Contextual Solvation Control for Nonlinear Kinetic Optimization in Dual-Cosolvent Electrolytes for Aqueous Zinc Metal Batteries

Contextual Solvation Control for Nonlinear Kinetic Optimization in Dual-Cosolvent Electrolytes for Aqueous Zinc Metal Batteries | 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 Contextual Solvation Control for Nonlinear Kinetic Optimization in Dual-Cosolvent Electrolytes for Aqueous Zinc Metal Batteries Qingyu Yan, Erhai Hu, Jinpeng Song, Gang Wu, Beier Jia, Danyang Wang, and 8 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-8234367/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 Cosolvent engineering for aqueous Zn metal batteries has traditionally emphasized thermodynamic stabilization, whereas the kinetic dimension of Zn²⁺ charge transfer—particularly in multi-cosolvent systems—remains far less understood. Here, we uncover a contextual solvation control mechanism in a dual-cosolvent electrolyte pairing a strong cosolvent (dimethyl sulfoxide, DMSO) with a weak cosolvent (dimethyl carbonate, DMC). Mechanistically, the outer-shell weak cosolvent imposes mild yet favorable interactions that modulate Zn–ligand binding and facilitate solvent exchange, while simultaneously promoting the formation of a thin, well-regulated SEI that accelerates interfacial charge transfer kinetics. This contextual regulation preserves thermodynamic stability while, more importantly, enabling a nonlinear kinetic optimization that emerges exclusively at specific strong-to-weak cosolvent ratios. Using a multi-descriptor kinetic framework, we show that the dual-cosolvent regime lowers the reorganization energy and charge-transfer barrier by ~ 40% relative to single-cosolvent systems. As a result, the electrolyte supports stable Zn plating/stripping for over 2000 hours with suppressed dendrite formation. Full cells paired with vanadium-based cathodes further exhibit enhanced capacity retention, long-term cycling stability, and markedly improved rate performance. Physical sciences/Energy science and technology/Energy storage/Batteries Physical sciences/Materials science/Materials for energy and catalysis/Batteries Physical sciences/Materials science/Materials for energy and catalysis/Electrochemistry aqueous zinc batteries zinc metal anode cosolvent engineering kinetics optimization dual-cosolvent electrolyte Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 1. Introduction The global transition toward renewable energy generation has highlighted the urgent need for safe, cost-effective, and sustainable energy storage systems. 1 , 2 Among various candidates, aqueous zinc metal batteries (ZMBs) have attracted significant attention for large-scale grid applications owing to the intrinsic advantages of zinc metal—low redox potential (–0.76 V vs. SHE), high theoretical capacity (820 mAh g⁻¹), natural abundance, and water-compatible chemistry. These features make ZMBs a promising alternative to lithium-based technologies, especially for stationary storage where safety and cost are paramount. 3 , 4 However, despite these merits, the zinc anode remains the bottleneck that hinders practical deployment. Two fundamental challenges dominate (Fig. 1 a): (1) Side reactions, particularly the hydrogen evolution reaction (HER), which arise from water’s narrow electrochemical stability window and thermodynamic instability on the Zn surface; and (2) Uncontrolled zinc dendrite formation, associated with non-uniform nucleation and anisotropic Zn deposition, which closely relates to the kinetic aspect. These phenomena jointly deteriorate cycling life and threaten operational stability. 5 , 6 To address these challenges, extensive efforts have been directed toward engineering the anode–electrolyte interfacial environment, including modifying the anode surface, tuning the separator chemistry, and—most effectively—optimizing the electrolyte composition. 7 , 8 Electrolyte engineering directly governs zinc-ion solvation structure, interfacial adsorption behavior, and the surrounding water network. In recent years, the cosolvent strategy—introducing a controlled fraction of organic molecules into aqueous electrolytes—has emerged as a simple yet versatile approach. By partially replacing water with organic components, such electrolytes combine the safety and ionic conductivity of aqueous media with the expanded electrochemical stability window and tunable solvation environment of organic systems (Fig. 1 a). 