{"paper_id":"137956d9-e4df-47a6-86e6-29ff44d8483e","body_text":"Decoupling ionic transfer kinetics via undercoordinated constraints for energy-efficient and high-quality zinc electrowinning | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Decoupling ionic transfer kinetics via undercoordinated constraints for energy-efficient and high-quality zinc electrowinning Wei Zhang, Hao Cheng, Zheng Li, Guoxuan Li, Zibo Chen, Xinyi Li, and 6 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-7829869/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted You are reading this latest preprint version Abstract Zinc electrowinning (ZE), a carbon-intensive process, suffers from high energy consumption due to the parasitic hydrogen evolution reaction (HER) and poor deposit quality. Conventional adsorption-based additives fail to simultaneously deliver high current efficiency (CE) and low cell voltage, sustaining energy inefficiency. To address this limitation, we propose an electrolyte engineering through undercoordinated topology constraint (UTC) to regulate Zn 2+ and proton transfer kinetics. Using weakly-coordinating additives, UTC weakens SO 4 2− -Zn 2+ interactions while preserving locally continuous but long-range disordered hydrogen bond (HB) networks, thereby increasing the translational freedom ( f trans ) of Zn 2+ and restricting proton transport. The resulting kinetics decoupling facilitates zinc deposition and suppresses HER at high current densities, thereby elevating CE and saving energy. Implemented with acetonitrile (ACN) as a model molecule, the decoupled ion transport homogenizes the interfacial ion and field distribution and directs the growth of corrosion-resistant (101)-faceted deposits. And the ACN-induced UTC enables ZE to achieve 94.3% CE with an energy demand of 2531.4 kWh t − 1 at 500 A m − 2 (40 ℃), a factor of only 1.55 above the theoretical minimum. It also demonstrates robust performance under extreme F − contamination (1 g L − 1 ), simultaneously boosting CE by 11.96% and slashing energy consumption by 12.87% at 700 A m − 2 . This work establishes electrolyte topology engineering as a powerful pathway to sustainable and energy-efficient metal electrowinning. Physical sciences/Chemistry/Physical chemistry/Reaction kinetics and dynamics Physical sciences/Engineering/Chemical engineering Physical sciences/Chemistry/Electrochemistry Physical sciences/Chemistry/Materials chemistry Zinc electrowinning electrolyte topology engineering hydrogen evolution reaction transfer kinetics energy consumption Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Introduction Zinc, the fourth most produced metal (over 13,000 kt annually, 210,000 kt reserves), is 90% refined by hydrometallurgy, where electrowinning consumes 80% of sectoral energy and jeopardizes net-zero goals 1 – 4 . Current zinc electrowinning (ZE) intensity (2800–3400 kWh t - 1 ) substantially exceeds the theoretical minimum (1633 kWh t - 1 ) by up to twofold, directly hindering decarbonization 5 , 6 . Energy-efficient ZE demands high current efficiency (CE), low cell voltage, and high-quality deposits (Fig. 1 a), yet persistent cathodic hydrogen evolution reaction (HER) remains the primary obstacle 7 , 8 . HER proceeds via both direct H + reduction and electrochemical water splitting, aggravated by zinc self-corrosion and impurity-driven galvanic attack 9 . These parasitic processes consume electrons, reduce CE and raise voltage, imposing a prohibitive energy burden magnified in multi-electrode cells (Fig. 1 b). Thus, suppressing HER is pivotal for energy-efficient ZE and drives the current research. Electrolyte engineering has pursued mitigation through functional additives. The competitive adsorption of H + and Zn 2+ on the cathode interface underlies the design of adsorption-type additives 8 , 10 – 13 . Despite extensive research, industrial ZE still relies on traditional protein-based additives such as gelatin and glue 11 , 14 . In acidic media, these colloidal additives become cationic and selectively adsorb onto the cathode under an electric field, jointly suppressing HER and templating zinc crystallization. However, their performance is highly concentration-sensitive, with ppm-level effects governed by steric hindrance and surface coverage. This sensitivity impedes Zn 2+ transport and obstructs interfacial reduction, increasing cell voltage by 56–144 mV and lowering CE by 30–49% 14,15 . Consequently, adsorption-dependent mechanisms impose inherent limits on efficiency gains, and dosage-sensitive operation undermines scale-up. These constraints underscore the need for additive strategies beyond interfacial adsorption. Electrolyte building-block design along the Zn 2+ to Zn 0 pathway offers a targeted route to regulate ZE 16–18 . High acid/zinc electrolytes (130–180 g L - 1 H 2 SO 4 , 45–70 g L - 1 Zn 2+ ) favor SO 4 2- coordination and hinder Zn 2+ desolvation (Fig. 1 c). At high current density, sluggish Zn 2+ transport contrasts with rapid H + /H 2 O migration, thereby accelerating HER 19 – 21 . High Gutmann donor number (DN) additives suppress HER but over-stabilize Zn 2+ solvation, impeding deposition 22 , 23 . Low DN additives weaken hydration and accelerate desolvation but the excess disrupts electric double layer (EDL) and shells, elevating barriers 24 – 27 . By contrast, weakly-coordinating additives are promising for ZE, but their role in reconciling zinc deposition with HER kinetics at industrial current densities remains unresolved. From a classical physics view, these trade-offs reflect constraints on ionic degrees of freedom (DOF): translational ( f trans ), rotational ( f rot ), and vibrational ( f vib ) 28 , 29 . Under electric fields, translational motion dominates bulk-to-interface transport, with solvent exchange and progressive desolvation as the primary kinetic barriers 30 . Thus, solvation and coordination constrain both Zn 2+ and H + mobility. Weakly-coordinating additives preserve higher f trans , accelerating interfacial processes. The key challenge, therefore, is to design constraints that selectively raise f trans for Zn 2+ while decreasing it for H + . Such selective decoupling would promote efficient deposition while inhibiting HER for industrial energy-efficient ZE. In aqueous solution, Zn 2+ exists primarily as Zn(H 2 O) 6 2+ 30 . Relative to hydration, ligands with stronger affinity than H 2 O impose powerful constraints, inducing overcoordination, whereas weaker interactions yield undercoordination. Abundant SO 4 2- in ZE electrolytes drives strong electrostatic binding and inevitable overcoordination, lowering f trans for Zn 2+ . Conversely, finely tuned undercoordination weakens interaction strength while preserving the solvation topology, elevating Zn 2+ transport. For protons, Zundel (H 5 O 2 + ) and Eigen (H 9 O 4 + ) species diffuse through defect migration along hydrogen bond (HB) networks 21 , 31 . Quantum fluctuations delocalize protons over multiple HBs, while solvent polarization lowers the transfer barrier, jointly accounting for their intrinsically high f trans . Introducing weakly-coordinating molecules interrupts long-range transfer but maintains local hopping. Unlike overcoordination, which terminates HB pathways, such undercoordination preserves topological continuity of HB networks yet overall reduces f trans of protons. Thus, ionic transport is governed not by structural reorganization but by topological inheritance, where subtle undercoordination adapts existing networks to decouple Zn 2+ and H + transport with high selectivity. Herein, we propose an undercoordinated topology constraint (UTC) strategy mediated by electrolyte additives with low donor numbers (< 18 kcal mol - 1 ) to decouple the opposing f trans requirements of Zn 2+ and H + . Unlike traditional solvation-shell reconstruction or HB network disruption, UTC creates metastable Zn 2+ solvation clusters through undercoordinated ligand-field modulation. This weakens coordination strength and reduces SO 4 2- density while maintaining local HB connectivity. The design couples topological entropy with reaction kinetics: elevated f trans enhances entropy and lowers the Zn 2+ desolvation barrier, facilitating the zinc deposition, while regulated HBs frustrate Grotthuss proton long-range conduction, suppressing HER. By optimizing ion transport kinetics, this modification would markedly improve the CE and minimize energy usage. Implemented with acetonitrile (ACN), the UTC strategy achieved a high CE of 94.3% with an energy consumption of 2531.4 kWh t - 1 at 500 A m - 2 and 40 ℃. Moreover, halide impurities (e.g., F - , Cl - ) pose a critical challenge in ZE by accelerating HER and corrosion, forcing costly purification to adhere to ~ 100 mg L⁻¹ F - limits 9 . The UTC strategy substantially extends the tolerance of electrolyte to halide impurities. Even under harsh conditions with F–rich electrolyte (1 g L - 1 ), the system delivered an 11.96% increase in CE and a 390.7 kWh t - 1 reduction in energy consumption at 700 A m - 2 compared with the unmodified electrolyte. This work demonstrates electrolyte topology engineering as a powerful and sustainable approach to advance industrial metal electrowinning. Results Principles of electrolyte design and implementation for industrial ZE An unconstrained ion has three translational DOF ( f trans = 3) along the x , y , and z axes 32 , 33 . Each coordination bond within the solvation removes one f trans . Since each bond connects two ions, and the total bond number equals half the coordination number ( z ). The residual translational freedom ( f r ) is thus defined in Eq. (1). Here, f r = 0 denotes an ideally full ordination. Positive f r indicates undercoordination with faster kinetics, and negative f r reflects overcoordination with hindered mobility. In real electrolytes, competitive ligand coordination complicates this situation 34 , 35 . Ligand type, size, and binding strength critically modulate f trans . Assuming a single ligand type per ion, we introduce a weighted correction factor ( α ) to capture intrinsic ligand effects, yielding Eq. (2). This descriptor captures the full trajectory of cations from bulk solvation through diffusion to interfacial desolvation (Fig. 1 c). Taking Zn 2+ hydration as the baseline ( α = 0), α is positive for overcoordination and negative for undercoordination, correlating with the Gutmann DN. Using H 2 O (DN = 18 kcal mol - 1 ) as the reference (Fig. 1 d) 36 , additives with DN > 18 kcal mol - 1 ( α > 0) induce strong Zn 2+ coordination, reconstructing compact solvation structures and fragmenting HB networks. Such overcoordination reduces translational freedom ( f r ’< 0) for both Zn 2+ and H + , slowing Zn 2+ transport while suppressing HER. This DOF reduction is effective in batteries but collapses under the high current densities required for industrial electrowinning. To address this limitation, an UTC strategy ( f r ’ >0) is proposed to selectively relax Zn 2+ coordination. By employing additives with DN < 18 kcal mol - 1 ( α < 0), UTC preserves the parent electrolyte framework while expanding the Zn 2+ solvation shells and maintaining locally continuous HB networks (Fig. 1 d). The weaker coordination enhances electrostatic flexibility and topological entropy, thereby accelerating Zn 2+ diffusion and desolvation. Simultaneously, undercoordination induces HB rigidity, suppressing ligand exchange and restricting parasitic H + flux. In this way, UTC decouples the f trans of Zn 2+ and H + , enabling rapid field response and high-efficiency zinc electrowinning. To elucidate the structural basis of improved ionic freedom, we introduced acetonitrile (ACN) as a model molecule into the electrolyte. ACN combines industrial accessibility with mild ligand strength (DN = 14.1 kcal mol - 1 ) 36 . Moreover, its intrinsically low viscosity and broad thermal window enable superior adaptability to complex electrolytes and harsh ZE conditions. Quantum chemical calculations confirm that SO 4 2- exhibits the strongest binding affinity (Fig. 2 a), interacting robustly with Zn 2+ , H 3 O + , and H 2 O. In contrast, ACN displays the minimal binding energy, underscoring its weak interaction with cations. Thus, SO 4 2- imposes a dominant electrostatic constraint, significantly limiting f r ’ of cations, whereas HBs effects exhibit subtler differences. Rigid potential scans (Fig. 2 b) and electrostatic potential (ESP) distributions (Fig. 2 c) highlight these distinctions. The H 2 O-H 2 O HB (H-H) is slightly stronger (-0.161 eV) and shorter (1.85 Å) than the H 2 O-ACN interaction (H-A, -0.159 eV, 1.95 Å). Quantum chemical analysis attributes these weaker interactions to electron density redistribution 37 . While H-H and H-A bonds show comparable geometries, their electronic features differ markedly. As shown in Fig. 2 c, positive charge localizes on the H and negative charge on the O in H-H interactions, partially canceling at the HB interface. In contrast, H-A interactions localize negative charge on H 2 O and positive charge on ACN, imparting a negative electrostatic character at the HB site. This favors H + localization between H 2 O and ACN, rather than between two H 2 O molecules, thereby inducing topological rigidity. Molecular dynamics (MD) simulations further explained the structural evolution of ACN-containing electrolytes at 313 K. The reduction in total energy confirms enhanced thermodynamic stability with ACN (Supplementary Fig. 1a). While the number of H-H bonds decreases (Fig. 2 d), their average lifetime increases to 2.37 ps (Supplementary Fig. 1b). Conversely, H-A bonds exhibit a substantially shorter lifetime of 1.14 ps. Probability distributions show that ACN-containing electrolytes develop a higher population of shorter HBs (Fig. 2 e) and smaller HB angles (Supplementary Fig. 1c). It indicates that ACN strengthened H 2 O-H 2 O interactions while H 2 O-ACN interactions remain weak. Notably, ACN promotes the formation of locally continuous HB networks characterized by short-range order but long-range disorder. Though shorter HBs could in principle facilitate proton transfer, the resulting topological networks suppress Grotthuss -type long-range conduction, reducing f r ’ of protons while maintaining overall ionic conductivity. Radial distribution functions (RDFs) and coordination numbers (CNs) further clarify the structural modifications induced by ACN. ACN resides in the second solvation shell of both H 3 O + and Zn 2+ (Figs. 2 f, g). For H 3 O + , binding distances with H 2 O (0.164 nm) and SO 4 2- (0.160 nm) remain unchanged after ACN introduction. However, the CN of H 2 O decreases from 0.672 to 0.643, while that of SO 4 2- increases from 0.356 to 0.367. For Zn 2+ , the CN of H 2 O rises from 5.176 to 5.466 at 0.212 nm, whereas the CN of SO 4 2- declines from 0.824 to 0.536 at 0.206 nm. Notably, ACN markedly diminishes the local SO 4 2- density near Zn 2+ (Fig. 2 g). These results demonstrate that acts indirectly from the second solvation shell, subtly modulating the local ionic environment (Supplementary Fig. 2). The strong electrostatic interactions in unmodified electrolytes produce tightly bound solvation shells that restrict DOF for Zn 2+ , elevating the desolvation energy barrier (E de ) (Fig. 2 h). At high current densities, sluggish Zn 2+ diffusion, desolvation, and electron transfer create severe interfacial concentration gradients. Local Zn 2+ depletion allows protons to dominate the reduction process, lowering the CE. Conversely, ACN weakens Zn 2+ -SO 4 2- electrostatic interactions, substantially reducing the desolvation barrier (E de ’) and enabling more uniform Zn 2+ flux at the interface. Advanced in-situ spectroscopy further corroborates these findings. SO 4 2- characteristic peaks remain stable below 50 ℃ in the presence of ACN (Supplementary Figs. 3, 4). Temperature-dependent Raman spectra reveal a critical structural transition in Supplementary Fig. 5. The symmetric stretching mode of SO 4 2- ( V (SO 4 2- )) shifts from 964 cm - 1 to 978 cm - 1 upon ACN addition. According to the Eigen-Tamm model, V (SO 4 2- ) bands can be deconvoluted into contact ion pairs (CIPs, Zn 2+ (H 2 O) 5 (OSO 3 2- )) and solvent-separated ion pairs (SSIPs, Zn 2+ (H 2 O) 6 ·(SO 4 2- )) 38,39 . The blue shift signifies that SO 4 2- experiences increased difficulty penetrating Zn 2+ solvation shells due to the dragging effect of ACN, resulting in an expanded topological Zn 2+ solvation shell. Parallel shifts in V (HSO 3 - ) bands also confirm ACN can weaken electrostatic attractions 40 . These spectroscopic findings directly corroborate MD simulations. Additionally, the OH stretching vibration ( V (OH), 3300–3700 cm - 1 ) exhibits significant modification with ACN addition (Supplementary Fig. 4). At fixed additive concentration, V (OH) undergoes progressive blue shifts with increasing temperature. The shift primarily reflects HB weakening caused by intensified thermal molecular motion 41 . And we systematically probed ACN concentration effects on HBs at 40 ℃ (Fig. 3 ), replicating industrial ZE conditions. Generally, the broad V (OH) band comprises contributions from strong (~ 3500 cm - 1 ), medium (~ 3570 cm - 1 ) and weak (~ 3684 cm - 1 ) HBs 42 . Two-dimensional infrared spectrometer (2D-IR) correlation spectroscopy reveals the