2 A g−1 and retains 74.3 % of capacity after 1900 cycles at 2 A g−1. Moreover, the correlation between the pre-inserted cations in the cathode and the issues (e.g., side-products and dendrites) of the Zn anode has been revealed, providing new insight into designing high-performance cathodes for Zn ion batteries.

Reconstruction of zinc-metal battery solvation structures operating from −50 ~ +100 °C

Serious solvation effect of zinc ions has been considered as the cause of the severe side reactions (hydrogen evolution, passivation, dendrites, and etc.) of aqueous zinc metal batteries. Even though the regulation of cationic solvation structure has been widely studied, effects of the anionic solvation structures on the zinc metal were rarely examined. Herein, co-reconstruction of anionic and cationic solvation structures was realized through constructing a new multi-component electrolyte (Zn(BF4)2-glycerol-boric acid-chitosan-polyacrylamide, simplified as ZGBCP), which incorporates double crosslinking network via the esterification, protonation and polymerization reactions, thereby combining multiple advantages of ‘liquid-like’ high conductivity, ‘gel-like’ robust interface, and ‘solid-like’ high Zn2+ transfer number. Based on the ZGBCP electrolyte, the Zn anodes achieve record-low polarization and stable cycling. Furthermore, the ZGBCP electrolyte renders the AZMBs ultrawide working temperature (−50 °C ~ +100 °C) and ultralong cycle life (30000 cycles), which further validates the feasibility of the dual solvation structure strategy and provides a innovative perspective for the development of high-performance AZMBs.

Ultrathin Protection Layer via Rapid Sputtering Strategy for Stable Aqueous Zinc Ion Batteries

AbstractSurface side reactions and time‐consuming modification methods hinder the practical application of zinc‐ion batteries. This study introduces an ultrathin protection layer for the Zn anode via a rapid sputtering method. The dopants on the CN10@Zn anode create surface dipoles and local variations in charge distribution, facilitating zinc ion migration to pyrrolic nitrogen dopant sites with reduced adsorption barriers. Additionally, hydroxyl oxygen dopants enhance the hydrophilicity of the sputtering layer, forming a strong adhesion with the zinc anode and improving ion accessibility. This results in dense nucleation sites for uniform zinc deposition. Consequently, the sputtered layer achieves a Coulombic efficiency of 99.8% over 2,700 cycles in Cu||Zn cells and a lifespan of up to 2,100 h in zinc symmetric cells. When paired with Na0.65Mn2O4 cathodes, the sputtered layer retains 89% capacity over 1,000 cycles at 1 A g−1. This study presents a promising method for rapidly fabricating ultrathin electrode materials.

Non‐Epitaxial Electrodeposition of Overall 99% (002) Plane Achieves Extreme and Direct Utilization of 95% Zn Anode and By‐Product as Cathode

Zn anode protection in Zn‐ion batteries (ZIBs) face great challenges of high Zn utilization rate (i.e., depth of discharge, DOD) and high current density due to the large difficulty in obtaining an extreme overall RTC (relative texture coefficient) of Zn (002) plane. Through the potent interaction of Mn(III)aq and H+ with distinct Zn crystal planes under an electric field, large‐size Zn foils with a breakthrough (002) plane RTC of 99% (i.e., close to Zn single crystal) are electrodeposited on texture‐less substrates, which is also applicable from recycled Zn. The ultra‐high (002) plane RTC remarkably enhances cyclic performance of the Zn anode (70% DOD @ 45.5 mA cm‐2), and the DOD is even up to 95% (@ 28.1 mA cm‐2) with an electrolyte additive of polyaniline. Furthermore, MnO2, the by‐product of electrodeposition, is directly used as cathode of both coin cell and pouch battery, surpassing the cyclic performance exhibited by the majority of Zn||MnO2 batteries in previous instances. These results demonstrate the great potential of our strategy for high‐performance, low‐cost and large‐scale ZIBs.

Non-Epitaxial Electrodeposition of Overall 99 % (002) Plane Achieves Extreme and Direct Utilization of 95 % Zn Anode and By-Product as Cathode.

Zn anode protection in Zn-ion batteries (ZIBs) face great challenges of high Zn utilization rate (i.e., depth of discharge, DOD) and high current density due to the large difficulty in obtaining an extreme overall RTC (relative texture coefficient) of Zn (002) plane. Through the potent interaction of Mn(III)aq and H+ with distinct Zn crystal planes under an electric field, large-size Zn foils with a breakthrough (002) plane RTC of 99 % (i.e., close to Zn single crystal) are electrodeposited on texture-less substrates, which is also applicable from recycled Zn. The ultra-high (002) plane RTC remarkably enhances cyclic performance of the Zn anode (70 % DOD @ 45.5 mA cm-2), and the DOD is even up to 95 % (@ 28.1 mA cm-2) with an electrolyte additive of polyaniline. Furthermore, MnO2, the by-product of electrodeposition, is directly used as cathode of both coin cell and pouch battery, surpassing the cyclic performance exhibited by the majority of Zn||MnO2 batteries in previous instances. These results demonstrate the great potential of our strategy for high-performance, low-cost and large-scale ZIBs.