9 Most early studies have concentrated on the thermodynamic aspect of cosolvent design, aiming primarily on adjusting the primary solvation shell to suppress HER and widen the Zn plating/stripping stability window. 10 – 12 This focus is understandable, as establishing a stable thermodynamic environment is the prerequisite for enabling reversible Zn deposition. However, as thermodynamic stabilization becomes better understood, attention has gradually shifted toward the kinetic dimension—how electrolyte composition influences charge transfer dynamics. Electrochemical kinetics not only dictates the rate capability of ZMBs but also governs Zn nucleation behavior, growth morphology, and ultimately dendrite formation. 13 , 14 Several recent studies have begun to explore such effects in single-cosolvent systems. For example, Huang et al. selected ethylene carbonate (EC) with a highest dielectric constant and weakest ion-pair interactions to induce a kinetic compensation effect that enhances Zn²⁺ transfer. 15 Chen et al. designed a medium-ion-association electrolyte with a moderate contact-ion-pair (CIP) ratio, achieving a balance between charge transfer kinetics and solid-electrolyte interphace (SEI) formation. 16 Nevertheless, single-cosolvent systems inherently offer limited tunability and often exhibit trade-offs between thermodynamics and kinetics. To overcome these limitations, multi-cosolvent systems have recently been proposed. For instance, dual-cosolvent electrolytes such as dimethyl sulfoxide (DMSO)–acetonitrile (AN), 17 anthraquinone-1-sulfonate (AQS)- ethylene glycol (EG), 18 and high-entropy electrolytes 19 , 20 incorporating dual salts or dual strong cosolvents have been designed to suppress water activity and construct inorganic–organic gradient SEI layers. Despite this growing interest, the interplay between different cosolvents remains poorly understood. In most reported systems, combining two strong cosolvents yields only a simple additive effect in restricting water decomposition. However, the reality is far more complex—the interactions among water, salts, and two distinct cosolvents can fundamentally reshape solvation structures and ion-transport dynamics in ways that are not linearly predictable. Therefore, in this work, we present a systematic investigation of dual-cosolvent electrolytes, focusing on their coupled influence on both thermodynamic stability and, more importantly, the charge transfer kinetics of zinc deposition. As illustrated in Fig. 1 b, commonly used cosolvents in ZMBs can be broadly categorized as strong or weak based on their donor number (DN) and dielectric constant (ε): a) Strong cosolvents possess high DN and ε, allowing them to coordinate directly with Zn²⁺ in the primary solvation shell, thereby weakening the Zn–H₂O interaction and suppressing parasitic reactions. b) Weak cosolvents with low DN and ε, contribute indirectly by modifying the outer solvation environment and potentially promoting CIPs through reduced ion dissociation. 21 In this study, we reveal how the contrasting characteristics of strong and weak cosolvents interplay to regulate Zn²⁺ charge transfer kinetics. We elucidate a contextual control mechanism unique to the dual-cosolvent electrolyte—one that does not fundamentally alter the primary Zn²⁺ coordination motifs, but instead operates through weak, favorable interactions originating from the outer solvation shell and through the formation of a well-regulated interphase. These coupled, context-dependent effects give rise to a nonlinear kinetic response to the strong–weak cosolvent ratio, with the dual-cosolvent formulation delivering the maximum enhancement and lowering the kinetic barrier by ~ 40% relative to single-cosolvent systems. As a result, Zn‖Zn symmetric cells demonstrate stable cycling over 2000 hours with minimal overpotential, and Cu‖Zn half cells achieve an average Coulombic efficiency (CE) of 99.8% over 1000 cycles. Furthermore, a full cell using vanadium-based cathode achieved 83% capacity retention after 2000 cycles at 1 A g⁻¹ and markedly improved rate performance. Overall, this study deepens the mechanistic understanding of multi-component effects in aqueous zinc systems and establishes a rational design framework for next-generation electrolytes that simultaneously optimize thermodynamic stability and electrochemical kinetics. 