regulating effect of ACN 43 . Synchronous spectra show positive auto-peaks at 3500 cm - 1 and 3570 cm - 1 (Fig. 3 a), indicating ACN significantly perturbs strong and medium HBs, while weaker peaks at 3684 cm - 1 suggest minimal disruption of weak HBs. Positive cross-peaks (red) confirm synchronous enhancement of these HB modes. Asynchronous spectra (Fig. 3 b) resolve the sequential modification of HBs: strong (3500 cm - 1 ) → weak (3384 cm - 1 ) → medium (3570 cm - 1 ). This sequence reveals that ACN preferentially disrupts tetrahedral networks, liberating weakly bonded water monomers, that subsequently reorganize into medium or strong HBs. Raman spectra validate this HB classification established by FTIR with corresponding bands across 3000–3800 cm - 1 (Fig. 3 c) 44 . Quantitative analysis shows that the proportion of strong HBs increases monotonically with ACN concentration, while medium and weak HBs decrease concurrently (Fig. 3 d). The 1 H nuclear magnetic resonance (NMR) spectra reveal a downfield shift of H 2 O upon ACN addition, confirming de-shielding that reduces the influence of SO 4 2- on hydrogen electron density (Fig. 3 e). At higher ACN concentrations, this effect weakens, consistent with direct ACN-H 2 O coordination. Excessive ACN disrupts the topological continuity of HB networks, as evidenced by perturbations in -CH 3 signals (Supplementary Fig. 6). As illustrated in Fig. 3 f, ACN constrains proton hopping along HB networks. It is well known that the hydrated protons normally diffuse through structural defect migration via Eigen-Zundel-Eigen interconversion. ACN selectively suppresses long-range proton transport while preserving short-range transfer, thereby increasing HB rigidity and decreasing proton entropy. This fragmentation produces HB networks that are locally continuous but discontinuous at long-range, dynamically reducing f r ’ of protons. Investigations of HER and zinc electrodeposition behavior Physicochemical analyses confirm that ACN maintains electrolyte stability under ZE operating temperatures while exerting minimal influence on viscosity and conductivity (Supplementary Fig. 7). During ZE, deposition initiates on aluminum cathodes before propagating across zinc substrates. Corrosion measurements show that ACN negligibly affects aluminum dissolution but significantly suppresses zinc corrosion (Fig. 4 a). Specifically, the zinc corrosion rates reduce from 0.91 to 0.48 mg cm - 2 h - 1 at 1.8 M ACN. Linear sweep voltammetry (LSV) further quantifies HER suppression (Fig. 4 b). The proton reduction peak at -0.90 V progressively diminishes with increasing ACN concentration, accompanied by negative potential shifts that indicate inhibited proton reduction. Cathodic polarization triggers the co-reduction of Zn 2+ and protons. The required potential shifts negatively from − 1.06 V to -1.12 V at 5 mA cm - 2 with rising ACN concentration, demonstrating concurrent suppression of both processes. Control experiments with sodium sulfate validate this HER inhibition (Supplementary Fig. 8). Tafel analysis reveals that corrosion current density decreases by 56% from 87.10 to 38.28 mA cm - 2 , while corrosion potential shifts positively by 73 mV (Supplementary Fig. 4c and Supplementary Table 1). These results demonstrate that ACN effectively protects the electrode surface by constraining the f r ’ of protons, thereby suppressing HER and corrosion simultaneously. Electrochemical impedance spectroscopy (EIS) reveals that ACN increases charge transfer resistance (Supplementary Fig. 9). Distribution of relaxation times (DRT) analysis further deciphers interfacial evolution (Fig. 4 d). The high-frequency peak, corresponding to bulk electrolyte resistance 45 , 46 , intensifies with increasing ACN concentration, consistent with conductivity trends. The low-frequency charge-transfer peak undergoes concentration-dependent evolution. From 0 to 1.0 M ACN, it shifts toward lower frequencies with reduced intensity, indicating longer charge-transfer relaxation times. At concentrations above 1.0 M, a distinct adsorption process emerges, dominating interfacial dynamics. Differential capacitance measurements corroborate these findings (Fig. 4 e). Positive potential shifts decrease capacitance, consistent with preferential ACN adsorption on the electrode surface. The zero-charge potential ( φ 0 ) shifts positively, signifying reduced surface negative charge 47 , 48 . This behavior indicates that ACN displaces H 2 O/SO 4 2- , forming a newly oriented dipolar layer at the interface. Cyclic voltammetry (CV) identifies the nucleation potential for Zn 2+ reduction on aluminum electrodes (Fig. 4 f). The nucleation overpotential (NOP), defined as the difference between crossover and reduction potentials 11 , is 68 mV in the additive-free electrolyte. With increasing ACN concentration, NOP initially decreases but remains below 68 mV up to 1 M, then gradually rises. Zinc deposition overpotentials also increase monotonically with ACN concentration. Galvanostatic profiles at 500 A m - 2 confirm electrode stability in ACN-modified electrolytes, with potential variations reflecting altered kinetics (Fig. 4 g). Chronoamperometry further elucidates deposition dynamics. As shown in Supplementary Fig. 10, current density initially rises before decaying to a steady state. And the rise corresponds to nucleation and growth, while the decay reflects diffusion layer thickening and overlap. Higher applied potentials reduce the time (t m ) required to reach limiting current density (I m ). These features confirm diffusion-controlled 3D nucleation 45 . Scharifker-Hills modeling classifies the process as instantaneous nucleation (3DI) (Fig. 4 h) 49 . Increasing t m with ACN concentration indicates a buffered Zn 2+ concentration gradient (Supplementary Fig. 10), which promotes dense and fine-grained deposits by enabling uniform nucleation. At excess ACN concentration, however, interfacial blocking from over-adsorption counteracts this benefit. Thus, ACN dosage must be carefully optimized to balance f r ’ of cations in both bulk electrolyte and at the interface. Zinc electrowinning performance improvement with UTC ZE cells were assembled to validate the UTC strategy. Firstly, three-electrode measurements show that ACN minimally affects the Pb-Ag anode oxygen evolution reaction (OER) overpotential while reducing operational voltage at 500 A m - 2 (Supplementary Fig. 11), attributed to activation of the anode passivation layer. Full-cell testing reveals a strong concentration dependence. CE peaks at 94.30% with 1.0 M ACN at 500 A m - 2 (Fig. 5 a). Concurrently, cell voltage and energy consumption decrease to 2.84 V and 2508.3 kWh t - 1 at 1.8 M ACN (Figs. 5 b, c). At higher current densities, however, these benefits diminish due to Zn 2+ f r ’ limitations and ACN-induced interfacial effects. At 1500 A m - 2 , UTC electrolytes show only a 5.34% CE loss, a 60 mV voltage increase, and a 263.5 kWh t - 1 energy penalty relative to ACN-free systems (Supplementary Figs. 12a-c). It demonstrates competitive advantages over existing additives (Supplementary Table 2). Stepwise current testing further confirms operational robustness (Supplementary Figs .12d-f). Industrial ZE electrolytes contain halide impurities from mineral processing, where chloride and fluoride impurities accelerate electrode corrosion and reduce CE by increasing voltage and energy consumption. Conventional practice requires stringent impurity control (500 mg L - 1 Cl - , 100 mg L - 1 F - ) via energy-intensive purification 9 , 50 . Remarkably, ACN mitigates halide effects of industrial contaminants (Supplementary Figs. 12g-l). At 700 A m - 2 with 1 M ACN and 1 g L - 1 F - , UTC increases CE by 11.96% and reduces energy consumption by 390.7 kWh t - 1 , approaching fluoride-free baseline performance and demonstrating unprecedented impurity tolerance. Deposit quality is equally critical for industrial feasibility. Poor zinc layers exhibiting spalling, porosity or cracks complicate downstream processing. At increasing current density, deposits without ACN become progressively rougher, whereas optimal ACN concentrations eliminate corrosion pits and yield smooth, compact surfaces (Fig. 5 d, Supplementary Fig. 13). Excess ACN (> 1.0 M) reverses this effect producing coarse ridge-valley morphologies with interlocking grains (Supplementary Fig. 14). This distinct morphology stems from adsorption-mediated competitive crystal growth across zinc facets. Higher-resolution SEM further elucidates the morphological transitions (Figs. 5 e, f). In additive-free electrolytes, SEM reveals widespread corrosion cavities and heterogeneous surface texture (Figs. 5e1, e2). At higher magnification, zinc predominantly grows as distorted hexagonal (002) platelets aligned parallel to the electrode, adopting terraced pyramidal stacking (Figs. 5f1, f2). This hierarchical growth mode drives pronounced coarsening and morphological irregularity. At optimal ACN concentrations, corrosion cavities are eliminated and surface uniformity is markedly improved (Figs. 5e3, e4). Although sparse inclined hexagonal grains remain, most crystallites reorient into angled platelet morphologies relative to the surface (Figs. 5f3, f4). Beyond this threshold, however, deposits exhibit roughness (Figs. 5e5, e6), with pronounced crystallite coarsening and interlocking morphologies (Figs. 5f5, f6). XRD analysis confirms that ACN drives preferential crystal reorientation from (002) to (101) planes (Fig. 5 g). Theoretically, (002)-textured zinc promotes planar growth but suffers from weak adatom bonding (Supplementary Fig. 15) 51 , promoting lattice distortion and porous deposits through epitaxial breakdown. By contrast, (101) planes support dense lateral growth kinetics, producing uniform compact deposits. Extended 24 h deposition in flow-electrolyte electrolytic cells validates this epitaxial (101) growth advantage: stable voltage profiles and reduced cell potentials confirm the operational efficacy of UTC (Figs. 5 h, i). Time-resolved electrochemical analysis reveals the impact of ACN on zinc deposition dynamics. As shown in Figs. 6 a, b, peaks P1 and P2 correspond to intrinsic electrolyte impedance, while peaks P2 and P5 represent interfacial charge-transfer processes. At the early stage, heteroepitaxial zinc deposition occurs on aluminum cathodes, characterized by prolonged relaxation times. Once the aluminum is fully covered, homoepitaxial zinc deposition dominates, leading to significantly shorter charge-transfer relaxation. In ACN-free electrolytes, loose and porous deposits generate additional P3 peaks (Fig. 6 a), confirming morphology-dependent electrochemical signatures. Then, finite element simulations (COMSOL Multiphysics) further validate these findings. In the absence of ACN, steep Zn 2+ concentration gradients at 500 A m - 2 drive uneven growth due to imbalance between reduction kinetics and mass transport (Figs. 6 c, d). With 1 M ACN, however, uniform electrode morphology ensures homogeneous electric field distribution and suppressed Zn 2+ concentration gradients. Enhanced f r ’ for Zn 2+ weakens SO 4 2- interactions, accelerating desolvation and lowering interfacial SO 4 2- concentration (Supplementary Fig. 16). Critically, ACN also reduces proton flux at the electrode interface (Supplementary Fig. 17), directly mitigating corrosion pit formation observed in Fig. 5 e. Time-dependent morphological evolution reveals distinct deposition mechanisms. In ACN-free electrolytes, zinc preferentially nucleates at aluminum electrode edges and propagates inward as porous structures (Supplementary Figs. 18, 19). Even after 40 min, the incomplete coverage persists due to intrinsic porosity. By contrast, ACN enables uniform, compact deposition across the electrode surface. Granular differences are reflected in SEM analysis (Fig. 6 e), confirming crystallographic and densification variations observed earlier (Figs. 5 e, f). Confocal laser scanning microscope (CLSM) further quantify surface contrasts. Electrolytes without ACN produce micro-scale protrusions and deep potholes and defects originating from both corrosion and non-uniform deposition inhomogeneity (Ra = 1.397 µm, Fig. 6 f and Supplementary Fig. 20). ACN-regulated deposition yields smooth surfaces (Ra = 1.236 µm), demonstrating that the UTC strategy improves both morphology and surface integrity. Mechanistically, zinc deposition proceeds through five distinct stages after desolvation: adatom diffusion, mixed 2D growth, 3D spiral dislocation growth, and merging and densification (Fig. 6 g). ACN lowers desolvation barriers, enriching interfacial zinc adatoms that preferentially align on angled (101) facets. Subsequent nanoplatelet stacking and merging produce compact, corrosion-resistant deposits that resist proton penetration while enhancing mechanical robustness. Discussion In summary, we propose an UTC strategy to regulate cationic degrees of freedom (DOF) for enhanced electric field responsiveness in zinc electrowinning. Ion transport across the electrolyte-to-interface transition is fundamentally governed by translational freedom ( f r ’). Within this framework, UTC is defined as indirect modulation of Zn 2+ solvation using weakly-coordinating additives (DN < 18 kcal mol - 1 ), thereby raising f r ’ relative to fully hydrated Zn(H 2 O) 6 2+ ( f r ’ = 0). ACN exemplifies this principle: residing in the secondary solvation shell, it weakens primary-shell ligand interactions while preserving locally continuous but long-range disordered hydrogen bond networks. This dual effect increases f r ’ for Zn 2+ while lowering f r ’ for H + , thereby coupling topological entropy with reaction kinetics. With 1 M ACN, ZE achieves a CE of 94.3% with an energy consumption of 2531.4 kWh t - 1 at 500 A m - 2 and 40 ℃. Even under extreme conditions (1 g L - 1 F - , 10× industrial threshold) at 700 A m - 2 , the system sustains 90.84% efficiency with an energy demand of 2644.9 kWh t - 1 . This represents a 390.7 kWh t - 1 reduction compared with ACN-free electrolytes. In addition, ACN homogenizes interfacial Zn 2+ concentration and electric field distribution, steering epitaxial reorientation toward (101)-faceted crystalline growth and producing compact, corrosion-resistant deposits. These findings establish electrolyte topology engineering as a powerful approach to achieving energy-efficient zinc electrowinning at industrial current densities, with broad potential for optimizing electrolyte structures and advancing sustainable metal deposition. Methods Chemicals Zinc sulfate heptahydrate (ZnSO 4 ·7H 2 O), concentrated sulfuric acid (H 2 SO 4 , 98%), acetonitrile (CH 3 CN, ACN), sodium sulfate (Na 2 SO 4 ), sodium chloride (NaCl), and sodium fluoride (NaF) were obtained from Sinopharm Chemical Reagent Co., Ltd. All reagents were analytical grade and used without further purification. Zinc electrowinning-specific aluminum cathodes and lead-silver alloy anodes were obtained from Suzhou Shuertai Co., Ltd. Zn electrowinning experiments First, the electrolytes containing 50 g L - 1 of Zn 2+ , 150 g L - 1 of H 2 SO 4 and 0-1.8 M ACN were prepared. Halide-containing electrolytes incorporated specified NaCl/NaF concentrations. Al cathodes and Pb-Ag anodes (1 cm 2 active area) were welded to copper leads and epoxy-encapsulated. Electrodes were polished sequentially with 1500- and 2000-grit abrasive paper prior to use. Electrowinning employed 150 mL static electrolyte with 2 cm electrode spacing at 40 ℃ for 3 h. Systematic current density variations were applied during deposition. Post-electrolysis, cell voltage profiles were recorded. Cathodic deposits were detached, mass-quantified, and characterized for current efficiency (CE, η ) and energy consumption ( W ). The corresponding formulae are as Eq. (3), (4) 6,14 : Where q is the electrochemical equivalent of zinc, 1.2195 g (A h) - 1 . I denotes the applied current (A). t represents the electrowinning duration (h). m is the mass of zinc deposited on the cathode (g). And U corresponds to the cell voltage. Characterizations Fourier transform infrared (FTIR) spectra were acquired using a Bruker INVENIO S spectrometer (ATR-DTGS detector, 4000 − 600 cm - 1 ). Temperature-dependent and in-situ FTIR measurements employed the same system. Raman spectroscopy utilized a WiTech alpha300R microscope (532 nm excitation, 40 ℃). 