An artificial sulfonated polyaniline coating for high stable and dendrite-free zinc anode

Designing the performance of artificial solid electrolyte interphase (ASEI) is critical for addressing issues at the Zn anode-electrolyte of aqueous zinc batteries (AZBs). Inspired by the anti-corrosion strategy of metal substrate, a self-doping sulfonated polyaniline (S-PANI) is constructed on the surface of zinc foil by a facile scraping method. The synergistic effect of nitrogen and sulfonic acid groups in S-PANI coating layer, accompanies microchannels in the polymer network is favorable for the fast Zn2+ ion transport, uniform and stable Zn deposition. As a result, the Zn anode with S-PANI coating can achieve high average coulombic efficiency of 98.0% over 150 cycles and superior cycling performance up to 1500 h at a 0.5 mA cm-2 and 0.5 mAh cm-2. Moreover, the full battery coupled with PTO organic cathode also demonstrates superior cycling stable performance. This work opens effective approach for the application of conductive polymer coating in Zn anode protection.

Gel biopolymer electrolyte for high-voltage, durable, and flexible Zn/K dual-ion pouch cells

Zinc-ion rechargeable battery (ZIRB) is a promising candidate for future energy storage systems due to its cost-effectiveness, operational safety, and environmental friendliness. However, the commercial-scale application of ZIRB is hindered by its insufficient energy efficiency, poor rate capability, and inferior cycling stability. Here, we introduce a gel biopolymer electrolyte (GBE) empowered Zn/K dual-ion battery with exceptional cycling and rate performance. Calling for sustainability, this cellulose-encapsulated bisalt electrolyte presents strong mechanical robustness that inhibits Zn dendrite growth and promotes anodic plating/stripping reversibility. Sandwiching the GBE between a potassium manganese hexacyanoferrate (KMnHCF) cathode and a Zn anode, the coin-cell configuration of KMnHCF|GBE|Zn demonstrates a high voltage discharge plateau of 1.80 V, an initial capacity of up to 65 mAh g−1, and excellent cycling stability with capacity retention of 92 % after 1,000 cycles. Furthermore, the superior durability, flexibility, safety, and endurance with extreme conditions (e.g., bending, puncturing, and cutting) demonstrated by KMnHCF|GBE|Zn pouch-cell enables its future application in wearable electronics.

Stabilizing Zinc Anode through Ion Selection Sieving for Aqueous Zn-Ion Batteries.

Uncontrollable dendrite growth and corrosion induced by reactive water molecules and sulfate ions (SO42-) seriously hindered the practical application of aqueous zinc ion batteries (AZIBs). Here we construct artificial solid electrolyte interfaces (SEIs) realized by sodium and calcium bentonite with a layered structure anchored to anodes (NB@Zn and CB@Zn). This artificial SEI layer functioning as a protective coating to isolate activated water molecules, provides high-speed transport channels for Zn2+, and serves as an ionic sieve to repel negatively charged anions while attracting positively charged cations. The theoretical results show that the bentonite electrodes exhibit a higher binding energy for Zn2+. This demonstrates that the bentonite protective layer enhances the Zn-ion deposition kinetics. Consequently, the NB@Zn//MnO2 and CB@Zn//MnO2 full-battery capacities are 96.7 and 70.4 mAh g-1 at 2.0 A g-1 after 1000 cycles, respectively. This study aims to stabilize Zn anodes and improve the electrochemical performance of AZIBs by ion-selection sieving.

Tailoring the Whole Deposition Process from Hydrated Zn2+ to Zn0 for Stable and Reversible Zn Anode

The practical application of aqueous zinc‐ion batteries (ZIBs) indeed faces challenges primarily attributed to the inherent side reactions and dendrite growth associated with the Zn anode. In the present work, N‐Methylmethanesulfonamide (NMS) is introduced to optimize the transfer, desolvation, and reduction of Zn2+, achieving highly stable and reversible Zn plating/stripping. The NMS molecule can substitute one H2O molecule in the solvation structure of hydrated Zn2+ and be preferentially chemisorbed on the Zn surface to protect Zn anode against corrosion and hydrogen evolution reaction (HER), thereby suppressing byproducts formation. Additionally, a robust N‐rich organic and inorganic (ZnS and ZnCO3) hybrid solid electrolyte interphase is in situ generated on Zn anode due to the decomposition of NMS, resulting in enhanced Zn2+ transport kinetics and uniform Zn2+ deposition. Consequently, aqueous cells with the NMS achieve a long lifespan of 2300 h at 1 mA cm−2 and 1 mAh cm−2, high cumulative plated capacity of 3.25 Ah cm−2, and excellent reversibility with an average coulombic efficiency (CE) of 99.7% over 800 cycles.