2. Results 2.1. Thermodynamics and Kinetics of Cosolvent Electrolyte From Fig. 1 b, we selected DMSO and dimethyl carbonate (DMC) as the focus of the current study. DMSO is a strongly coordinating, high-permittivity polar aprotic solvent with excellent solvating ability for a wide range of salts, and is one of the most extensively studied cosolvents for zinc batteries due to its capability to replace water molecules in the Zn²⁺ solvation shell. 11 , 22 , 23 In contrast, DMC, a widely used organic carbonate solvent in lithium-ion battery (LIB) electrolytes, primarily serves as a low-viscosity diluent that enhances ionic conductivity and improves electrolyte fluidity. 24 The distinct physicochemical characteristics of these two solvents make them a representative pair of strong and weak cosolvents, enabling systematic investigation into their interactions and potential synergistic effects on electrolyte structure and electrochemical performance. According to density functional theory (DFT) calculations, the binding energies of DMSO, H₂O, and DMC toward Zn²⁺ are − 1.27 eV, − 0.60 eV, 15 and − 0.40 eV, 21 respectively (Fig. 1 c). These results clearly confirm the strongly coordinating nature of DMSO and the weak coordination ability of DMC relative to the reference solvent, water. To investigate the synergistic effect of dual cosolvents on zinc deposition—which remains insufficiently understood due to limited prior research— we examined the effects of varying the ratio between a strong (DMSO) and a weak (DMC) cosolvent on both the thermodynamics and kinetics of Zn²⁺. We first evaluated the thermodynamic stability by measuring the CE of Cu‖Zn half cells containing electrolytes with different total cosolvent contents and various DMSO/DMC ratios (Figure S1 ). The results are summarized in Fig. 1 d, where DMSO and DMC are abbreviated as D and M, respectively, and the numbers preceding each letter indicate their volume percentage in the electrolyte. All electrolytes were formulated with 1 M Zn(OTf)₂, chosen for its favorable salting-in effect that facilitates dissolution in organic-rich systems. Each data point represents the average CE from three independent measurements, with error bars indicating the corresponding standard deviation. From left to right in Fig. 1 d, the DMSO content increases gradually from 0 vol% to 50 vol%. It is evident that the CE improves significantly with increasing cosolvent concentration, demonstrating enhanced thermodynamic stability. However, when the total cosolvent content is fixed and the ratio between DMSO and DMC is varied, the CE remains relatively stable. This indicates that both strong and weak cosolvents contribute positively to suppressing parasitic reactions and enhancing thermodynamic stability. Having established that both DMSO and DMC enhance thermodynamic stability and that dual-cosolvent formulations maintain similarly high CE across composition, we then turned to how the cosolvent ratio modulates kinetics. In battery systems, overall electrochemical kinetics can be broadly divided into two regimes: diffusion kinetics and charge transfer kinetics. According to previous studies on aqueous ZMB, 25–27 at low to moderate current densities, the charge transfer process typically dominates as the rate-determining step, whereas at very high current densities, ion diffusion through the electrolyte becomes the primary limitation. Since most practical operating conditions fall within the charge transfer-controlled regime, this study focuses on the charge transfer kinetics at the Zn anode/electrolyte interface. To comprehensively evaluate the kinetic behavior, three complementary descriptors were employed (Fig. 2 a): (1) the intrinsic descriptor, Marcus reorganization energy (λ), which reflects the fundamental electron-transfer barrier; (2) the extrinsic descriptor, charge transfer resistance (Rct); and (3) the macroscopic performance indicator, the overpotential (η) observed during Zn‖Zn symmetric cell cycling. The Marcus reorganization energy (λ) serves as a fundamental parameter describing electron-transfer kinetics, originating from Marcus theory. 