1 H NMR data were recorded on Bruker 600 MHz spectrometers at 40 ℃ using coaxial D 2 O inserts for field referencing. Thermal properties were analyzed by differential scanning calorimetry (DSC, METTLER TOLEDO TGA/DSC 3+). Viscosity and conductivity measurements used an NDJ-9S viscometer and DDSJ-379L conductivity meter, respectively (40 ℃). Surface characterization employed field emission scanning electron microscopy (FE-SEM, TESCAN, 30 keV), confocal laser scanning microscopy (CLSM, Olympus OLS4100), and custom optical microscopy (AOSVI NX30T-HK830). Crystallographic analysis used X-ray diffraction (XRD, Panalytical Empyrean) with Cu Kα radiation and a scan rate of 5° min - 1 . Electrochemical measurements All electrochemical measurements used a CS2350M workstation with a three-electrode configuration (50 mL electrolyte, 40 ℃). Square aluminum electrodes (10×10×0.1 mm) served as working electrodes, with Ag/AgCl reference and platinum counter electrodes. Self-corrosion rates were determined by mass loss after 2 h immersion of Al/Zn plates in test electrolytes (20 mL). The hydrogen evolution reaction (HER) behavior was analyzed via linear sweep voltammetry (LSV, 1 mV s - 1 ). Tafel analysis employed 5 mV s - 1 scans from − 0.9 to -0.2 V vs. Ag/AgCl. EIS measurements at open-circuit potential (0.01 Hz-100 kHz, 5 mV amplitude) provided data for distribution of relaxation times (DRT) analysis. Differential capacitance was measured at 1000 Hz. Deposition kinetics were characterized by chronoamperometry (CA) with potential steps from OCP to deposition potentials, cyclic voltammetry (CV, -0.5 V to -1.35 V vs. Ag/AgCl, 5 mVs − 1 ), and galvanostatic profiling at 500 A m - 2 . Quantum chemistry calculations The quantum chemistry calculations were conducted by Gaussian software. The geometry optimization used the B3LYP/def2-SVP level, while single-point energy calculations applied B3LYP/def2-TZVP. The SMD continuum model simulated solvation effects. Grimme’s D3 dispersion correction with Becke-Johnson damping accounted for van der Waals interactions. The VMD package visualized electrostatic potential (ESP) iso-surfaces and molecular orbitals 52 . MD simulation Molecular dynamics (MD) simulations were performed using GROMACS software with a time step of 1fs 53 . Nonbonded interactions, including van der Waals and electrostatic forces, were calculated with a cutoff distance of 1.0 nm. Electrostatic interactions were treated using the particle mesh Ewald (PME) method for enhanced accuracy. Simulations were conducted in a cubic box of 6 × 6 × 6 nm 3 under periodic boundary conditions. The OPC3 water model and GAFF/Merz force fields were applied to describe the solvent and ionic parameters, respectively 54 . Temperature was maintained at 313 K using the V-rescale thermostat with a coupling time of 2 ns in the NPT ensemble. Each system was equilibrated for 30 ns, followed by an additional 5 ns of production simulation for data collection. Hydrogen bonds were identified based on geometric criteria: a donor-acceptor distance less than 3.5 Å and a donor-hydrogen-acceptor angle less than 30°. Finite element simulations Finite element simulations modeled electric fields, ion concentrations, and hydrogen ion flux using COMSOL Multiphysics 6.2 55,56 . The ion concentration follows the first law of Fick's diffusion, while the electromigration follows the Nernst-Planck relation. Analyses involving electrode kinetics were introduced to solve the Butler-Volmer equation. Both models are based on a simplified geometric configuration of the study space. Each electrode is 10 µm in length, with a 7 µm gap between them. On the surface of the negative electrode, three ellipses (semi-major axis 0.45 µm, semi-minor axis 0.8 µm) are uniformly distributed to represent surface protrusions typical of metal electrodes. The simulation domain primarily encompasses the electrode-electrolyte interface. All simulations are conducted at a constant temperature of 313 K. A zero-potential boundary condition is applied at the positive electrode, while the negative electrode is assigned the cell polarization voltage to establish the driving potential for ion transport. Declarations Data availability The data that support the findings of this study are available from the corresponding author upon reasonable request. Acknowledgements The authors gratefully acknowledge the financial support provided by the Fundamental Research Funds for the National Natural Science Foundation of China (No. 52474384), the Central Universities of Central South University (No. 2025ZZTS0082). Thank Shiyanjia Lab (www.shiyanjia.com) for the test including Raman, NMR, et al. And we also thank eceshi (www.eceshi.com) for support during the quantum chemistry calculations calculation, MD and Finite element simulations. Author contributions W.Z., G.Z. and Z.T. conceptualized the project and provided the vital guidance. H.C., Z.L., G.L. and Z.C. executed the characterizations, electrochemical measurements and theoretical analysis. H.C., X.L., H.Y., J.Z., Z.F. and Z.L. provided the experimental assistance. H.C. wrote the initial paper approved by all the authors. All authors contributed to the discussion of the results. Competing interests The authors declare no competing interests. Additional information Supplementary information The online version contains supplementary material available at http://doi.org/... Correspondence and requests for materials should be addressed to Wei Zhang, Guangmin Zhou or Zhongliang Tian. Reprints and permission information is available at http://www.nature.com/reprints References Deng, Z. et al. Global carbon emissions and decarbonization in 2024. Nat. Rev. Earth Environ. 6 , 231-233 (2025). Innocenti, A., Bresser, D., Garche, J. & Passerini, S. A critical discussion of the current availability of lithium and zinc for use in batteries. Nat. Commun. 15 , 4068 (2024). Monteiro, J. K. L. S., Majuste, D., Porto, M. P., Freitas, A. M. & Gomes, R. A. M. Zinc cathodes produced with highly-variable DC current simulated from solar irradiance data. Hydrometallurgy 215 , 10597 (2023). Li, J. et al. Redesigning electrification of china's ammonia and methanol industry to balance decarbonization with power system security. Nat. Energy 10 , 762-773 (2025). Gomes, R. A. M. et al. Use of hybrid renewable energy system with organic photovoltaic cells in zinc electrowinning. J. Cleaner Prod. 293 , 125333 (2021). Xu, X. et al. Improve the energy efficiency: Effects of additives on longtime zinc electrowinning. Hydrometallurgy 193 , 105326 (2020). Yang, Y., Yang, H., Zhuc, R. & Zhou, H. High reversibility at high current density: The zinc electrodeposition principle behind the \"trick\". Energy Environ. Sci. 16 , 2723 (2023). Ji, Q. et al. An environmentally friendly and high current efficiency acid mist inhibitor for zinc electrowinning. Mater. Res. Express 10 , 076507 (2023). Shen, G., Chang, L., Jiang, C., Shao, Y. & Chen, B. Effects of F − ions on the electrochemical and interface behavior of cathodes in zinc electrowinning. J. Electroanal. Chem. 939 , 117480 (2023). I. Epelboin, M. Ksouri, E. Lejay & Wiart, R. A study of the elementary steps of electron-transfer during the electrocrystallization of zinc. Electrochim. Acta 20 , 603-605 (1975). Soroura, N., Zhang, W., Ghalia, E. & Houlachi, G. A review of organic additives in zinc electrodeposition process (performance and evaluation). Hydrometallurgy 171 , 320-332 (2017). Sorour, N., Su, C., Ghali, E. & Houlachi, G. Effect of ionic liquid additives on oxygen evolution reaction and corrosion behavior of Pb-Ag anode in zinc electrowinning. Electrochim. Acta 258 , 631-638 (2017). Yu, H. et al. Reversible adsorption with oriented arrangement of a zwitterionic additive stabilizes electrodes for ultralong-life Zn-ion batteries. Energy Environ. Sci. 16 , 2684-2695 (2023). Lin, G. et al. Roles of tannic acid and gelatin in Zn electrowinning and their inhibition mechanisms investigated via electrochemical methods. Hydrometallurgy 195 , 105390 (2020). Wu, X., Liu, Z. & Liu, X. The effects of additives on the electrowinning of zinc from sulphate solutions with high fluoride concentration. Hydrometallurgy 141 , 31-35 (2014). Guo, Y. et al. Dynamic covalent bonds regulate zinc plating/stripping behaviors for high-performance zinc ion batteries. Angew. Chem. Int. Ed. 63 , e202406597 (2024). Dong, D., Wang, T., Sun, Y., Fan, J. & Lu, Y.C. Hydrotropic solubilization of zinc acetates for sustainable aqueous battery electrolytes. Nat. Sustain. 6 , 1474-1484 (2023). Zhao, C.-X., Li, Z., Chen, B., Chen, F. & Wang, C. Self-adaptive electrolytes for fast-charging batteries. Nat. Energy 10 , 904-913 (2025). Qiu, M. et al. Tailoring water structure with high-tetrahedral-entropy for antifreezing electrolytes and energy storage at −80 °C. Nat. Commun. 14 , 601 (2023). Tuckerman, M. E., Marx, D. & Parrinello, M. The nature and transport mechanism of hydrated hydroxide ions in aqueous solution. Nature 417 , 925-929 (2002). Marx, D., Tuckerman, M. E., Hutter, J. r. & Parrinello, M. The nature of the hydrated excess proton in water. Nature 397 , 601-604 (1999). Li, M. et al. Comprehensive H 2 O molecules regulation via deep eutectic solvents for ultra-stable zinc. Angew. Chem. Int. Ed. 62 , e202215552 (2023). Wu, M. et al. Highly reversible and stable Zn metal anodes realized using a trifluoroacetamide electrolyte additive. Energy Environ. Sci. 17 , 619-629 (2024). Zhang, R. et al. Weakly solvating aqueous-based electrolyte facilitated by a soft co-solvent for extreme temperature operations of zinc-ion batteries. Energy Environ. Sci. 17 , 4569-4581 (2024). Wang, X. et al. Weak solvation effects and molecular-rich layers induced water-poor helmholtz layers boost highly stable Zn anode. Energy Storage Mater. 73 , 103856 (2024). Shi, X. et al. A weakly solvating electrolyte towards practical rechargeable aqueous zinc-ion batteries. Nat. Commun. 15 , 302 (2024). Zheng, J. et al. Critical solvation structures arrested active molecules for reversible Zn electrochemistry. Nano-Micro Letters 16 , 145 (2024). Yang, H. et al. A compliant metastructure design with reconfigurability up to six degrees of freedom. Nat. Commun. 16 , 719 (2025). Kamba, M., Shimizu, R. & Aikawa, K. Nanoscale feedback control of six degrees of freedom of a near-sphere. Nat. Commun. 14 , 7943 (2023). Cao, J. et al. Strategies of regulating Zn 2+ solvation structures for dendrite-free and side reaction-suppressed zinc-ion batteries. Energy Environ. Sci. 15 , 499-528 (2022). Tian, Y. et al. Visualizing eigen/zundel cations and their interconversion in monolayer water on metal surfaces. Science 377 , 315-319 (2022). Xu, H., Cabriolu, R. & Smit, B. Effects of degrees of freedom on calculating diffusion properties in nanoporous materials. J. Chem. Theory Comput. 18 , 2826-2835 (2022). Liu, T., Ding, J., Xu, J., Zhao, D. & Qiu, X. Design and dynamics analysis of three-degree-of-freedom kinematic mechanism for helicopter attitude simulation. Sci. Rep. 15 , 7463 (2025). Yang, H. et al. Reunderstanding aqueous Zn electrochemistry from interfacial specific adsorption of solvation structures. Energy Environ. Sci. 16 , 2910-2923 (2023). Zhang, M. et al. Dynamically interfacial pH-buffering effect enabled by n-methylimidazole molecules as spontaneous proton pumps toward highly reversible zinc-metal anodes. Adv. Mater. 35 , 2208630 (2023). Cataldo, F. A revision of the gutmann donor numbers of a series of phosphoramides including tepa. Eur. Chem. Bull. 4 , 92-97 (2015). Wang, Y. et al. Solvent control of water O−H bonds for highly reversible zinc ion batteries. Nat. Commun. 14 , 2720 (2023). Xu, C. et al. Fast single metal cation conduction in ion-water aggregated aqueous battery electrolytes. Nat. Commun. 16 , 4574 (2025). Yang, H. et al. A metal-organic framework as a multifunctional ionic sieve membrane for long-life aqueous zinc-iodide batteries. Adv. Mater. 32 , 2004240 (2020). Qin, Y. et al. In situ construction of irox nanofilm on tiox for boosting low-Ir catalysis in practical pem electrolyze. Adv. Energy Mater. 15 , 2405636 (2025). Zhang, J. et al. Adhesive zwitterionic poly(ionic liquid) with unprecedented organic solvent resistance. Adv. Mater. 36 , 202403039 (2024). Gomes, R. J. et al. Modulating water hydrogen bonding within a non-aqueous environment controls its reactivity in electrochemical transformations. Nat. Catal. 7 , 689-701 (2024). Dou, Q. et al. Unveiling solvation structure and desolvation dynamics of hybrid electrolytes for ultralong cyclability and facile kinetics of Zn-Al alloy anodes. Energy Environ. Sci. 15 , 4572-45883 (2022). Li, T. C. et al. A universal additive strategy to reshape electrolyte solvation structure toward reversible Zn storage. Adv. Energy Mater. 12 , 2103231 (2022). Chang, L. et al. High-entropy solvation chemistry towards affordable and practical Ah-level zinc metal battery. Nat. Commun. 16 , 6134 (2025). Huang, J. et al. Interfacial biomacromolecular engineering toward stable Ah-level aqueous zinc batteries. Adv. Mater. 36 , 2406257 (2024). Brown, M. A., Goel, A. & Abbas, Z. Effect of electrolyte concentration on the stern layer thickness at a charged interface. Angew. Chem. Int. Ed. 55 , 3790-3794 (2016). Song, Y. et al. Bilateral in-situ functionalization towards Ah-scale aqueous zinc metal batteries. Nat. Commun. 16 , 3142 (2025). Zhao, Y. et al. Tailoring grain boundary stability of zinc-titanium alloy for long-lasting aqueous zinc batteries. Nat. Commun. 14 , 7080 (2023). Cheng, H. et al. Significantly enhanced dehalogenation selectivity in near-neutral zinc sulfate electrolytes by diffusion dialysis. J. Membr. Sci. 563 , 142-148 (2018). Liu, Z. et al. Construct robust epitaxial growth of(101) textured zinc metal anode for long life and high capacity in mild aqueous zinc-ion batteries. Adv. Mater. 36 , 2305988 (2024). Schäfer, A., Huber, C. & Ahlrichs, R. Fully optimized contracted gaussian basis sets of triple zeta valence quality for atoms Li to Kr. J. Chem. Phys. 100 , 5829-5835 (1994). Berendsen, H. J. C., Spoel, D. v. d. & Drunen, R. v. Gromacs: A message-passing parallel molecular dynamics implementation. Comput. Phys. Commun. 91 , 43-56 (1995). Li, Z., Song, L. F., Li, P. & Merz, K. M. Systematic parametrization of divalent metal ions for the opc3, opc, tip3p-fb, and tip4p-fb water models. J. Chem. Theory Comput. 16 , 4429-4442 (2020). Wang, D. et al. Localized anion-cation aggregated aqueous electrolytes with accelerated kinetics for low-temperature zinc metal batteries. Angew. Chem. Int. Ed. 62 , e202315834 (2023). Lin, H. et al. Interfacial regulation via configuration screening of a disodium naphthalenedisulfonate additive enabled high-performance wide-pH Zn-based batteries. Energy Environ. Sci. 18 , 1282-1293 (2025). Additional Declarations There is NO Competing Interest. Supplementary Files Supplementaryinformation.docx Supplementary Information Cite Share Download PDF Status: Under Review Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. 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Red and blue regions denote positive and negative correlation signals respectively. \\u003cstrong\\u003ec \\u003c/strong\\u003eRaman spectra of O-H stretching modes of water molecules in electrolytes with varying ACN content. \\u003cstrong\\u003ed\\u003c/strong\\u003e Relative proportions of strong, medium, and weak HBs obtained from Raman spectral fitting (c). \\u003cstrong\\u003ee\\u003c/strong\\u003e \\u003csup\\u003e1\\u003c/sup\\u003eH NMR chemical shifts for water in different electrolytes. \\u003cstrong\\u003ef\\u003c/strong\\u003e Proposed mechanism by which ACN reorganizes HB networks and suppresses HER.\\u003c/p\\u003e\",\"description\":\"\",\"filename\":\"3.png\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-7829869/v1/6696280c27a73516fd748671.png\"},{\"id\":95538202,\"identity\":\"0dfbe471-e0a9-4dd5-b383-d163a5ceaf1e\",\"added_by\":\"auto\",\"created_at\":\"2025-11-10 11:03:26\",\"extension\":\"png\",\"order_by\":4,\"title\":\"Figure 4\",\"display\":\"\",\"copyAsset\":false,\"role\":\"figure\",\"size\":341362,\"visible\":true,\"origin\":\"\",\"legend\":\"\\u003cp\\u003e\\u003cstrong\\u003eReaction behavior of hydrogen and zinc at the electrolyte-cathode interface. a\\u003c/strong\\u003e Self-corrosion rates of aluminum and zinc in different electrolytes. \\u003cstrong\\u003eb, c \\u003c/strong\\u003eLSV curves (b)\\u003csup\\u003e \\u003c/sup\\u003eand Tafel curves (c)\\u003csup\\u003e \\u003c/sup\\u003eof aluminum electrode in various electrolytes. \\u003cstrong\\u003ed\\u003c/strong\\u003e DRT analysis derived from EIS data. \\u003cstrong\\u003ee-g\\u003c/strong\\u003e Differential capacitance profiles (e), CV curves (f), and galvanostatic voltage profiles at 500 A m\\u003csup\\u003e-2\\u003c/sup\\u003e (g) for aluminum electrodes in different electrolytes. \\u003cstrong\\u003eh\\u003c/strong\\u003e Experimental dimensionless transients compared with theoretical 3D nucleation models for zinc electrowinning. \\u003cstrong\\u003ei\\u003c/strong\\u003e Schematic illustration of zinc nucleation and growth mechanisms.\\u003c/p\\u003e\",\"description\":\"\",\"filename\":\"4.png\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-7829869/v1/e9f488762fab80e73f9aa95e.png\"},{\"id\":95654094,\"identity\":\"981a0f94-a6f7-4dff-8988-de9a8028da91\",\"added_by\":\"auto\",\"created_at\":\"2025-11-11 16:09:41\",\"extension\":\"png\",\"order_by\":5,\"title\":\"Figure 5\",\"display\":\"\",\"copyAsset\":false,\"role\":\"figure\",\"size\":522727,\"visible\":true,\"origin\":\"\",\"legend\":\"\\u003cp\\u003e\\u003cstrong\\u003ePractical zinc electrowinning performance.\\u003c/strong\\u003e \\u003cstrong\\u003ea-c\\u003c/strong\\u003e CE (a), cell voltage (b), and energy consumption (c) of zinc electrowinning for 3 h in electrolytes with different ACN concentrations. \\u003cstrong\\u003ed-g\\u003c/strong\\u003e Macroscopic photographs (d), SEM images (e, f), XRD (g) patterns of deposited products after electrowinning at 500 A m\\u003csup\\u003e-2\\u003c/sup\\u003e for 3 h in electrolytes with varied ACN concentrations. \\u003cstrong\\u003eh\\u003c/strong\\u003e Schematic of the laboratory-scale electrolytic cell with circulating electrolyte for long-term electrowinning operations. \\u003cstrong\\u003ei\\u003c/strong\\u003e Cell voltage stability during 24 h zinc electrowinning at 500 A m\\u003csup\\u003e-2\\u003c/sup\\u003e, 40 ℃ in electrolytes without and with 1 M ACN.