Tailoring the Whole Deposition Process from Hydrated Zn2+ to Zn0 for Stable and Reversible Zn Anode.

The practical application of aqueous zinc-ion batteries (ZIBs) indeed faces challenges primarily attributed to the inherent side reactions and dendrite growth associated with the Zn anode. In the present work, N-Methylmethanesulfonamide (NMS) is introduced to optimize the transfer, desolvation, and reduction of Zn2+, achieving highly stable and reversible Zn plating/stripping. The NMS molecule can substitute one H2O molecule in the solvation structure of hydrated Zn2+ and be preferentially chemisorbed on the Zn surface to protect Zn anode against corrosion and hydrogen evolution reaction (HER), thereby suppressing byproducts formation. Additionally, a robust N-rich organic and inorganic (ZnS and ZnCO3) hybrid solid electrolyte interphase is in situ generated on Zn anode due to the decomposition of NMS, resulting in enhanced Zn2+ transport kinetics and uniform Zn2+ deposition. Consequently, aqueous cells with the NMS achieve a long lifespan of 2300 h at 1 mA cm-2 and 1 mAh cm-2, high cumulative plated capacity of 3.25 Ah cm-2, and excellent reversibility with an average coulombic efficiency (CE) of 99.7 % over 800 cycles.

Pyrrole as a multi-functional additive to concurrently stabilize Zn anode and cathode via interphase regulation towards advanced aqueous zinc-ion battery

The advancement of aqueous zinc-ion batteries (AZIBs) is impeded by challenges encompassing cathodic and anodic aspects, such as limited capacity and dendrite formation, constraining their broader utilization. Herein, pyrrole, an economically viable and readily accessible compound, is proposed as a versatile electrolyte additive to address these challenges. Experiments and DFT calculations reveal that pyrrole and its derivatives preferentially adsorb onto zinc foil, facilitating the formation of a pyrrole-based solid electrolyte interphase (SEI), which effectively guides uniform Zn2+ deposition through strong attraction force and suppresses hydrogen evolution reactions and parasitic reactions. On the cathode side, the additive promotes the formation of a durable cathode electrolyte interphase (CEI) enriched with poly-pyrrole (Ppy) analogues. Such layer significantly contributes to extra capacity of both polyaniline (PANI) and MnO2 cathodes by leveraging the electrochemical reactivity of Ppy towards Zn2+ and improves their cyclic stability. Consequently, a dendrite-free Zn anode is realized with an extended cyclic lifespan surpassing 6000 h in Zn//Zn cell, coupled with an average Coulombic efficiency of 99.7 % in Cu//Zn cell. Moreover, the PANI//Zn and MnO2//Zn full cells demonstrate enhanced capacities along with improved cycling stability. This work provides a new additive strategy towards concurrent stabilization of cathode and Zn anode in AZIBs.

Suitable Stereoscopic Configuration of Electrolyte Additive Enabling Highly Reversible and High-Rate Zn Anodes.

Electrolyte additive engineering is a crucial method for enhancing the performance of aqueous zinc-ion batteries (AZIBs). Recently, most research predominantly focuses on the role of functional groups in regulating electrolytes, often overlooking the impact of molecule stereoscopic configuration. Herein, two isomeric sugar alcohols, mannitol and sorbitol, are employed as electrolyte additives to investigate the impact of the stereoscopic configuration of additives on the ZnSO4 electrolyte. Experimental analysis and theoretical calculations reveal that the primary factor for improving Zn anode performance is the regulation of the solvation sheath by these additives. Among the isomers, mannitol exhibits stronger binding energies with Zn2+ ions and water molecules due to its more suitable stereoscopic configuration. These enhanced bindings allow mannitol to coordinate with Zn2+, contributing to solvation structure formation and reducing the active H2O molecules in the bulk electrolyte, resulting in suppressed parasitic reactions and inhibited dendritic growth. As a result, the zinc electrodes in mannitol-modified electrolyte exhibit excellent cycling stability of 1600 h at 1 mA cm-2 and 900 h at 10 mA cm-2, respectively. Hence, this study provides novel insights into the importance of suitable stereoscopic molecule configurations in the design of electrolyte additives for highly reversible and high-rate Zn anodes.