28 It represents the energy required to reorganize the solvation environment of both the redox species and surrounding solvent molecules during electron transfer. A smaller λ indicates a lower degree of structural rearrangement and therefore a faster charge transfer process. Unlike empirical kinetic descriptors such as the exchange current density (i₀) obtained from the Butler–Volmer (B–V) model, λ provides a mechanistic and physically meaningful insight into the interfacial electron-transfer barrier, directly linked to solvation structure and molecular reorganization at the interface. 26 In this work, λ was quantified using the Marcus–Hush–Chidsey (MHC) model 29 – 31 fitted to linear sweep voltammetry (LSV) data. 32 As shown in Fig. 2 b and Figure S2, the MHC fitting of the LSV curves exhibits high R² values, validating the robustness of this approach in describing the Zn²⁺ charge transfer process. As summarized in Fig. 2 a, λ exhibits a clear nonlinear U-shaped trend with varying strong/weak cosolvent ratios. Upon decreasing the fraction of DMSO and increasing that of DMC, the reorganization energy initially decreases, reaching a minimum in the mixed-cosolvent regime, and then increases again as the weak cosolvent becomes dominant. This observation clearly demonstrates that the cosolvent synergy is not a simple additive effect, but rather arises from a nonlinear interplay between the distinct solvation characteristics and inter-cosolvent interactions. To verify whether this intrinsic trend is reflected at the electrochemical interface, we further examined the Rct obtained from EIS measurements (Figure S3). Consistent with λ, R ct also decreases in the mixed-cosolvent region and increases again toward both single-cosolvent extremes. Because Rct reflects the extrinsic response under practical measurement conditions—incorporating contributions from the solvation, local ion transport, and interfacial structure—the parallel trend with λ strongly suggests that the dual-cosolvent system indeed provides a more favorable environment for Zn²⁺ charge transfer. Finally, these kinetic advantages are directly manifested in the overpotential (η) measured during Zn‖Zn symmetric cycling. The overpotential follows the same U-shaped dependence as λ and Rct, with the lowest η observed in the mixed-cosolvent formulation. Since η integrates both intrinsic desolvation kinetics and practical deposition behavior, this agreement confirms that the improved kinetics are not limited to fundamental electron transfer, but are fully translated into real performance under operational cycling conditions. Collectively, the excellent correspondence across intrinsic (λ), extrinsic (Rct), and macroscopic (η) descriptors demonstrates that optimal kinetic performance emerges uniquely in the dual-cosolvent regime, and validates the robustness of the multi-level kinetic evaluation framework employed in this study. To further validate the conclusions, the activation energy (Eₐ)—a key descriptor of the desolvation barrier—was calculated using the Arrhenius relationship between charge transfer rate and temperature. 33 As shown in Fig. 2 c, the extracted activation energies for the single-cosolvent systems—50 D and 50 M—were 56.06 kJ mol⁻¹ and 50.31 kJ mol⁻¹, respectively. In contrast, the representative dual-cosolvent electrolyte (25 D 25 M) exhibited a markedly lower Eₐ of 30.33 kJ mol⁻¹, corresponding to an approximately 40% reduction in the kinetic barrier. This substantial decrease confirms that the synergistic solvation environment in the mixed electrolyte greatly facilitates ion desolvation and accelerates charge transfer kinetics at the Zn interface. To gain further insight into the interfacial processes, we analyzed the distribution of relaxation times (DRT), which was derived from the EIS spectra to deconvolute overlapping electrochemical processes in the frequency domain. DRT analysis enables separation of different resistive and capacitive contributions 34 , 35 —such as diffusion, charge transfer, and interphase—without relying on an assumed equivalent circuit (Figure S4). As shown in Fig. 2 d, the dual-cosolvent electrolyte displays significantly reduced relaxation peaks in both the charge transfer (~ 10 − 2 s) and interphase regions (~ 