\\u003c/p\\u003e\",\"description\":\"\",\"filename\":\"5.png\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-7829869/v1/d85262d7fcc203c9ca5fee99.png\"},{\"id\":95538204,\"identity\":\"0b79bda9-6768-4bd0-b3ae-4c921e75cba5\",\"added_by\":\"auto\",\"created_at\":\"2025-11-10 11:03:27\",\"extension\":\"png\",\"order_by\":6,\"title\":\"Figure 6\",\"display\":\"\",\"copyAsset\":false,\"role\":\"figure\",\"size\":521892,\"visible\":true,\"origin\":\"\",\"legend\":\"\\u003cp\\u003e\\u003cstrong\\u003eMechanistic insights into ACN-enabled zinc deposition at 500 A m\\u003c/strong\\u003e\\u003csup\\u003e\\u003cstrong\\u003e-2\\u003c/strong\\u003e\\u003c/sup\\u003e\\u003cstrong\\u003e.\\u003c/strong\\u003e \\u003cstrong\\u003ea, b\\u003c/strong\\u003e Time-resolved DRT analysis of aluminum cathodes in electrolytes without (a) and with (b) 1 M ACN. \\u003cstrong\\u003ec, d\\u003c/strong\\u003e FEM of the electric field distributions (c) and Zn\\u003csup\\u003e2+\\u003c/sup\\u003e concentration gradients (d) near the cathode. \\u003cstrong\\u003ee\\u003c/strong\\u003e Morphological evolution of zinc deposits during electrowinning. \\u003cstrong\\u003ef\\u003c/strong\\u003e CLSM images of deposited zinc layers after 90 min of electrowinning. \\u003cstrong\\u003eg\\u003c/strong\\u003e Schematic illustration of epitaxial zinc nucleation on the aluminum cathode.\\u003c/p\\u003e\",\"description\":\"\",\"filename\":\"6.png\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-7829869/v1/c927762b88f19c7438f59305.png\"},{\"id\":95660003,\"identity\":\"4074259b-c26c-4603-985b-5d1cb1670810\",\"added_by\":\"auto\",\"created_at\":\"2025-11-11 16:30:22\",\"extension\":\"pdf\",\"order_by\":0,\"title\":\"\",\"display\":\"\",\"copyAsset\":false,\"role\":\"manuscript-pdf\",\"size\":3471185,\"visible\":true,\"origin\":\"\",\"legend\":\"\",\"description\":\"\",\"filename\":\"manuscript.pdf\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-7829869/v1/b632d3db-f95a-4d5f-9c5f-46fc40b196f2.pdf\"},{\"id\":95538206,\"identity\":\"a05f7ddb-6bc0-425f-ad6c-b56d374c4d02\",\"added_by\":\"auto\",\"created_at\":\"2025-11-10 11:03:27\",\"extension\":\"docx\",\"order_by\":1,\"title\":\"\",\"display\":\"\",\"copyAsset\":false,\"role\":\"supplement\",\"size\":16146635,\"visible\":true,\"origin\":\"\",\"legend\":\"Supplementary Information\",\"description\":\"\",\"filename\":\"Supplementaryinformation.docx\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-7829869/v1/196ff93d91f544c797e77780.docx\"}],\"financialInterests\":\"There is \\u003cb\\u003eNO\\u003c/b\\u003e Competing Interest.\",\"formattedTitle\":\"Decoupling ionic transfer kinetics via undercoordinated constraints for energy-efficient and high-quality zinc electrowinning\",\"fulltext\":[{\"header\":\"Introduction\",\"content\":\"\\u003cp\\u003eZinc, the fourth most produced metal (over 13,000 kt annually, 210,000 kt reserves), is 90% refined by hydrometallurgy, where electrowinning consumes 80% of sectoral energy and jeopardizes net-zero goals\\u003csup\\u003e\\u003cspan additionalcitationids=\\\"CR2 CR3\\\" citationid=\\\"CR1\\\" class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u0026ndash;\\u003cspan citationid=\\\"CR4\\\" class=\\\"CitationRef\\\"\\u003e4\\u003c/span\\u003e\\u003c/sup\\u003e. Current zinc electrowinning (ZE) intensity (2800\\u0026ndash;3400 kWh t\\u003csup\\u003e-\\u003cspan citationid=\\\"CR1\\\" class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e) substantially exceeds the theoretical minimum (1633 kWh t\\u003csup\\u003e-\\u003cspan citationid=\\\"CR1\\\" class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e) by up to twofold, directly hindering decarbonization\\u003csup\\u003e\\u003cspan citationid=\\\"CR5\\\" class=\\\"CitationRef\\\"\\u003e5\\u003c/span\\u003e,\\u003cspan citationid=\\\"CR6\\\" class=\\\"CitationRef\\\"\\u003e6\\u003c/span\\u003e\\u003c/sup\\u003e. Energy-efficient ZE demands high current efficiency (CE), low cell voltage, and high-quality deposits (Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig1\\\" class=\\\"InternalRef\\\"\\u003e1\\u003c/span\\u003ea), yet persistent cathodic hydrogen evolution reaction (HER) remains the primary obstacle\\u003csup\\u003e\\u003cspan citationid=\\\"CR7\\\" class=\\\"CitationRef\\\"\\u003e7\\u003c/span\\u003e,\\u003cspan citationid=\\\"CR8\\\" class=\\\"CitationRef\\\"\\u003e8\\u003c/span\\u003e\\u003c/sup\\u003e. HER proceeds via both direct H\\u003csup\\u003e+\\u003c/sup\\u003e reduction and electrochemical water splitting, aggravated by zinc self-corrosion and impurity-driven galvanic attack\\u003csup\\u003e\\u003cspan citationid=\\\"CR9\\\" class=\\\"CitationRef\\\"\\u003e9\\u003c/span\\u003e\\u003c/sup\\u003e. These parasitic processes consume electrons, reduce CE and raise voltage, imposing a prohibitive energy burden magnified in multi-electrode cells (Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig1\\\" class=\\\"InternalRef\\\"\\u003e1\\u003c/span\\u003eb). Thus, suppressing HER is pivotal for energy-efficient ZE and drives the current research.\\u003c/p\\u003e\\u003cp\\u003eElectrolyte engineering has pursued mitigation through functional additives. The competitive adsorption of H\\u003csup\\u003e+\\u003c/sup\\u003e and Zn\\u003csup\\u003e2+\\u003c/sup\\u003e on the cathode interface underlies the design of adsorption-type additives\\u003csup\\u003e\\u003cspan citationid=\\\"CR8\\\" class=\\\"CitationRef\\\"\\u003e8\\u003c/span\\u003e,\\u003cspan additionalcitationids=\\\"CR11 CR12\\\" citationid=\\\"CR10\\\" class=\\\"CitationRef\\\"\\u003e10\\u003c/span\\u003e\\u0026ndash;\\u003cspan citationid=\\\"CR13\\\" class=\\\"CitationRef\\\"\\u003e13\\u003c/span\\u003e\\u003c/sup\\u003e. Despite extensive research, industrial ZE still relies on traditional protein-based additives such as gelatin and glue\\u003csup\\u003e\\u003cspan citationid=\\\"CR11\\\" class=\\\"CitationRef\\\"\\u003e11\\u003c/span\\u003e,\\u003cspan citationid=\\\"CR14\\\" class=\\\"CitationRef\\\"\\u003e14\\u003c/span\\u003e\\u003c/sup\\u003e. In acidic media, these colloidal additives become cationic and selectively adsorb onto the cathode under an electric field, jointly suppressing HER and templating zinc crystallization. However, their performance is highly concentration-sensitive, with ppm-level effects governed by steric hindrance and surface coverage. This sensitivity impedes Zn\\u003csup\\u003e2+\\u003c/sup\\u003e transport and obstructs interfacial reduction, increasing cell voltage by 56\\u0026ndash;144 mV and lowering CE by 30\\u0026ndash;49%\\u003csup\\u003e14,15\\u003c/sup\\u003e. Consequently, adsorption-dependent mechanisms impose inherent limits on efficiency gains, and dosage-sensitive operation undermines scale-up. These constraints underscore the need for additive strategies beyond interfacial adsorption.\\u003c/p\\u003e\\u003cp\\u003eElectrolyte building-block design along the Zn\\u003csup\\u003e2+\\u003c/sup\\u003e to Zn\\u003csup\\u003e0\\u003c/sup\\u003e pathway offers a targeted route to regulate ZE\\u003csup\\u003e16\\u0026ndash;18\\u003c/sup\\u003e. High acid/zinc electrolytes (130\\u0026ndash;180 g L\\u003csup\\u003e-\\u003cspan citationid=\\\"CR1\\\" class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e H\\u003csub\\u003e2\\u003c/sub\\u003eSO\\u003csub\\u003e4\\u003c/sub\\u003e, 45\\u0026ndash;70 g L\\u003csup\\u003e-\\u003cspan citationid=\\\"CR1\\\" class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e Zn\\u003csup\\u003e2+\\u003c/sup\\u003e) favor SO\\u003csub\\u003e4\\u003c/sub\\u003e\\u003csup\\u003e2-\\u003c/sup\\u003e coordination and hinder Zn\\u003csup\\u003e2+\\u003c/sup\\u003e desolvation (Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig1\\\" class=\\\"InternalRef\\\"\\u003e1\\u003c/span\\u003ec). At high current density, sluggish Zn\\u003csup\\u003e2+\\u003c/sup\\u003e transport contrasts with rapid H\\u003csup\\u003e+\\u003c/sup\\u003e/H\\u003csub\\u003e2\\u003c/sub\\u003eO migration, thereby accelerating HER\\u003csup\\u003e\\u003cspan additionalcitationids=\\\"CR20\\\" citationid=\\\"CR19\\\" class=\\\"CitationRef\\\"\\u003e19\\u003c/span\\u003e\\u0026ndash;\\u003cspan citationid=\\\"CR21\\\" class=\\\"CitationRef\\\"\\u003e21\\u003c/span\\u003e\\u003c/sup\\u003e. High \\u003cem\\u003eGutmann\\u003c/em\\u003e donor number (DN) additives suppress HER but over-stabilize Zn\\u003csup\\u003e2+\\u003c/sup\\u003e solvation, impeding deposition\\u003csup\\u003e\\u003cspan citationid=\\\"CR22\\\" class=\\\"CitationRef\\\"\\u003e22\\u003c/span\\u003e,\\u003cspan citationid=\\\"CR23\\\" class=\\\"CitationRef\\\"\\u003e23\\u003c/span\\u003e\\u003c/sup\\u003e. Low DN additives weaken hydration and accelerate desolvation but the excess disrupts electric double layer (EDL) and shells, elevating barriers\\u003csup\\u003e\\u003cspan additionalcitationids=\\\"CR25 CR26\\\" citationid=\\\"CR24\\\" class=\\\"CitationRef\\\"\\u003e24\\u003c/span\\u003e\\u0026ndash;\\u003cspan citationid=\\\"CR27\\\" class=\\\"CitationRef\\\"\\u003e27\\u003c/span\\u003e\\u003c/sup\\u003e. By contrast, weakly-coordinating additives are promising for ZE, but their role in reconciling zinc deposition with HER kinetics at industrial current densities remains unresolved. From a classical physics view, these trade-offs reflect constraints on ionic degrees of freedom (DOF): translational (\\u003cem\\u003ef\\u003c/em\\u003e\\u003csub\\u003etrans\\u003c/sub\\u003e), rotational (\\u003cem\\u003ef\\u003c/em\\u003e\\u003csub\\u003erot\\u003c/sub\\u003e), and vibrational (\\u003cem\\u003ef\\u003c/em\\u003e\\u003csub\\u003evib\\u003c/sub\\u003e)\\u003csup\\u003e\\u003cspan citationid=\\\"CR28\\\" class=\\\"CitationRef\\\"\\u003e28\\u003c/span\\u003e,\\u003cspan citationid=\\\"CR29\\\" class=\\\"CitationRef\\\"\\u003e29\\u003c/span\\u003e\\u003c/sup\\u003e. Under electric fields, translational motion dominates bulk-to-interface transport, with solvent exchange and progressive desolvation as the primary kinetic barriers\\u003csup\\u003e\\u003cspan citationid=\\\"CR30\\\" class=\\\"CitationRef\\\"\\u003e30\\u003c/span\\u003e\\u003c/sup\\u003e. Thus, solvation and coordination constrain both Zn\\u003csup\\u003e2+\\u003c/sup\\u003e and H\\u003csup\\u003e+\\u003c/sup\\u003e mobility. Weakly-coordinating additives preserve higher \\u003cem\\u003ef\\u003c/em\\u003e\\u003csub\\u003etrans\\u003c/sub\\u003e, accelerating interfacial processes. The key challenge, therefore, is to design constraints that selectively raise \\u003cem\\u003ef\\u003c/em\\u003e\\u003csub\\u003etrans\\u003c/sub\\u003e for Zn\\u003csup\\u003e2+\\u003c/sup\\u003e while decreasing it for H\\u003csup\\u003e+\\u003c/sup\\u003e. Such selective decoupling would promote efficient deposition while inhibiting HER for industrial energy-efficient ZE.\\u003c/p\\u003e\\u003cp\\u003eIn aqueous solution, Zn\\u003csup\\u003e2+\\u003c/sup\\u003e exists primarily as Zn(H\\u003csub\\u003e2\\u003c/sub\\u003eO)\\u003csub\\u003e6\\u003c/sub\\u003e\\u003csup\\u003e2+ 30\\u003c/sup\\u003e. Relative to hydration, ligands with stronger affinity than H\\u003csub\\u003e2\\u003c/sub\\u003eO impose powerful constraints, inducing overcoordination, whereas weaker interactions yield undercoordination. Abundant SO\\u003csub\\u003e4\\u003c/sub\\u003e\\u003csup\\u003e2-\\u003c/sup\\u003e in ZE electrolytes drives strong electrostatic binding and inevitable overcoordination, lowering \\u003cem\\u003ef\\u003c/em\\u003e\\u003csub\\u003etrans\\u003c/sub\\u003e for Zn\\u003csup\\u003e2+\\u003c/sup\\u003e. Conversely, finely tuned undercoordination weakens interaction strength while preserving the solvation topology, elevating Zn\\u003csup\\u003e2+\\u003c/sup\\u003e transport. For protons, Zundel (H\\u003csub\\u003e5\\u003c/sub\\u003eO\\u003csub\\u003e2\\u003c/sub\\u003e\\u003csup\\u003e+\\u003c/sup\\u003e) and Eigen (H\\u003csub\\u003e9\\u003c/sub\\u003eO\\u003csub\\u003e4\\u003c/sub\\u003e\\u003csup\\u003e+\\u003c/sup\\u003e) species diffuse through defect migration along hydrogen bond (HB) networks\\u003csup\\u003e\\u003cspan citationid=\\\"CR21\\\" class=\\\"CitationRef\\\"\\u003e21\\u003c/span\\u003e,\\u003cspan citationid=\\\"CR31\\\" class=\\\"CitationRef\\\"\\u003e31\\u003c/span\\u003e\\u003c/sup\\u003e. Quantum fluctuations delocalize protons over multiple HBs, while solvent polarization lowers the transfer barrier, jointly accounting for their intrinsically high \\u003cem\\u003ef\\u003c/em\\u003e\\u003csub\\u003etrans\\u003c/sub\\u003e. Introducing weakly-coordinating molecules interrupts long-range transfer but maintains local hopping. Unlike overcoordination, which terminates HB pathways, such undercoordination preserves topological continuity of HB networks yet overall reduces \\u003cem\\u003ef\\u003c/em\\u003e\\u003csub\\u003etrans\\u003c/sub\\u003e of protons. Thus, ionic transport is governed not by structural reorganization but by topological inheritance, where subtle undercoordination adapts existing networks to decouple Zn\\u003csup\\u003e2+\\u003c/sup\\u003e and H\\u003csup\\u003e+\\u003c/sup\\u003e transport with high selectivity.\\u003c/p\\u003e\\u003cp\\u003eHerein, we propose an undercoordinated topology constraint (UTC) strategy mediated by electrolyte additives with low donor numbers (\\u0026lt;\\u0026thinsp;18 kcal mol\\u003csup\\u003e-\\u003cspan citationid=\\\"CR1\\\" class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e) to decouple the opposing \\u003cem\\u003ef\\u003c/em\\u003e\\u003csub\\u003etrans\\u003c/sub\\u003e requirements of Zn\\u003csup\\u003e2+\\u003c/sup\\u003e and H\\u003csup\\u003e+\\u003c/sup\\u003e. Unlike traditional solvation-shell reconstruction or HB network disruption, UTC creates metastable Zn\\u003csup\\u003e2+\\u003c/sup\\u003e solvation clusters through undercoordinated ligand-field modulation. This weakens coordination strength and reduces SO\\u003csub\\u003e4\\u003c/sub\\u003e\\u003csup\\u003e2-\\u003c/sup\\u003e density while maintaining local HB connectivity. The design couples topological entropy with reaction kinetics: elevated \\u003cem\\u003ef\\u003c/em\\u003e\\u003csub\\u003etrans\\u003c/sub\\u003e enhances entropy and lowers the Zn\\u003csup\\u003e2+\\u003c/sup\\u003e desolvation barrier, facilitating the zinc deposition, while regulated HBs frustrate \\u003cem\\u003eGrotthuss\\u003c/em\\u003e proton long-range conduction, suppressing HER. By optimizing ion transport kinetics, this modification would markedly improve the CE and minimize energy usage. Implemented with acetonitrile (ACN), the UTC strategy achieved a high CE of 94.3% with an energy consumption of 2531.4 kWh t\\u003csup\\u003e-\\u003cspan citationid=\\\"CR1\\\" class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e at 500 A m\\u003csup\\u003e-\\u003cspan citationid=\\\"CR2\\\" class=\\\"CitationRef\\\"\\u003e2\\u003c/span\\u003e\\u003c/sup\\u003e and 40 ℃. Moreover, halide impurities (e.g., F\\u003csup\\u003e-\\u003c/sup\\u003e, Cl\\u003csup\\u003e-\\u003c/sup\\u003e) pose a critical challenge in ZE by accelerating HER and corrosion, forcing costly purification to adhere to ~\\u0026thinsp;100 mg L⁻\\u0026sup1; F\\u003csup\\u003e-\\u003c/sup\\u003e limits\\u003csup\\u003e\\u003cspan citationid=\\\"CR9\\\" class=\\\"CitationRef\\\"\\u003e9\\u003c/span\\u003e\\u003c/sup\\u003e. The UTC strategy substantially extends the tolerance of electrolyte to halide impurities. Even under harsh conditions with F\\u0026ndash;rich electrolyte (1 g L\\u003csup\\u003e-\\u003cspan citationid=\\\"CR1\\\" class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e), the system delivered an 11.96% increase in CE and a 390.7 kWh t\\u003csup\\u003e-\\u003cspan citationid=\\\"CR1\\\" class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e reduction in energy consumption at 700 A m\\u003csup\\u003e-\\u003cspan citationid=\\\"CR2\\\" class=\\\"CitationRef\\\"\\u003e2\\u003c/span\\u003e\\u003c/sup\\u003e compared with the unmodified electrolyte. This work demonstrates electrolyte topology engineering as a powerful and sustainable approach to advance industrial metal electrowinning.\\u003c/p\\u003e\"},{\"header\":\"Results\",\"content\":\"\\u003cdiv id=\\\"Sec3\\\" class=\\\"Section2\\\"\\u003e\\n \\u003ch2\\u003ePrinciples of electrolyte design and implementation for industrial ZE\\u003c/h2\\u003e\\n \\u003cp\\u003eAn unconstrained ion has three translational DOF (\\u003cem\\u003ef\\u003c/em\\u003e\\u003csub\\u003etrans\\u003c/sub\\u003e = 3) along the \\u003cem\\u003ex\\u003c/em\\u003e, \\u003cem\\u003ey\\u003c/em\\u003e, and \\u003cem\\u003ez\\u003c/em\\u003e axes\\u003csup\\u003e\\u003cspan class=\\\"CitationRef\\\"\\u003e32\\u003c/span\\u003e,\\u003cspan class=\\\"CitationRef\\\"\\u003e33\\u003c/span\\u003e\\u003c/sup\\u003e. Each coordination bond within the solvation removes one \\u003cem\\u003ef\\u003c/em\\u003e\\u003csub\\u003etrans\\u003c/sub\\u003e. Since each bond connects two ions, and the total bond number equals half the coordination number (\\u003cem\\u003ez\\u003c/em\\u003e). The residual translational freedom (\\u003cem\\u003ef\\u003c/em\\u003e\\u003csub\\u003er\\u003c/sub\\u003e) is thus defined in Eq. (1). Here, \\u003cem\\u003ef\\u003c/em\\u003e\\u003csub\\u003er\\u003c/sub\\u003e = 0 denotes an ideally full ordination. Positive \\u003cem\\u003ef\\u003c/em\\u003e\\u003csub\\u003er\\u003c/sub\\u003e indicates undercoordination with faster kinetics, and negative \\u003cem\\u003ef\\u003c/em\\u003e\\u003csub\\u003er\\u003c/sub\\u003e reflects overcoordination with hindered mobility. In real electrolytes, competitive ligand coordination complicates this situation\\u003csup\\u003e\\u003cspan class=\\\"CitationRef\\\"\\u003e34\\u003c/span\\u003e,\\u003cspan class=\\\"CitationRef\\\"\\u003e35\\u003c/span\\u003e\\u003c/sup\\u003e. Ligand type, size, and binding strength critically modulate \\u003cem\\u003ef\\u003c/em\\u003e\\u003csub\\u003etrans\\u003c/sub\\u003e. Assuming a single ligand type per ion, we introduce a weighted correction factor (\\u003cem\\u003e\\u0026alpha;\\u003c/em\\u003e) to capture intrinsic ligand effects, yielding Eq.\\u0026nbsp;(2).\\u003c/p\\u003e\\n \\u003cp\\u003e\\u003cimg src=\\\"data:image/png;base64,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\\\" style=\\\"width: 421px; height: 106.191px;\\\" width=\\\"421\\\" height=\\\"106.191\\\"\\u003e\\u003c/p\\u003e\\n \\u003cp\\u003eThis descriptor captures the full trajectory of cations from bulk solvation through diffusion to interfacial desolvation (Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e1\\u003c/span\\u003ec). Taking Zn\\u003csup\\u003e2+\\u003c/sup\\u003e hydration as the baseline (\\u003cem\\u003e\\u0026alpha;\\u003c/em\\u003e\\u0026thinsp;=\\u0026thinsp;0), \\u003cem\\u003e\\u0026alpha;\\u003c/em\\u003e is positive for overcoordination and negative for undercoordination, correlating with the \\u003cem\\u003eGutmann\\u003c/em\\u003e DN. Using H\\u003csub\\u003e2\\u003c/sub\\u003eO (DN\\u0026thinsp;=\\u0026thinsp;18 kcal mol\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e) as the reference (Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e1\\u003c/span\\u003ed)\\u003csup\\u003e\\u003cspan class=\\\"CitationRef\\\"\\u003e36\\u003c/span\\u003e\\u003c/sup\\u003e, additives with DN\\u0026thinsp;\\u0026gt;\\u0026thinsp;18 kcal mol\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e (\\u003cem\\u003e\\u0026alpha;\\u003c/em\\u003e\\u0026thinsp;\\u0026gt;\\u0026thinsp;0) induce strong Zn\\u003csup\\u003e2+\\u003c/sup\\u003e coordination, reconstructing compact solvation structures and fragmenting HB networks. Such overcoordination reduces translational freedom (\\u003cem\\u003ef\\u003c/em\\u003e\\u003csub\\u003er\\u003c/sub\\u003e\\u0026rsquo;\\u0026lt; 0) for both Zn\\u003csup\\u003e2+\\u003c/sup\\u003e and H\\u003csup\\u003e+\\u003c/sup\\u003e, slowing Zn\\u003csup\\u003e2+\\u003c/sup\\u003e transport while suppressing HER. This DOF reduction is effective in batteries but collapses under the high current densities required for industrial electrowinning.\\u003c/p\\u003e\\n \\u003cp\\u003eTo address this limitation, an UTC strategy (\\u003cem\\u003ef\\u003c/em\\u003e\\u003csub\\u003er\\u003c/sub\\u003e\\u0026rsquo; \\u0026gt;0) is proposed to selectively relax Zn\\u003csup\\u003e2+\\u003c/sup\\u003e coordination. By employing additives with DN\\u0026thinsp;\\u0026lt;\\u0026thinsp;18 kcal mol\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e (\\u003cem\\u003e\\u0026alpha;\\u003c/em\\u003e\\u0026thinsp;\\u0026lt;\\u0026thinsp;0), UTC preserves the parent electrolyte framework while expanding the Zn\\u003csup\\u003e2+\\u003c/sup\\u003e solvation shells and maintaining locally continuous HB networks (Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e1\\u003c/span\\u003ed). The weaker coordination enhances electrostatic flexibility and topological entropy, thereby accelerating Zn\\u003csup\\u003e2+\\u003c/sup\\u003e diffusion and desolvation. Simultaneously, undercoordination induces HB rigidity, suppressing ligand exchange and restricting parasitic H\\u003csup\\u003e+\\u003c/sup\\u003e flux. In this way, UTC decouples the \\u003cem\\u003ef\\u003c/em\\u003e\\u003csub\\u003etrans\\u003c/sub\\u003e of Zn\\u003csup\\u003e2+\\u003c/sup\\u003e and H\\u003csup\\u003e+\\u003c/sup\\u003e, enabling rapid field response and high-efficiency zinc electrowinning.\\u003c/p\\u003e\\n \\u003cp\\u003eTo elucidate the structural basis of improved ionic freedom, we introduced acetonitrile (ACN) as a model molecule into the electrolyte. ACN combines industrial accessibility with mild ligand strength (DN\\u0026thinsp;=\\u0026thinsp;14.1 kcal mol\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e)\\u003csup\\u003e36\\u003c/sup\\u003e. Moreover, its intrinsically low viscosity and broad thermal window enable superior adaptability to complex electrolytes and harsh ZE conditions. Quantum chemical calculations confirm that SO\\u003csub\\u003e4\\u003c/sub\\u003e\\u003csup\\u003e2-\\u003c/sup\\u003e exhibits the strongest binding affinity (Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e2\\u003c/span\\u003ea), interacting robustly with Zn\\u003csup\\u003e2+\\u003c/sup\\u003e, H\\u003csub\\u003e3\\u003c/sub\\u003eO\\u003csup\\u003e+\\u003c/sup\\u003e, and H\\u003csub\\u003e2\\u003c/sub\\u003eO. In contrast, ACN displays the minimal binding energy, underscoring its weak interaction with cations. Thus, SO\\u003csub\\u003e4\\u003c/sub\\u003e\\u003csup\\u003e2-\\u003c/sup\\u003e imposes a dominant electrostatic constraint, significantly limiting \\u003cem\\u003ef\\u003c/em\\u003e\\u003csub\\u003er\\u003c/sub\\u003e\\u0026rsquo; of cations, whereas HBs effects exhibit subtler differences. Rigid potential scans (Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e2\\u003c/span\\u003eb) and electrostatic potential (ESP) distributions (Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e2\\u003c/span\\u003ec) highlight these distinctions. The H\\u003csub\\u003e2\\u003c/sub\\u003eO-H\\u003csub\\u003e2\\u003c/sub\\u003eO HB (H-H) is slightly stronger (-0.161 eV) and shorter (1.85 \\u0026Aring;) than the H\\u003csub\\u003e2\\u003c/sub\\u003eO-ACN interaction (H-A, -0.159 eV, 1.95 \\u0026Aring;). Quantum chemical analysis attributes these weaker interactions to electron density redistribution\\u003csup\\u003e\\u003cspan class=\\\"CitationRef\\\"\\u003e37\\u003c/span\\u003e\\u003c/sup\\u003e. While H-H and H-A bonds show comparable geometries, their electronic features differ markedly. As shown in Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e2\\u003c/span\\u003ec, positive charge localizes on the H and negative charge on the O in H-H interactions, partially canceling at the HB interface. In contrast, H-A interactions localize negative charge on H\\u003csub\\u003e2\\u003c/sub\\u003eO and positive charge on ACN, imparting a negative electrostatic character at the HB site. This favors H\\u003csup\\u003e+\\u003c/sup\\u003e localization between H\\u003csub\\u003e2\\u003c/sub\\u003eO and ACN, rather than between two H\\u003csub\\u003e2\\u003c/sub\\u003eO molecules, thereby inducing topological rigidity.\\u003c/p\\u003e\\n \\u003cp\\u003eMolecular dynamics (MD) simulations further explained the structural evolution of ACN-containing electrolytes at 313 K. The reduction in total energy confirms enhanced thermodynamic stability with ACN (Supplementary Fig. 1a). While the number of H-H bonds decreases (Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e2\\u003c/span\\u003ed), their average lifetime increases to 2.37 ps (Supplementary Fig. 1b). Conversely, H-A bonds exhibit a substantially shorter lifetime of 1.14 ps. Probability distributions show that ACN-containing electrolytes develop a higher population of shorter HBs (Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e2\\u003c/span\\u003ee) and smaller HB angles (Supplementary Fig.\\u0026nbsp;1c). It indicates that ACN strengthened H\\u003csub\\u003e2\\u003c/sub\\u003eO-H\\u003csub\\u003e2\\u003c/sub\\u003eO interactions while H\\u003csub\\u003e2\\u003c/sub\\u003eO-ACN interactions remain weak. Notably, ACN promotes the formation of locally continuous HB networks characterized by short-range order but long-range disorder. Though shorter HBs could in principle facilitate proton transfer, the resulting topological networks suppress \\u003cem\\u003eGrotthuss\\u003c/em\\u003e-type long-range conduction, reducing \\u003cem\\u003ef\\u003c/em\\u003e\\u003csub\\u003er\\u003c/sub\\u003e\\u0026rsquo; of protons while maintaining overall ionic conductivity.\\u003c/p\\u003e\\n \\u003cp\\u003eRadial distribution functions (RDFs) and coordination numbers (CNs) further clarify the structural modifications induced by ACN. ACN resides in the second solvation shell of both H\\u003csub\\u003e3\\u003c/sub\\u003eO\\u003csup\\u003e+\\u003c/sup\\u003e and Zn\\u003csup\\u003e2+\\u003c/sup\\u003e (Figs. \\u003cspan class=\\\"InternalRef\\\"\\u003e2\\u003c/span\\u003ef, g). For H\\u003csub\\u003e3\\u003c/sub\\u003eO\\u003csup\\u003e+\\u003c/sup\\u003e, binding distances with H\\u003csub\\u003e2\\u003c/sub\\u003eO (0.164 nm) and SO\\u003csub\\u003e4\\u003c/sub\\u003e\\u003csup\\u003e2-\\u003c/sup\\u003e (0.160 nm) remain unchanged after ACN introduction. However, the CN of H\\u003csub\\u003e2\\u003c/sub\\u003eO decreases from 0.672 to 0.643, while that of SO\\u003csub\\u003e4\\u003c/sub\\u003e\\u003csup\\u003e2-\\u003c/sup\\u003e increases from 0.356 to 0.367. For Zn\\u003csup\\u003e2+\\u003c/sup\\u003e, the CN of H\\u003csub\\u003e2\\u003c/sub\\u003eO rises from 5.176 to 5.466 at 0.212 nm, whereas the CN of SO\\u003csub\\u003e4\\u003c/sub\\u003e\\u003csup\\u003e2-\\u003c/sup\\u003e declines from 0.824 to 0.536 at 0.206 nm. Notably, ACN markedly diminishes the local SO\\u003csub\\u003e4\\u003c/sub\\u003e\\u003csup\\u003e2-\\u003c/sup\\u003e density near Zn\\u003csup\\u003e2+\\u003c/sup\\u003e (Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e2\\u003c/span\\u003eg). These results demonstrate that acts indirectly from the second solvation shell, subtly modulating the local ionic environment (Supplementary Fig.\\u0026nbsp;2). The strong electrostatic interactions in unmodified electrolytes produce tightly bound solvation shells that restrict DOF for Zn\\u003csup\\u003e2+\\u003c/sup\\u003e, elevating the desolvation energy barrier (E\\u003csub\\u003ede\\u003c/sub\\u003e) (Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e2\\u003c/span\\u003eh). At high current densities, sluggish Zn\\u003csup\\u003e2+\\u003c/sup\\u003e diffusion, desolvation, and electron transfer create severe interfacial concentration gradients. Local Zn\\u003csup\\u003e2+\\u003c/sup\\u003e depletion allows protons to dominate the reduction process, lowering the CE. Conversely, ACN weakens Zn\\u003csup\\u003e2+\\u003c/sup\\u003e-SO\\u003csub\\u003e4\\u003c/sub\\u003e\\u003csup\\u003e2-\\u003c/sup\\u003e electrostatic interactions, substantially reducing the desolvation barrier (E\\u003csub\\u003ede\\u003c/sub\\u003e\\u0026rsquo;) and enabling more uniform Zn\\u003csup\\u003e2+\\u003c/sup\\u003e flux at the interface.\\u003c/p\\u003e\\n \\u003cp\\u003eAdvanced \\u003cem\\u003ein-situ\\u003c/em\\u003e spectroscopy further corroborates these findings. SO\\u003csub\\u003e4\\u003c/sub\\u003e\\u003csup\\u003e2-\\u003c/sup\\u003e characteristic peaks remain stable below 50 ℃ in the presence of ACN (Supplementary Figs. 3, 4). Temperature-dependent Raman spectra reveal a critical structural transition in Supplementary Fig. 5. The symmetric stretching mode of SO\\u003csub\\u003e4\\u003c/sub\\u003e\\u003csup\\u003e2-\\u003c/sup\\u003e (\\u003cem\\u003eV\\u003c/em\\u003e (SO\\u003csub\\u003e4\\u003c/sub\\u003e\\u003csup\\u003e2-\\u003c/sup\\u003e)) shifts from 964 cm\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e to 978 cm\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e upon ACN addition. According to the \\u003cem\\u003eEigen-Tamm\\u003c/em\\u003e model, \\u003cem\\u003eV\\u003c/em\\u003e (SO\\u003csub\\u003e4\\u003c/sub\\u003e\\u003csup\\u003e2-\\u003c/sup\\u003e) bands can be deconvoluted into contact ion pairs (CIPs, Zn\\u003csup\\u003e2+\\u003c/sup\\u003e(H\\u003csub\\u003e2\\u003c/sub\\u003eO)\\u003csub\\u003e5\\u003c/sub\\u003e(OSO\\u003csub\\u003e3\\u003c/sub\\u003e\\u003csup\\u003e2-\\u003c/sup\\u003e)) and solvent-separated ion pairs (SSIPs, Zn\\u003csup\\u003e2+\\u003c/sup\\u003e(H\\u003csub\\u003e2\\u003c/sub\\u003eO)\\u003csub\\u003e6\\u003c/sub\\u003e\\u0026middot;(SO\\u003csub\\u003e4\\u003c/sub\\u003e\\u003csup\\u003e2-\\u003c/sup\\u003e))\\u003csup\\u003e38,39\\u003c/sup\\u003e. The blue shift signifies that SO\\u003csub\\u003e4\\u003c/sub\\u003e\\u003csup\\u003e2-\\u003c/sup\\u003e experiences increased difficulty penetrating Zn\\u003csup\\u003e2+\\u003c/sup\\u003e solvation shells due to the dragging effect of ACN, resulting in an expanded topological Zn\\u003csup\\u003e2+\\u003c/sup\\u003e solvation shell. Parallel shifts in \\u003cem\\u003eV\\u003c/em\\u003e (HSO\\u003csub\\u003e3\\u003c/sub\\u003e\\u003csup\\u003e-\\u003c/sup\\u003e) bands also confirm ACN can weaken electrostatic attractions\\u003csup\\u003e\\u003cspan class=\\\"CitationRef\\\"\\u003e40\\u003c/span\\u003e\\u003c/sup\\u003e. These spectroscopic findings directly corroborate MD simulations. Additionally, the OH stretching vibration (\\u003cem\\u003eV\\u003c/em\\u003e (OH), 3300\\u0026ndash;3700 cm\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e) exhibits significant modification with ACN addition (Supplementary Fig. 4). At fixed additive concentration, \\u003cem\\u003eV\\u003c/em\\u003e (OH) undergoes progressive blue shifts with increasing temperature. The shift primarily reflects HB weakening caused by intensified thermal molecular motion\\u003csup\\u003e\\u003cspan class=\\\"CitationRef\\\"\\u003e41\\u003c/span\\u003e\\u003c/sup\\u003e. And we systematically probed ACN concentration effects on HBs at 40 ℃ (Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e3\\u003c/span\\u003e), replicating industrial ZE conditions.\\u003c/p\\u003e\\n \\u003cp\\u003eGenerally, the broad \\u003cem\\u003eV\\u003c/em\\u003e (OH) band comprises contributions from strong (~\\u0026thinsp;3500 cm\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e), medium (~\\u0026thinsp;3570 cm\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e) and weak (~\\u0026thinsp;3684 cm\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e) HBs\\u003csup\\u003e\\u003cspan class=\\\"CitationRef\\\"\\u003e42\\u003c/span\\u003e\\u003c/sup\\u003e. Two-dimensional infrared spectrometer (2D-IR) correlation spectroscopy reveals the regulating effect of ACN\\u003csup\\u003e\\u003cspan class=\\\"CitationRef\\\"\\u003e43\\u003c/span\\u003e\\u003c/sup\\u003e. Synchronous spectra show positive auto-peaks at 3500 cm\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e and 3570 cm\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e (Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e3\\u003c/span\\u003ea), indicating ACN significantly perturbs strong and medium HBs, while weaker peaks at 3684 cm\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e suggest minimal disruption of weak HBs. Positive cross-peaks (red) confirm synchronous enhancement of these HB modes. Asynchronous spectra (Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e3\\u003c/span\\u003eb) resolve the sequential modification of HBs: strong (3500 cm\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e) \\u0026rarr; weak (3384 cm\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e) \\u0026rarr; medium (3570 cm\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e). This sequence reveals that ACN preferentially disrupts tetrahedral networks, liberating weakly bonded water monomers, that subsequently reorganize into medium or strong HBs. Raman spectra validate this HB classification established by FTIR with corresponding bands across 3000\\u0026ndash;3800 cm\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e (Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e3\\u003c/span\\u003ec)\\u003csup\\u003e\\u003cspan class=\\\"CitationRef\\\"\\u003e44\\u003c/span\\u003e\\u003c/sup\\u003e. Quantitative analysis shows that the proportion of strong HBs increases monotonically with ACN concentration, while medium and weak HBs decrease concurrently (Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e3\\u003c/span\\u003ed).\\u003c/p\\u003e\\n \\u003cp\\u003eThe \\u003csup\\u003e\\u003cspan class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003eH nuclear magnetic resonance (NMR) spectra reveal a downfield shift of H\\u003csub\\u003e2\\u003c/sub\\u003eO upon ACN addition, confirming de-shielding that reduces the influence of SO\\u003csub\\u003e4\\u003c/sub\\u003e\\u003csup\\u003e2-\\u003c/sup\\u003e on hydrogen electron density (Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e3\\u003c/span\\u003ee). At higher ACN concentrations, this effect weakens, consistent with direct ACN-H\\u003csub\\u003e2\\u003c/sub\\u003eO coordination. Excessive ACN disrupts the topological continuity of HB networks, as evidenced by perturbations in -CH\\u003csub\\u003e3\\u003c/sub\\u003e signals (Supplementary Fig. 6). As illustrated in Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e3\\u003c/span\\u003ef, ACN constrains proton hopping along HB networks. It is well known that the hydrated protons normally diffuse through structural defect migration via Eigen-Zundel-Eigen interconversion. ACN selectively suppresses long-range proton transport while preserving short-range transfer, thereby increasing HB rigidity and decreasing proton entropy. This fragmentation produces HB networks that are locally continuous but discontinuous at long-range, dynamically reducing \\u003cem\\u003ef\\u003c/em\\u003e\\u003csub\\u003er\\u003c/sub\\u003e\\u0026rsquo; of protons.\\u003c/p\\u003e\\n\\u003c/div\\u003e\\n\\u003ch3\\u003eInvestigations of HER and zinc electrodeposition behavior\\u003c/h3\\u003e\\n\\u003cp\\u003ePhysicochemical analyses confirm that ACN maintains electrolyte stability under ZE operating temperatures while exerting minimal influence on viscosity and conductivity (Supplementary Fig. 7). During ZE, deposition initiates on aluminum cathodes before propagating across zinc substrates. Corrosion measurements show that ACN negligibly affects aluminum dissolution but significantly suppresses zinc corrosion (Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e4\\u003c/span\\u003ea). Specifically, the zinc corrosion rates reduce from 0.91 to 0.48 mg cm\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e2\\u003c/span\\u003e\\u003c/sup\\u003e h\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e at 1.8 M ACN. Linear sweep voltammetry (LSV) further quantifies HER suppression (Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e4\\u003c/span\\u003eb). The proton reduction peak at -0.90 V progressively diminishes with increasing ACN concentration, accompanied by negative potential shifts that indicate inhibited proton reduction. Cathodic polarization triggers the co-reduction of Zn\\u003csup\\u003e2+\\u003c/sup\\u003e and protons. The required potential shifts negatively from \\u0026minus;\\u0026thinsp;1.06 V to -1.12 V at 5 mA cm\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e2\\u003c/span\\u003e\\u003c/sup\\u003e with rising ACN concentration, demonstrating concurrent suppression of both processes. Control experiments with sodium sulfate validate this HER inhibition (Supplementary Fig. 8). Tafel analysis reveals that corrosion current density decreases by 56% from 87.10 to 38.28 mA cm\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e2\\u003c/span\\u003e\\u003c/sup\\u003e, while corrosion potential shifts positively by 73 mV (Supplementary Fig. 4c and Supplementary Table 1). These results demonstrate that ACN effectively protects the electrode surface by constraining the \\u003cem\\u003ef\\u003c/em\\u003e\\u003csub\\u003er\\u003c/sub\\u003e\\u0026rsquo; of protons, thereby suppressing HER and corrosion simultaneously.\\u003c/p\\u003e\\n\\u003cp\\u003eElectrochemical impedance spectroscopy (EIS) reveals that ACN increases charge transfer resistance (Supplementary Fig. 9). Distribution of relaxation times (DRT) analysis further deciphers interfacial evolution (Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e4\\u003c/span\\u003ed). The high-frequency peak, corresponding to bulk electrolyte resistance\\u003csup\\u003e\\u003cspan class=\\\"CitationRef\\\"\\u003e45\\u003c/span\\u003e,\\u003cspan class=\\\"CitationRef\\\"\\u003e46\\u003c/span\\u003e\\u003c/sup\\u003e, intensifies with increasing ACN concentration, consistent with conductivity trends. The low-frequency charge-transfer peak undergoes concentration-dependent evolution. From 0 to 1.0 M ACN, it shifts toward lower frequencies with reduced intensity, indicating longer charge-transfer relaxation times. At concentrations above 1.0 M, a distinct adsorption process emerges, dominating interfacial dynamics. Differential capacitance measurements corroborate these findings (Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e4\\u003c/span\\u003ee). Positive potential shifts decrease capacitance, consistent with preferential ACN adsorption on the electrode surface. The zero-charge potential (\\u003cem\\u003e\\u0026phi;\\u003c/em\\u003e\\u003csub\\u003e0\\u003c/sub\\u003e) shifts positively, signifying reduced surface negative charge\\u003csup\\u003e\\u003cspan class=\\\"CitationRef\\\"\\u003e47\\u003c/span\\u003e,\\u003cspan class=\\\"CitationRef\\\"\\u003e48\\u003c/span\\u003e\\u003c/sup\\u003e. This behavior indicates that ACN displaces H\\u003csub\\u003e2\\u003c/sub\\u003eO/SO\\u003csub\\u003e4\\u003c/sub\\u003e\\u003csup\\u003e2-\\u003c/sup\\u003e, forming a newly oriented dipolar layer at the interface.\\u003c/p\\u003e\\n\\u003cp\\u003eCyclic voltammetry (CV) identifies the nucleation potential for Zn\\u003csup\\u003e2+\\u003c/sup\\u003e reduction on aluminum electrodes (Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e4\\u003c/span\\u003ef). The nucleation overpotential (NOP), defined as the difference between crossover and reduction potentials\\u003csup\\u003e\\u003cspan class=\\\"CitationRef\\\"\\u003e11\\u003c/span\\u003e\\u003c/sup\\u003e, is 68 mV in the additive-free electrolyte. With increasing ACN concentration, NOP initially decreases but remains below 68 mV up to 1 M, then gradually rises. Zinc deposition overpotentials also increase monotonically with ACN concentration. Galvanostatic profiles at 500 A m\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e2\\u003c/span\\u003e\\u003c/sup\\u003e confirm electrode stability in ACN-modified electrolytes, with potential variations reflecting altered kinetics (Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e4\\u003c/span\\u003eg). Chronoamperometry further elucidates deposition dynamics. As shown in Supplementary Fig.\\u0026nbsp;10, current density initially rises before decaying to a steady state. And the rise corresponds to nucleation and growth, while the decay reflects diffusion layer thickening and overlap. Higher applied potentials reduce the time (t\\u003csub\\u003em\\u003c/sub\\u003e) required to reach limiting current density (I\\u003csub\\u003em\\u003c/sub\\u003e). These features confirm diffusion-controlled 3D nucleation\\u003csup\\u003e\\u003cspan class=\\\"CitationRef\\\"\\u003e45\\u003c/span\\u003e\\u003c/sup\\u003e. \\u003cem\\u003eScharifker-Hills\\u003c/em\\u003e modeling classifies the process as instantaneous nucleation (3DI) (Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e4\\u003c/span\\u003eh)\\u003csup\\u003e\\u003cspan class=\\\"CitationRef\\\"\\u003e49\\u003c/span\\u003e\\u003c/sup\\u003e. Increasing t\\u003csub\\u003em\\u003c/sub\\u003e with ACN concentration indicates a buffered Zn\\u003csup\\u003e2+\\u003c/sup\\u003e concentration gradient (Supplementary Fig. 10), which promotes dense and fine-grained deposits by enabling uniform nucleation. At excess ACN concentration, however, interfacial blocking from over-adsorption counteracts this benefit. Thus, ACN dosage must be carefully optimized to balance \\u003cem\\u003ef\\u003c/em\\u003e\\u003csub\\u003er\\u003c/sub\\u003e\\u0026rsquo; of cations in both bulk electrolyte and at the interface.\\u003c/p\\u003e\\n\\u003ch3\\u003eZinc electrowinning performance improvement with UTC\\u003c/h3\\u003e\\n\\u003cp\\u003eZE cells were assembled to validate the UTC strategy. Firstly, three-electrode measurements show that ACN minimally affects the Pb-Ag anode oxygen evolution reaction (OER) overpotential while reducing operational voltage at 500 A m\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e2\\u003c/span\\u003e\\u003c/sup\\u003e (Supplementary Fig. 11), attributed to activation of the anode passivation layer. Full-cell testing reveals a strong concentration dependence. CE peaks at 94.30% with 1.0 M ACN at 500 A m\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e2\\u003c/span\\u003e\\u003c/sup\\u003e (Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e5\\u003c/span\\u003ea). Concurrently, cell voltage and energy consumption decrease to 2.84 V and 2508.3 kWh t\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e at 1.8 M ACN (Figs. \\u003cspan class=\\\"InternalRef\\\"\\u003e5\\u003c/span\\u003eb, c). At higher current densities, however, these benefits diminish due to Zn\\u003csup\\u003e2+\\u003c/sup\\u003e \\u003cem\\u003ef\\u003c/em\\u003e\\u003csub\\u003er\\u003c/sub\\u003e\\u0026rsquo; limitations and ACN-induced interfacial effects. At 1500 A m\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e2\\u003c/span\\u003e\\u003c/sup\\u003e, UTC electrolytes show only a 5.34% CE loss, a 60 mV voltage increase, and a 263.5 kWh t\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e energy penalty relative to ACN-free systems (Supplementary Figs. 12a-c). It demonstrates competitive advantages over existing additives (Supplementary Table 2). Stepwise current testing further confirms operational robustness (Supplementary Figs .12d-f). Industrial ZE electrolytes contain halide impurities from mineral processing, where chloride and fluoride impurities accelerate electrode corrosion and reduce CE by increasing voltage and energy consumption. Conventional practice requires stringent impurity control (500 mg L\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e Cl\\u003csup\\u003e-\\u003c/sup\\u003e, 100 mg L\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e F\\u003csup\\u003e-\\u003c/sup\\u003e) via energy-intensive purification\\u003csup\\u003e\\u003cspan class=\\\"CitationRef\\\"\\u003e9\\u003c/span\\u003e,\\u003cspan class=\\\"CitationRef\\\"\\u003e50\\u003c/span\\u003e\\u003c/sup\\u003e. Remarkably, ACN mitigates halide effects of industrial contaminants (Supplementary Figs.\\u0026nbsp;12g-l). At 700 A m\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e2\\u003c/span\\u003e\\u003c/sup\\u003e with 1 M ACN and 1 g L\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e F\\u003csup\\u003e-\\u003c/sup\\u003e, UTC increases CE by 11.96% and reduces energy consumption by 390.7 kWh t\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e, approaching fluoride-free baseline performance and demonstrating unprecedented impurity tolerance.\\u003c/p\\u003e\\n\\u003cp\\u003eDeposit quality is equally critical for industrial feasibility. Poor zinc layers exhibiting spalling, porosity or cracks complicate downstream processing. At increasing current density, deposits without ACN become progressively rougher, whereas optimal ACN concentrations eliminate corrosion pits and yield smooth, compact surfaces (Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e5\\u003c/span\\u003ed, Supplementary Fig. 13). Excess ACN (\\u0026gt;\\u0026thinsp;1.0 M) reverses this effect producing coarse ridge-valley morphologies with interlocking grains (Supplementary Fig. 14). This distinct morphology stems from adsorption-mediated competitive crystal growth across zinc facets. Higher-resolution SEM further elucidates the morphological transitions (Figs. \\u003cspan class=\\\"InternalRef\\\"\\u003e5\\u003c/span\\u003ee, f). In additive-free electrolytes, SEM reveals widespread corrosion cavities and heterogeneous surface texture (Figs. 5e1, e2). At higher magnification, zinc predominantly grows as distorted hexagonal (002) platelets aligned parallel to the electrode, adopting terraced pyramidal stacking (Figs. 5f1, f2). This hierarchical growth mode drives pronounced coarsening and morphological irregularity. At optimal ACN concentrations, corrosion cavities are eliminated and surface uniformity is markedly improved (Figs. 5e3, e4). Although sparse inclined hexagonal grains remain, most crystallites reorient into angled platelet morphologies relative to the surface (Figs. 5f3, f4). Beyond this threshold, however, deposits exhibit roughness (Figs. 5e5, e6), with pronounced crystallite coarsening and interlocking morphologies (Figs. 5f5, f6). XRD analysis confirms that ACN drives preferential crystal reorientation from (002) to (101) planes (Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e5\\u003c/span\\u003eg). Theoretically, (002)-textured zinc promotes planar growth but suffers from weak adatom bonding (Supplementary Fig.\\u0026nbsp;15)\\u003csup\\u003e\\u003cspan class=\\\"CitationRef\\\"\\u003e51\\u003c/span\\u003e\\u003c/sup\\u003e, promoting lattice distortion and porous deposits through epitaxial breakdown. By contrast, (101) planes support dense lateral growth kinetics, producing uniform compact deposits. Extended 24 h deposition in flow-electrolyte electrolytic cells validates this epitaxial (101) growth advantage: stable voltage profiles and reduced cell potentials confirm the operational efficacy of UTC (Figs. \\u003cspan class=\\\"InternalRef\\\"\\u003e5\\u003c/span\\u003eh, i).\\u003c/p\\u003e\\n\\u003cp\\u003eTime-resolved electrochemical analysis reveals the impact of ACN on zinc deposition dynamics. As shown in Figs. \\u003cspan class=\\\"InternalRef\\\"\\u003e6\\u003c/span\\u003ea, b, peaks P1 and P2 correspond to intrinsic electrolyte impedance, while peaks P2 and P5 represent interfacial charge-transfer processes. At the early stage, heteroepitaxial zinc deposition occurs on aluminum cathodes, characterized by prolonged relaxation times. Once the aluminum is fully covered, homoepitaxial zinc deposition dominates, leading to significantly shorter charge-transfer relaxation. In ACN-free electrolytes, loose and porous deposits generate additional P3 peaks (Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e6\\u003c/span\\u003ea), confirming morphology-dependent electrochemical signatures. Then, finite element simulations (COMSOL Multiphysics) further validate these findings. In the absence of ACN, steep Zn\\u003csup\\u003e2+\\u003c/sup\\u003e concentration gradients at 500 A m\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e2\\u003c/span\\u003e\\u003c/sup\\u003e drive uneven growth due to imbalance between reduction kinetics and mass transport (Figs. \\u003cspan class=\\\"InternalRef\\\"\\u003e6\\u003c/span\\u003ec, d). With 1 M ACN, however, uniform electrode morphology ensures homogeneous electric field distribution and suppressed Zn\\u003csup\\u003e2+\\u003c/sup\\u003e concentration gradients. Enhanced \\u003cem\\u003ef\\u003c/em\\u003e\\u003csub\\u003er\\u003c/sub\\u003e\\u0026rsquo; for Zn\\u003csup\\u003e2+\\u003c/sup\\u003e weakens SO\\u003csub\\u003e4\\u003c/sub\\u003e\\u003csup\\u003e2-\\u003c/sup\\u003e interactions, accelerating desolvation and lowering interfacial SO\\u003csub\\u003e4\\u003c/sub\\u003e\\u003csup\\u003e2-\\u003c/sup\\u003e concentration (Supplementary Fig. 16). Critically, ACN also reduces proton flux at the electrode interface (Supplementary Fig. 17), directly mitigating corrosion pit formation observed in Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e5\\u003c/span\\u003ee.\\u003c/p\\u003e\\n\\u003cp\\u003eTime-dependent morphological evolution reveals distinct deposition mechanisms. In ACN-free electrolytes, zinc preferentially nucleates at aluminum electrode edges and propagates inward as porous structures (Supplementary Figs. 18, 19). Even after 40 min, the incomplete coverage persists due to intrinsic porosity. By contrast, ACN enables uniform, compact deposition across the electrode surface. Granular differences are reflected in SEM analysis (Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e6\\u003c/span\\u003ee), confirming crystallographic and densification variations observed earlier (Figs. \\u003cspan class=\\\"InternalRef\\\"\\u003e5\\u003c/span\\u003ee, f). Confocal laser scanning microscope (CLSM) further quantify surface contrasts. Electrolytes without ACN produce micro-scale protrusions and deep potholes and defects originating from both corrosion and non-uniform deposition inhomogeneity (Ra\\u0026thinsp;=\\u0026thinsp;1.397 \\u0026micro;m, Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e6\\u003c/span\\u003ef and Supplementary Fig. 20). ACN-regulated deposition yields smooth surfaces (Ra\\u0026thinsp;=\\u0026thinsp;1.236 \\u0026micro;m), demonstrating that the UTC strategy improves both morphology and surface integrity. Mechanistically, zinc deposition proceeds through five distinct stages after desolvation: adatom diffusion, mixed 2D growth, 3D spiral dislocation growth, and merging and densification (Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e6\\u003c/span\\u003eg). ACN lowers desolvation barriers, enriching interfacial zinc adatoms that preferentially align on angled (101) facets. Subsequent nanoplatelet stacking and merging produce compact, corrosion-resistant deposits that resist proton penetration while enhancing mechanical robustness.\\u003c/p\\u003e\"},{\"header\":\"Discussion\",\"content\":\"\\u003cp\\u003eIn summary, we propose an UTC strategy to regulate cationic degrees of freedom (DOF) for enhanced electric field responsiveness in zinc electrowinning. Ion transport across the electrolyte-to-interface transition is fundamentally governed by translational freedom (\\u003cem\\u003ef\\u003c/em\\u003e\\u003csub\\u003er\\u003c/sub\\u003e\\u0026rsquo;). Within this framework, UTC is defined as indirect modulation of Zn\\u003csup\\u003e2+\\u003c/sup\\u003e solvation using weakly-coordinating additives (DN\\u0026thinsp;\\u0026lt;\\u0026thinsp;18 kcal mol\\u003csup\\u003e-\\u003cspan citationid=\\\"CR1\\\" class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e), thereby raising \\u003cem\\u003ef\\u003c/em\\u003e\\u003csub\\u003er\\u003c/sub\\u003e\\u0026rsquo; relative to fully hydrated Zn(H\\u003csub\\u003e2\\u003c/sub\\u003eO)\\u003csub\\u003e6\\u003c/sub\\u003e\\u003csup\\u003e2+\\u003c/sup\\u003e (\\u003cem\\u003ef\\u003c/em\\u003e\\u003csub\\u003er\\u003c/sub\\u003e\\u0026rsquo; = 0). ACN exemplifies this principle: residing in the secondary solvation shell, it weakens primary-shell ligand interactions while preserving locally continuous but long-range disordered hydrogen bond networks. This dual effect increases \\u003cem\\u003ef\\u003c/em\\u003e\\u003csub\\u003er\\u003c/sub\\u003e\\u0026rsquo; for Zn\\u003csup\\u003e2+\\u003c/sup\\u003e while lowering \\u003cem\\u003ef\\u003c/em\\u003e\\u003csub\\u003er\\u003c/sub\\u003e\\u0026rsquo; for H\\u003csup\\u003e+\\u003c/sup\\u003e, thereby coupling topological entropy with reaction kinetics. With 1 M ACN, ZE achieves a CE of 94.3% with an energy consumption of 2531.4 kWh t\\u003csup\\u003e-\\u003cspan citationid=\\\"CR1\\\" class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e at 500 A m\\u003csup\\u003e-\\u003cspan citationid=\\\"CR2\\\" class=\\\"CitationRef\\\"\\u003e2\\u003c/span\\u003e\\u003c/sup\\u003e and 40 ℃. Even under extreme conditions (1 g L\\u003csup\\u003e-\\u003cspan citationid=\\\"CR1\\\" class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e F\\u003csup\\u003e-\\u003c/sup\\u003e, 10\\u0026times; industrial threshold) at 700 A m\\u003csup\\u003e-\\u003cspan citationid=\\\"CR2\\\" class=\\\"CitationRef\\\"\\u003e2\\u003c/span\\u003e\\u003c/sup\\u003e, the system sustains 90.84% efficiency with an energy demand of 2644.9 kWh t\\u003csup\\u003e-\\u003cspan citationid=\\\"CR1\\\" class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e. This represents a 390.7 kWh t\\u003csup\\u003e-\\u003cspan citationid=\\\"CR1\\\" class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e reduction compared with ACN-free electrolytes. In addition, ACN homogenizes interfacial Zn\\u003csup\\u003e2+\\u003c/sup\\u003e concentration and electric field distribution, steering epitaxial reorientation toward (101)-faceted crystalline growth and producing compact, corrosion-resistant deposits. These findings establish electrolyte topology engineering as a powerful approach to achieving energy-efficient zinc electrowinning at industrial current densities, with broad potential for optimizing electrolyte structures and advancing sustainable metal deposition.\\u003c/p\\u003e\"},{\"header\":\"Methods\",\"content\":\"\\u003cdiv id=\\\"Sec8\\\" class=\\\"Section2\\\"\\u003e\\n \\u003ch2\\u003eChemicals\\u003c/h2\\u003e\\n \\u003cp\\u003eZinc sulfate heptahydrate (ZnSO\\u003csub\\u003e4\\u003c/sub\\u003e\\u0026middot;7H\\u003csub\\u003e2\\u003c/sub\\u003eO), concentrated sulfuric acid (H\\u003csub\\u003e2\\u003c/sub\\u003eSO\\u003csub\\u003e4\\u003c/sub\\u003e, 98%), acetonitrile (CH\\u003csub\\u003e3\\u003c/sub\\u003eCN, ACN), sodium sulfate (Na\\u003csub\\u003e2\\u003c/sub\\u003eSO\\u003csub\\u003e4\\u003c/sub\\u003e), sodium chloride (NaCl), and sodium fluoride (NaF) were obtained from Sinopharm Chemical Reagent Co., Ltd. All reagents were analytical grade and used without further purification. Zinc electrowinning-specific aluminum cathodes and lead-silver alloy anodes were obtained from Suzhou Shuertai Co., Ltd.\\u003c/p\\u003e\\n\\u003c/div\\u003e\\n\\u003ch3\\u003eZn electrowinning experiments\\u003c/h3\\u003e\\n\\u003cp\\u003eFirst, the electrolytes containing 50 g L\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e of Zn\\u003csup\\u003e2+\\u003c/sup\\u003e, 150 g L\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e of H\\u003csub\\u003e2\\u003c/sub\\u003eSO\\u003csub\\u003e4\\u003c/sub\\u003e and 0-1.8 M ACN were prepared. Halide-containing electrolytes incorporated specified NaCl/NaF concentrations. Al cathodes and Pb-Ag anodes (1 cm\\u003csup\\u003e2\\u003c/sup\\u003e active area) were welded to copper leads and epoxy-encapsulated. Electrodes were polished sequentially with 1500- and 2000-grit abrasive paper prior to use. Electrowinning employed 150 mL static electrolyte with 2 cm electrode spacing at 40 ℃ for 3 h. Systematic current density variations were applied during deposition. Post-electrolysis, cell voltage profiles were recorded. Cathodic deposits were detached, mass-quantified, and characterized for current efficiency (CE, \\u003cem\\u003e\\u0026eta;\\u003c/em\\u003e) and energy consumption (\\u003cem\\u003eW\\u003c/em\\u003e). The corresponding formulae are as Eq.\\u0026nbsp;(3), (4)\\u003csup\\u003e6,14\\u003c/sup\\u003e:\\u003c/p\\u003e\\n\\u003cp\\u003e\\u003cimg 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\\\" width=\\\"568\\\" height=\\\"130\\\"\\u003e\\u003c/p\\u003e\\n\\u003cp\\u003eWhere q is the electrochemical equivalent of zinc, 1.2195 g (A h)\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e. \\u003cem\\u003eI\\u003c/em\\u003e denotes the applied current (A). \\u003cem\\u003et\\u003c/em\\u003e represents the electrowinning duration (h). \\u003cem\\u003em\\u003c/em\\u003e is the mass of zinc deposited on the cathode (g). And \\u003cem\\u003eU\\u003c/em\\u003e corresponds to the cell voltage.\\u003c/p\\u003e\\n\\u003ch3\\u003eCharacterizations\\u003c/h3\\u003e\\n\\u003cp\\u003eFourier transform infrared (FTIR) spectra were acquired using a Bruker INVENIO S spectrometer (ATR-DTGS detector, 4000\\u0026thinsp;\\u0026minus;\\u0026thinsp;600 cm\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e). Temperature-dependent and in-situ FTIR measurements employed the same system. Raman spectroscopy utilized a WiTech alpha300R microscope (532 nm excitation, 40 ℃). \\u003csup\\u003e1\\u003c/sup\\u003eH NMR data were recorded on Bruker 600 MHz spectrometers at 40 ℃ using coaxial D\\u003csub\\u003e2\\u003c/sub\\u003eO inserts for field referencing. Thermal properties were analyzed by differential scanning calorimetry (DSC, METTLER TOLEDO TGA/DSC 3+). Viscosity and conductivity measurements used an NDJ-9S viscometer and DDSJ-379L conductivity meter, respectively (40 ℃). Surface characterization employed field emission scanning electron microscopy (FE-SEM, TESCAN, 30 keV), confocal laser scanning microscopy (CLSM, Olympus OLS4100), and custom optical microscopy (AOSVI NX30T-HK830). Crystallographic analysis used X-ray diffraction (XRD, Panalytical Empyrean) with Cu K\\u0026alpha; radiation and a scan rate of 5\\u0026deg; min\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e.\\u003c/p\\u003e\\n\\u003cdiv id=\\\"Sec11\\\" class=\\\"Section2\\\"\\u003e\\n \\u003ch2\\u003eElectrochemical measurements\\u003c/h2\\u003e\\n \\u003cp\\u003eAll electrochemical measurements used a CS2350M workstation with a three-electrode configuration (50 mL electrolyte, 40 ℃). Square aluminum electrodes (10\\u0026times;10\\u0026times;0.1 mm) served as working electrodes, with Ag/AgCl reference and platinum counter electrodes. Self-corrosion rates were determined by mass loss after 2 h immersion of Al/Zn plates in test electrolytes (20 mL). The hydrogen evolution reaction (HER) behavior was analyzed via linear sweep voltammetry (LSV, 1 mV s\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e). Tafel analysis employed 5 mV s\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e\\u003c/sup\\u003e scans from \\u0026minus;\\u0026thinsp;0.9 to -0.2 V vs. Ag/AgCl. EIS measurements at open-circuit potential (0.01 Hz-100 kHz, 5 mV amplitude) provided data for distribution of relaxation times (DRT) analysis. Differential capacitance was measured at 1000 Hz. Deposition kinetics were characterized by chronoamperometry (CA) with potential steps from OCP to deposition potentials, cyclic voltammetry (CV, -0.5 V to -1.35 V vs. Ag/AgCl, 5 mVs\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e), and galvanostatic profiling at 500 A m\\u003csup\\u003e-\\u003cspan class=\\\"CitationRef\\\"\\u003e2\\u003c/span\\u003e\\u003c/sup\\u003e.\\u003c/p\\u003e\\n\\u003c/div\\u003e\\n\\u003cdiv id=\\\"Sec12\\\" class=\\\"Section2\\\"\\u003e\\n \\u003ch2\\u003eQuantum chemistry calculations\\u003c/h2\\u003e\\n \\u003cp\\u003eThe quantum chemistry calculations were conducted by Gaussian software. The geometry optimization used the B3LYP/def2-SVP level, while single-point energy calculations applied B3LYP/def2-TZVP. The SMD continuum model simulated solvation effects. Grimme\\u0026rsquo;s D3 dispersion correction with Becke-Johnson damping accounted for van der Waals interactions. The VMD package visualized electrostatic potential (ESP) iso-surfaces and molecular orbitals\\u003csup\\u003e\\u003cspan class=\\\"CitationRef\\\"\\u003e52\\u003c/span\\u003e\\u003c/sup\\u003e.\\u003c/p\\u003e\\n\\u003c/div\\u003e\\n\\u003cdiv id=\\\"Sec13\\\" class=\\\"Section2\\\"\\u003e\\n \\u003ch2\\u003eMD simulation\\u003c/h2\\u003e\\n \\u003cp\\u003eMolecular dynamics (MD) simulations were performed using GROMACS software with a time step of 1fs\\u003csup\\u003e\\u003cspan class=\\\"CitationRef\\\"\\u003e53\\u003c/span\\u003e\\u003c/sup\\u003e. Nonbonded interactions, including van der Waals and electrostatic forces, were calculated with a cutoff distance of 1.0 nm. Electrostatic interactions were treated using the particle mesh Ewald (PME) method for enhanced accuracy. Simulations were conducted in a cubic box of 6 \\u0026times; 6 \\u0026times; 6 nm\\u003csup\\u003e3\\u003c/sup\\u003e under periodic boundary conditions. The OPC3 water model and GAFF/Merz force fields were applied to describe the solvent and ionic parameters, respectively\\u003csup\\u003e\\u003cspan class=\\\"CitationRef\\\"\\u003e54\\u003c/span\\u003e\\u003c/sup\\u003e. Temperature was maintained at 313 K using the V-rescale thermostat with a coupling time of 2 ns in the NPT ensemble. Each system was equilibrated for 30 ns, followed by an additional 5 ns of production simulation for data collection. Hydrogen bonds were identified based on geometric criteria: a donor-acceptor distance less than 3.5 \\u0026Aring; and a donor-hydrogen-acceptor angle less than 30\\u0026deg;.\\u003c/p\\u003e\\n\\u003c/div\\u003e\\n\\u003cdiv id=\\\"Sec14\\\" class=\\\"Section2\\\"\\u003e\\n \\u003ch2\\u003eFinite element simulations\\u003c/h2\\u003e\\n \\u003cp\\u003eFinite element simulations modeled electric fields, ion concentrations, and hydrogen ion flux using COMSOL Multiphysics 6.2 \\u003csup\\u003e55,56\\u003c/sup\\u003e. The ion concentration follows the first law of Fick\\u0026apos;s diffusion, while the electromigration follows the Nernst-Planck relation. Analyses involving electrode kinetics were introduced to solve the Butler-Volmer equation. Both models are based on a simplified geometric configuration of the study space. Each electrode is 10 \\u0026micro;m in length, with a 7 \\u0026micro;m gap between them. On the surface of the negative electrode, three ellipses (semi-major axis 0.45 \\u0026micro;m, semi-minor axis 0.8 \\u0026micro;m) are uniformly distributed to represent surface protrusions typical of metal electrodes. The simulation domain primarily encompasses the electrode-electrolyte interface. All simulations are conducted at a constant temperature of 313 K. A zero-potential boundary condition is applied at the positive electrode, while the negative electrode is assigned the cell polarization voltage to establish the driving potential for ion transport.\\u003c/p\\u003e\\n\\u003c/div\\u003e\"},{\"header\":\"Declarations\",\"content\":\"\\u003cp\\u003e\\u003cstrong\\u003eData availability\\u003c/strong\\u003e\\u003c/p\\u003e\\n\\u003cp\\u003eThe data that support the findings of this study are available from the corresponding author upon reasonable request.\\u003c/p\\u003e\\n\\u003cp\\u003e\\u003cstrong\\u003eAcknowledgements\\u003c/strong\\u003e\\u003c/p\\u003e\\n\\u003cp\\u003eThe authors gratefully acknowledge the financial support provided by the Fundamental Research Funds for the National Natural Science Foundation of China (No. 52474384), the Central Universities of Central South University (No. 2025ZZTS0082). Thank Shiyanjia Lab (www.shiyanjia.com) for the test including Raman, NMR, et al. And we also thank eceshi (www.eceshi.com) for support during the quantum chemistry calculations calculation, MD and Finite element simulations.\\u003c/p\\u003e\\n\\u003cp\\u003e\\u003cstrong\\u003eAuthor contributions\\u003c/strong\\u003e\\u003c/p\\u003e\\n\\u003cp\\u003eW.Z., G.Z. and Z.T. conceptualized the project and provided the vital guidance. H.C., Z.L., G.L. and Z.C. executed the characterizations, electrochemical measurements and theoretical analysis. H.C., X.L., H.Y., J.Z., Z.F. and Z.L. provided the experimental assistance. H.C. wrote the initial paper approved by all the authors. All authors contributed to the discussion of the results.\\u003c/p\\u003e\\n\\u003cp\\u003e\\u003cstrong\\u003eCompeting interests\\u003c/strong\\u003e\\u003c/p\\u003e\\n\\u003cp\\u003eThe authors declare no competing interests.\\u003c/p\\u003e\\n\\u003cp\\u003e\\u003cstrong\\u003eAdditional information\\u003c/strong\\u003e\\u003c/p\\u003e\\n\\u003cp\\u003e\\u003cstrong\\u003eSupplementary information\\u003c/strong\\u003e The online version contains supplementary material available at http://doi.org/...\\u003c/p\\u003e\\n\\u003cp\\u003e\\u003cstrong\\u003eCorrespondence\\u003c/strong\\u003e and requests for materials should be addressed to Wei Zhang, Guangmin Zhou or Zhongliang Tian.\\u0026nbsp;\\u003c/p\\u003e\\n\\u003cp\\u003e\\u003cstrong\\u003eReprints and permission information\\u003c/strong\\u003e is available at http://www.nature.com/reprints\\u003c/p\\u003e\"},{\"header\":\"References\",\"content\":\"\\u003col\\u003e\\n\\u003cli\\u003eDeng, Z. et al. Global carbon emissions and decarbonization in 2024. \\u003cem\\u003eNat. Rev. Earth Environ.\\u003c/em\\u003e \\u003cstrong\\u003e6\\u003c/strong\\u003e, 231-233 (2025).\\u003c/li\\u003e\\n\\u003cli\\u003eInnocenti, A., Bresser, D., Garche, J. \\u0026amp; Passerini, S. A critical discussion of the current availability of lithium and zinc for use in batteries. \\u003cem\\u003eNat. Commun.\\u003c/em\\u003e \\u003cstrong\\u003e15\\u003c/strong\\u003e, 4068 (2024).\\u003c/li\\u003e\\n\\u003cli\\u003eMonteiro, J. K. L. S., Majuste, D., Porto, M. P., Freitas, A. M. \\u0026amp; Gomes, R. A. M. Zinc cathodes produced with highly-variable DC current simulated from solar irradiance data. \\u003cem\\u003eHydrometallurgy\\u003c/em\\u003e \\u003cstrong\\u003e215\\u003c/strong\\u003e, 10597 (2023).\\u003c/li\\u003e\\n\\u003cli\\u003eLi, J. et al. Redesigning electrification of china\\u0026apos;s ammonia and methanol industry to balance decarbonization with power system security. \\u003cem\\u003eNat. Energy\\u003c/em\\u003e \\u003cstrong\\u003e10\\u003c/strong\\u003e, 762-773 (2025).\\u003c/li\\u003e\\n\\u003cli\\u003eGomes, R. A. M. et al. Use of hybrid renewable energy system with organic photovoltaic cells in zinc electrowinning. \\u003cem\\u003eJ. Cleaner Prod.\\u003c/em\\u003e \\u003cstrong\\u003e293\\u003c/strong\\u003e, 125333 (2021).\\u003c/li\\u003e\\n\\u003cli\\u003eXu, X. et al. Improve the energy efficiency: Effects of additives on longtime zinc electrowinning. \\u003cem\\u003eHydrometallurgy\\u003c/em\\u003e \\u003cstrong\\u003e193\\u003c/strong\\u003e, 105326 (2020).\\u003c/li\\u003e\\n\\u003cli\\u003eYang, Y., Yang, H., Zhuc, R. \\u0026amp; Zhou, H. High reversibility at high current density: The zinc electrodeposition principle behind the \\u0026quot;trick\\u0026quot;. \\u003cem\\u003eEnergy Environ. Sci.\\u003c/em\\u003e \\u003cstrong\\u003e16\\u003c/strong\\u003e, 2723 (2023).\\u003c/li\\u003e\\n\\u003cli\\u003eJi, Q. et al. An environmentally friendly and high current efficiency acid mist inhibitor for zinc electrowinning. \\u003cem\\u003eMater. Res. Express\\u003c/em\\u003e \\u003cstrong\\u003e10\\u003c/strong\\u003e, 076507 (2023).\\u003c/li\\u003e\\n\\u003cli\\u003eShen, G., Chang, L., Jiang, C., Shao, Y. \\u0026amp; Chen, B. Effects of F\\u003csup\\u003e\\u0026minus;\\u003c/sup\\u003e ions on the electrochemical and interface behavior of cathodes in zinc electrowinning. \\u003cem\\u003eJ. Electroanal. Chem.\\u003c/em\\u003e \\u003cstrong\\u003e939\\u003c/strong\\u003e, 117480 (2023).\\u003c/li\\u003e\\n\\u003cli\\u003eI. Epelboin, M. Ksouri, E. Lejay \\u0026amp; Wiart, R. A study of the elementary steps of electron-transfer during the electrocrystallization of zinc. \\u003cem\\u003eElectrochim. Acta\\u003c/em\\u003e \\u003cstrong\\u003e20\\u003c/strong\\u003e, 603-605 (1975).\\u003c/li\\u003e\\n\\u003cli\\u003eSoroura, N., Zhang, W., Ghalia, E. \\u0026amp; Houlachi, G. A review of organic additives in zinc electrodeposition process (performance and evaluation). \\u003cem\\u003eHydrometallurgy\\u003c/em\\u003e \\u003cstrong\\u003e171\\u003c/strong\\u003e, 320-332 (2017).\\u003c/li\\u003e\\n\\u003cli\\u003eSorour, N., Su, C., Ghali, E. \\u0026amp; Houlachi, G. Effect of ionic liquid additives on oxygen evolution reaction and corrosion behavior of Pb-Ag anode in zinc electrowinning. \\u003cem\\u003eElectrochim. Acta\\u003c/em\\u003e \\u003cstrong\\u003e258\\u003c/strong\\u003e, 631-638 (2017).\\u003c/li\\u003e\\n\\u003cli\\u003eYu, H. et al. Reversible adsorption with oriented arrangement of a zwitterionic additive stabilizes electrodes for ultralong-life Zn-ion batteries. \\u003cem\\u003eEnergy Environ. Sci.\\u003c/em\\u003e \\u003cstrong\\u003e16\\u003c/strong\\u003e, 2684-2695 (2023).\\u003c/li\\u003e\\n\\u003cli\\u003eLin, G. et al. Roles of tannic acid and gelatin in Zn electrowinning and their inhibition mechanisms investigated via electrochemical methods. \\u003cem\\u003eHydrometallurgy\\u003c/em\\u003e \\u003cstrong\\u003e195\\u003c/strong\\u003e, 105390 (2020).\\u003c/li\\u003e\\n\\u003cli\\u003eWu, X., Liu, Z. \\u0026amp; Liu, X. The effects of additives on the electrowinning of zinc from sulphate solutions with high fluoride concentration. \\u003cem\\u003eHydrometallurgy\\u003c/em\\u003e \\u003cstrong\\u003e141\\u003c/strong\\u003e, 31-35 (2014).\\u003c/li\\u003e\\n\\u003cli\\u003eGuo, Y. et al. Dynamic covalent bonds regulate zinc plating/stripping behaviors for high-performance zinc ion batteries. \\u003cem\\u003eAngew. Chem. Int. Ed.\\u003c/em\\u003e \\u003cstrong\\u003e63\\u003c/strong\\u003e, e202406597 (2024).\\u003c/li\\u003e\\n\\u003cli\\u003eDong, D., Wang, T., Sun, Y., Fan, J. \\u0026amp; Lu, Y.C. Hydrotropic solubilization of zinc acetates for sustainable aqueous battery electrolytes. \\u003cem\\u003eNat. Sustain.\\u003c/em\\u003e \\u003cstrong\\u003e6\\u003c/strong\\u003e, 1474-1484 (2023).\\u003c/li\\u003e\\n\\u003cli\\u003eZhao, C.-X., Li, Z., Chen, B., Chen, F. \\u0026amp; Wang, C. Self-adaptive electrolytes for fast-charging batteries. \\u003cem\\u003eNat. Energy\\u003c/em\\u003e \\u003cstrong\\u003e10\\u003c/strong\\u003e, 904-913 (2025).\\u003c/li\\u003e\\n\\u003cli\\u003eQiu, M. et al. Tailoring water structure with high-tetrahedral-entropy for antifreezing electrolytes and energy storage at \\u0026minus;80\\u0026thinsp;\\u0026deg;C. \\u003cem\\u003eNat. Commun.\\u003c/em\\u003e \\u003cstrong\\u003e14\\u003c/strong\\u003e, 601 (2023).\\u003c/li\\u003e\\n\\u003cli\\u003eTuckerman, M. E., Marx, D. \\u0026amp; Parrinello, M. The nature and transport mechanism of hydrated hydroxide ions in aqueous solution. \\u003cem\\u003eNature\\u003c/em\\u003e \\u003cstrong\\u003e417\\u003c/strong\\u003e, 925-929 (2002).\\u003c/li\\u003e\\n\\u003cli\\u003eMarx, D., Tuckerman, M. E., Hutter, J. r. \\u0026amp; Parrinello, M. The nature of the hydrated excess proton in water. \\u003cem\\u003eNature\\u003c/em\\u003e \\u003cstrong\\u003e397\\u003c/strong\\u003e, 601-604 (1999).\\u003c/li\\u003e\\n\\u003cli\\u003eLi, M. et al. Comprehensive H\\u003csub\\u003e2\\u003c/sub\\u003eO molecules regulation via deep eutectic solvents for ultra-stable zinc. \\u003cem\\u003eAngew. Chem. Int. Ed.\\u003c/em\\u003e \\u003cstrong\\u003e62\\u003c/strong\\u003e, e202215552 (2023).\\u003c/li\\u003e\\n\\u003cli\\u003eWu, M. et al. Highly reversible and stable Zn metal anodes realized using a trifluoroacetamide electrolyte additive. \\u003cem\\u003eEnergy Environ. Sci.\\u003c/em\\u003e \\u003cstrong\\u003e17\\u003c/strong\\u003e, 619-629 (2024).\\u003c/li\\u003e\\n\\u003cli\\u003eZhang, R. et al. Weakly solvating aqueous-based electrolyte facilitated by a soft co-solvent for extreme temperature operations of zinc-ion batteries. \\u003cem\\u003eEnergy Environ. Sci.\\u003c/em\\u003e \\u003cstrong\\u003e17\\u003c/strong\\u003e, 4569-4581 (2024).\\u003c/li\\u003e\\n\\u003cli\\u003eWang, X. et al. Weak solvation effects and molecular-rich layers induced water-poor helmholtz layers boost highly stable Zn anode. \\u003cem\\u003eEnergy Storage Mater.\\u003c/em\\u003e \\u003cstrong\\u003e73\\u003c/strong\\u003e, 103856 (2024).\\u003c/li\\u003e\\n\\u003cli\\u003eShi, X. et al. A weakly solvating electrolyte towards practical rechargeable aqueous zinc-ion batteries. \\u003cem\\u003eNat. Commun.\\u003c/em\\u003e \\u003cstrong\\u003e15\\u003c/strong\\u003e, 302 (2024).\\u003c/li\\u003e\\n\\u003cli\\u003eZheng, J. et al. Critical solvation structures arrested active molecules for reversible Zn electrochemistry. \\u003cem\\u003eNano-Micro Letters\\u003c/em\\u003e \\u003cstrong\\u003e16\\u003c/strong\\u003e, 145 (2024).\\u003c/li\\u003e\\n\\u003cli\\u003eYang, H. et al. A compliant metastructure design with reconfigurability up to six degrees of freedom. \\u003cem\\u003eNat. Commun.\\u003c/em\\u003e \\u003cstrong\\u003e16\\u003c/strong\\u003e, 719 (2025).\\u003c/li\\u003e\\n\\u003cli\\u003eKamba, M., Shimizu, R. \\u0026amp; Aikawa, K. Nanoscale feedback control of six degrees of freedom of a near-sphere. \\u003cem\\u003eNat. Commun.\\u003c/em\\u003e \\u003cstrong\\u003e14\\u003c/strong\\u003e, 7943 (2023).\\u003c/li\\u003e\\n\\u003cli\\u003eCao, J. et al. Strategies of regulating Zn\\u003csup\\u003e2+\\u003c/sup\\u003e solvation structures for dendrite-free and side reaction-suppressed zinc-ion batteries. \\u003cem\\u003eEnergy Environ. Sci.\\u003c/em\\u003e \\u003cstrong\\u003e15\\u003c/strong\\u003e, 499-528 (2022).\\u003c/li\\u003e\\n\\u003cli\\u003eTian, Y. et al. Visualizing eigen/zundel cations and their interconversion in monolayer water on metal surfaces. \\u003cem\\u003eScience\\u003c/em\\u003e \\u003cstrong\\u003e377\\u003c/strong\\u003e, 315-319 (2022).\\u003c/li\\u003e\\n\\u003cli\\u003eXu, H., Cabriolu, R. \\u0026amp; Smit, B. Effects of degrees of freedom on calculating diffusion properties in nanoporous materials. \\u003cem\\u003eJ. Chem. Theory Comput.\\u003c/em\\u003e \\u003cstrong\\u003e18\\u003c/strong\\u003e, 2826-2835 (2022).\\u003c/li\\u003e\\n\\u003cli\\u003eLiu, T., Ding, J., Xu, J., Zhao, D. \\u0026amp; Qiu, X. Design and dynamics analysis of three-degree-of-freedom kinematic mechanism for helicopter attitude simulation. \\u003cem\\u003eSci. Rep.\\u003c/em\\u003e \\u003cstrong\\u003e15\\u003c/strong\\u003e, 7463 (2025).\\u003c/li\\u003e\\n\\u003cli\\u003eYang, H. et al. Reunderstanding aqueous Zn electrochemistry from interfacial specific adsorption of solvation structures. \\u003cem\\u003eEnergy Environ. Sci.\\u003c/em\\u003e \\u003cstrong\\u003e16\\u003c/strong\\u003e, 2910-2923 (2023).\\u003c/li\\u003e\\n\\u003cli\\u003eZhang, M. et al. Dynamically interfacial pH-buffering effect enabled by n-methylimidazole molecules as spontaneous proton pumps toward highly reversible zinc-metal anodes. \\u003cem\\u003eAdv. Mater.\\u003c/em\\u003e \\u003cstrong\\u003e35\\u003c/strong\\u003e, 2208630 (2023).\\u003c/li\\u003e\\n\\u003cli\\u003eCataldo, F. A revision of the gutmann donor numbers of a series of phosphoramides including tepa. \\u003cem\\u003eEur. Chem. Bull.\\u003c/em\\u003e \\u003cstrong\\u003e4\\u003c/strong\\u003e, 92-97 (2015).\\u003c/li\\u003e\\n\\u003cli\\u003eWang, Y. et al. Solvent control of water O\\u0026minus;H bonds for highly reversible zinc ion batteries. \\u003cem\\u003eNat. Commun.\\u003c/em\\u003e \\u003cstrong\\u003e14\\u003c/strong\\u003e, 2720 (2023).\\u003c/li\\u003e\\n\\u003cli\\u003eXu, C. et al. Fast single metal cation conduction in ion-water aggregated aqueous battery electrolytes. \\u003cem\\u003eNat. Commun.\\u003c/em\\u003e \\u003cstrong\\u003e16\\u003c/strong\\u003e, 4574 (2025).\\u003c/li\\u003e\\n\\u003cli\\u003eYang, H. et al. A metal-organic framework as a multifunctional ionic sieve membrane for long-life aqueous zinc-iodide batteries. \\u003cem\\u003eAdv. Mater.\\u003c/em\\u003e \\u003cstrong\\u003e32\\u003c/strong\\u003e, 2004240 (2020).\\u003c/li\\u003e\\n\\u003cli\\u003eQin, Y. et al. In situ construction of irox nanofilm on tiox for boosting low-Ir catalysis in practical pem electrolyze. \\u003cem\\u003eAdv. Energy Mater.\\u003c/em\\u003e \\u003cstrong\\u003e15\\u003c/strong\\u003e, 2405636 (2025).\\u003c/li\\u003e\\n\\u003cli\\u003eZhang, J. et al. Adhesive zwitterionic poly(ionic liquid) with unprecedented organic solvent resistance. \\u003cem\\u003eAdv. Mater.\\u003c/em\\u003e \\u003cstrong\\u003e36\\u003c/strong\\u003e, 202403039 (2024).\\u003c/li\\u003e\\n\\u003cli\\u003eGomes, R. J. et al. Modulating water hydrogen bonding within a non-aqueous environment controls its reactivity in electrochemical transformations. \\u003cem\\u003eNat. Catal.\\u003c/em\\u003e \\u003cstrong\\u003e7\\u003c/strong\\u003e, 689-701 (2024).\\u003c/li\\u003e\\n\\u003cli\\u003eDou, Q. et al. Unveiling solvation structure and desolvation dynamics of hybrid electrolytes for ultralong cyclability and facile kinetics of Zn-Al alloy anodes. \\u003cem\\u003eEnergy Environ. Sci.\\u003c/em\\u003e \\u003cstrong\\u003e15\\u003c/strong\\u003e, 4572-45883 (2022).\\u003c/li\\u003e\\n\\u003cli\\u003eLi, T. C. et al. A universal additive strategy to reshape electrolyte solvation structure toward reversible Zn storage. \\u003cem\\u003eAdv. Energy Mater.\\u003c/em\\u003e \\u003cstrong\\u003e12\\u003c/strong\\u003e, 2103231 (2022).\\u003c/li\\u003e\\n\\u003cli\\u003eChang, L. et al. High-entropy solvation chemistry towards affordable and practical Ah-level zinc metal battery. \\u003cem\\u003eNat. Commun.\\u003c/em\\u003e \\u003cstrong\\u003e16\\u003c/strong\\u003e, 6134 (2025).\\u003c/li\\u003e\\n\\u003cli\\u003eHuang, J. et al. Interfacial biomacromolecular engineering toward stable Ah-level aqueous zinc batteries. \\u003cem\\u003eAdv. Mater.\\u003c/em\\u003e \\u003cstrong\\u003e36\\u003c/strong\\u003e, 2406257 (2024).\\u003c/li\\u003e\\n\\u003cli\\u003eBrown, M. A., Goel, A. \\u0026amp; Abbas, Z. Effect of electrolyte concentration on the stern layer thickness at a charged interface. \\u003cem\\u003eAngew. Chem. Int. Ed.\\u003c/em\\u003e \\u003cstrong\\u003e55\\u003c/strong\\u003e, 3790-3794 (2016).\\u003c/li\\u003e\\n\\u003cli\\u003eSong, Y. et al. Bilateral in-situ functionalization towards Ah-scale aqueous zinc metal batteries. \\u003cem\\u003eNat. Commun.\\u003c/em\\u003e \\u003cstrong\\u003e16\\u003c/strong\\u003e, 3142 (2025).\\u003c/li\\u003e\\n\\u003cli\\u003eZhao, Y. et al. Tailoring grain boundary stability of zinc-titanium alloy for long-lasting aqueous zinc batteries. \\u003cem\\u003eNat. Commun.\\u003c/em\\u003e \\u003cstrong\\u003e14\\u003c/strong\\u003e, 7080 (2023).\\u003c/li\\u003e\\n\\u003cli\\u003eCheng, H. et al. Significantly enhanced dehalogenation selectivity in near-neutral zinc sulfate electrolytes by diffusion dialysis. \\u003cem\\u003eJ. Membr. Sci.\\u003c/em\\u003e \\u003cstrong\\u003e563\\u003c/strong\\u003e, 142-148 (2018).\\u003c/li\\u003e\\n\\u003cli\\u003eLiu, Z. et al. Construct robust epitaxial growth of(101) textured zinc metal anode for long life and high capacity in mild aqueous zinc-ion batteries. \\u003cem\\u003eAdv. Mater.\\u003c/em\\u003e \\u003cstrong\\u003e36\\u003c/strong\\u003e, 2305988 (2024).\\u003c/li\\u003e\\n\\u003cli\\u003eSch\\u0026auml;fer, A., Huber, C. \\u0026amp; Ahlrichs, R. Fully optimized contracted gaussian basis sets of triple zeta valence quality for atoms Li to Kr. \\u003cem\\u003eJ. Chem. Phys.\\u003c/em\\u003e \\u003cstrong\\u003e100\\u003c/strong\\u003e, 5829-5835 (1994).\\u003c/li\\u003e\\n\\u003cli\\u003eBerendsen, H. J. C., Spoel, D. v. d. \\u0026amp; Drunen, R. v. Gromacs: A message-passing parallel molecular dynamics implementation. \\u003cem\\u003eComput. Phys. Commun.\\u003c/em\\u003e \\u003cstrong\\u003e91\\u003c/strong\\u003e, 43-56 (1995).\\u003c/li\\u003e\\n\\u003cli\\u003eLi, Z., Song, L. F., Li, P. \\u0026amp; Merz, K. M. Systematic parametrization of divalent metal ions for the opc3, opc, tip3p-fb, and tip4p-fb water models. \\u003cem\\u003eJ. Chem. Theory Comput.\\u003c/em\\u003e \\u003cstrong\\u003e16\\u003c/strong\\u003e, 4429-4442 (2020).\\u003c/li\\u003e\\n\\u003cli\\u003eWang, D. et al. Localized anion-cation aggregated aqueous electrolytes with accelerated kinetics for low-temperature zinc metal batteries. \\u003cem\\u003eAngew. Chem. Int. Ed.\\u003c/em\\u003e \\u003cstrong\\u003e62\\u003c/strong\\u003e, e202315834 (2023).\\u003c/li\\u003e\\n\\u003cli\\u003eLin, H. et al. Interfacial regulation via configuration screening of a disodium naphthalenedisulfonate additive enabled high-performance wide-pH Zn-based batteries. \\u003cem\\u003eEnergy Environ. Sci.\\u003c/em\\u003e \\u003cstrong\\u003e18\\u003c/strong\\u003e, 1282-1293 (2025).\\u003c/li\\u003e\\n\\u003c/ol\\u003e\"}],\"fulltextSource\":\"\",\"fullText\":\"\",\"funders\":[],\"hasAdminPriorityOnWorkflow\":false,\"hasManuscriptDocX\":true,\"hasOptedInToPreprint\":true,\"hasPassedJournalQc\":\"\",\"hasAnyPriority\":true,\"hideJournal\":false,\"highlight\":\"\",\"institution\":\"\",\"isAcceptedByJournal\":false,\"isAuthorSuppliedPdf\":false,\"isDeskRejected\":\"\",\"isHiddenFromSearch\":false,\"isInQc\":false,\"isInWorkflow\":false,\"isPdf\":false,\"isPdfUpToDate\":true,\"isWithdrawnOrRetracted\":false,\"journal\":{\"display\":true,\"email\":\"info@researchsquare.com\",\"identity\":\"nature-portfolio\",\"isNatureJournal\":true,\"hasQc\":false,\"allowDirectSubmit\":false,\"externalIdentity\":\"\",\"sideBox\":\"\",\"snPcode\":\"\",\"submissionUrl\":\"\",\"title\":\"Nature Portfolio\",\"twitterHandle\":\"\",\"acdcEnabled\":false,\"dfaEnabled\":false,\"editorialSystem\":\"ejp\",\"reportingPortfolio\":\"\",\"inReviewEnabled\":true,\"inReviewRevisionsEnabled\":false},\"keywords\":\"Zinc electrowinning, electrolyte topology engineering, hydrogen evolution reaction, transfer kinetics, energy consumption\",\"lastPublishedDoi\":\"10.21203/rs.3.rs-7829869/v1\",\"lastPublishedDoiUrl\":\"https://doi.org/10.21203/rs.3.rs-7829869/v1\",\"license\":{\"name\":\"CC BY 4.0\",\"url\":\"https://creativecommons.org/licenses/by/4.0/\"},\"manuscriptAbstract\":\"\\u003cp\\u003eZinc electrowinning (ZE), a carbon-intensive process, suffers from high energy consumption due to the parasitic hydrogen evolution reaction (HER) and poor deposit quality. Conventional adsorption-based additives fail to simultaneously deliver high current efficiency (CE) and low cell voltage, sustaining energy inefficiency. To address this limitation, we propose an electrolyte engineering through undercoordinated topology constraint (UTC) to regulate Zn\\u003csup\\u003e2+\\u003c/sup\\u003e and proton transfer kinetics. Using weakly-coordinating additives, UTC weakens SO\\u003csub\\u003e4\\u003c/sub\\u003e\\u003csup\\u003e2\\u0026minus;\\u003c/sup\\u003e-Zn\\u003csup\\u003e2+\\u003c/sup\\u003e interactions while preserving locally continuous but long-range disordered hydrogen bond (HB) networks, thereby increasing the translational freedom (\\u003cem\\u003ef\\u003c/em\\u003e\\u003csub\\u003etrans\\u003c/sub\\u003e) of Zn\\u003csup\\u003e2+\\u003c/sup\\u003e and restricting proton transport. The resulting kinetics decoupling facilitates zinc deposition and suppresses HER at high current densities, thereby elevating CE and saving energy. Implemented with acetonitrile (ACN) as a model molecule, the decoupled ion transport homogenizes the interfacial ion and field distribution and directs the growth of corrosion-resistant (101)-faceted deposits. And the ACN-induced UTC enables ZE to achieve 94.3% CE with an energy demand of 2531.4 kWh t\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e at 500 A m\\u003csup\\u003e\\u0026minus;\\u0026thinsp;2\\u003c/sup\\u003e (40 ℃), a factor of only 1.55 above the theoretical minimum. It also demonstrates robust performance under extreme F\\u003csup\\u003e\\u0026minus;\\u003c/sup\\u003e contamination (1 g L\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e), simultaneously boosting CE by 11.96% and slashing energy consumption by 12.87% at 700 A m\\u003csup\\u003e\\u0026minus;\\u0026thinsp;2\\u003c/sup\\u003e. This work establishes electrolyte topology engineering as a powerful pathway to sustainable and energy-efficient metal electrowinning.\\u003c/p\\u003e\",\"manuscriptTitle\":\"Decoupling ionic transfer kinetics via undercoordinated constraints for energy-efficient and high-quality zinc electrowinning\",\"msid\":\"\",\"msnumber\":\"\",\"nonDraftVersions\":[{\"code\":1,\"date\":\"2025-11-10 11:03:22\",\"doi\":\"10.21203/rs.3.rs-7829869/v1\",\"editorialEvents\":[],\"status\":\"published\",\"journal\":{\"display\":true,\"email\":\"info@researchsquare.com\",\"identity\":\"nature-communications\",\"isNatureJournal\":true,\"hasQc\":false,\"allowDirectSubmit\":false,\"externalIdentity\":\"NCOMMS\",\"sideBox\":\"Learn more about [Nature Communications](http://www.nature.com/ncomms/)\",\"snPcode\":\"\",\"submissionUrl\":\"https://mts-ncomms.nature.com/\",\"title\":\"Nature Communications\",\"twitterHandle\":\"\",\"acdcEnabled\":true,\"dfaEnabled\":true,\"editorialSystem\":\"ejp\",\"reportingPortfolio\":\"Nature Communications\",\"inReviewEnabled\":true,\"inReviewRevisionsEnabled\":false}}],\"origin\":\"\",\"ownerIdentity\":\"ce78241a-3818-4336-9191-8a414d0c65b1\",\"owner\":[],\"postedDate\":\"November 10th, 2025\",\"published\":true,\"recentEditorialEvents\":[],\"rejectedJournal\":[],\"revision\":\"\",\"amendment\":\"\",\"status\":\"under-review\",\"subjectAreas\":[{\"id\":56286735,\"name\":\"Physical sciences/Chemistry/Physical chemistry/Reaction kinetics and dynamics\"},{\"id\":56286736,\"name\":\"Physical sciences/Engineering/Chemical engineering\"},{\"id\":56286737,\"name\":\"Physical sciences/Chemistry/Electrochemistry\"},{\"id\":56286738,\"name\":\"Physical sciences/Chemistry/Materials chemistry\"}],\"tags\":[],\"updatedAt\":\"2025-11-10T11:03:22+00:00\",\"versionOfRecord\":[],\"versionCreatedAt\":\"2025-11-10 11:03:22\",\"video\":\"\",\"vorDoi\":\"\",\"vorDoiUrl\":\"\",\"workflowStages\":[]},\"version\":\"v1\",\"identity\":\"rs-7829869\",\"journalConfig\":\"researchsquare\"},\"__N_SSP\":true},\"page\":\"/article/[identity]/[[...version]]\",\"query\":{\"redirect\":\"/article/rs-7829869\",\"identity\":\"rs-7829869\",\"version\":[\"v1\"]},\"buildId\":\"8U1c8b4HqxoKbykW_rLl7\",\"isFallback\":false,\"isExperimentalCompile\":false,\"dynamicIds\":[84888],\"gssp\":true,\"scriptLoader\":[]}","source_license":"CC-BY-4.0","license_restricted":false}