10 − 3 s) compared with single-cosolvent systems, indicating minimized charge transfer resistance and enhanced mobility at interphase. Taken together, these results demonstrate that the dual-cosolvent electrolyte—comprising strongly coordinating DMSO and weakly interacting DMC—achieves a unique balance between thermodynamic stability and fast charge transfer kinetics, a combination rarely accessible in single-cosolvent systems that follow more linear compositional trends. Although electrolytes with the same total cosolvent content display similarly high CE independent of the strong–weak cosolvent ratio, their kinetic behavior shows a pronounced nonlinear optimization. This dual regulation of stability and kinetics ultimately underpins the superior zinc-deposition performance observed in the dual-cosolvent electrolyte. 2.2. Mechanistic Insights into Solvation and Interphase Regulation To elucidate the mechanistic origin of the unique kinetic optimization achieved in the dual-cosolvent electrolyte, a series of spectroscopic characterizations were conducted, such as Nuclear Magnetic Resonance (NMR), Fourier Transform Infrared Spectroscopy (FTIR), and X-ray absorption fine structure (XAFS). These techniques collectively provide complementary insights into the solvation structure and molecular interactions governing Zn²⁺ coordination and interfacial charge transfer. The ¹H NMR spectra were collected to probe the local hydrogen environment in both water molecules and the methyl groups of DMSO and DMC. The raw spectra are shown in Figure S5, and the extracted chemical shifts are summarized in Fig. 3 a. From the bare 1 M Zn(OTf)₂ aqueous electrolyte to the cosolvent-containing systems, a clear downfield shift of the water proton signal was observed, indicating a more restricted water environment caused by cosolvent incorporation. This shift reflects the reduction in water activity and the strengthening of hydrogen bonding within the reorganized solvation structure. When the overall cosolvent content was fixed but the ratio between DMSO and DMC was varied, only a slight additional downfield shift was detected. This minor shift likely arises from the deshielding effect of DMC, which possesses a low dielectric constant. Overall, both the strong cosolvent (DMSO) and weak cosolvent (DMC) suppress water activity by reconstructing the hydrogen-bonding framework and improving thermodynamic stability. For the methyl protons of DMC, an intriguing upfield–downfield trend was observed as the DMC content increased. At low DMC concentrations, DMC molecules are likely restricted by DMSO, leading to electron withdrawal and a downfield shift. At intermediate DMC content—within the dual-cosolvent regime—DMC experiences the freest solvation environment, where the DMSO–DMC interaction reaches an optimal balance, leading to an upfield shift. At higher DMC contents, however, more DMC molecules enter the Zn²⁺ solvation shell, lowering the local electron density and resulting in a downfield shift once again. This evolution demonstrates that a moderate DMC fraction allows for weakly binded DMC molecules in the outer solvation shell, which may act as a dynamic buffer during Zn²⁺ desolvation. Such species can facilitate solvent exchange and lower the reorganization energy (λ), consistent with the kinetic trends observed earlier. The methyl protons of DMSO show a similar overall shift pattern to that of water but with a larger magnitude, reflecting its direct participation in the Zn²⁺ primary solvation shell. The increased DMC content further induces a deshielding effect on DMSO, possibly due to interactions between primary-shell DMSO and outer-shell DMC molecules, which reduce the overall electron density around the DMSO hydrogen atoms. To complement the NMR results, FTIR spectroscopy was employed to examine the evolution of key vibrational modes related to solvent coordination. The O–H stretching vibration of water near 3500 cm⁻¹ exhibits a progressive red shift with increasing DMSO content (Figure S6), signifying the formation of stronger hydrogen-bond networks and restricted water dynamics as DMSO participates in solvation. The C = O stretching mode (ν(C = O)) of DMC (Fig. 3 b), centered around 1750 cm⁻¹, remains largely unchanged when the DMC content is below 25 vol%, suggesting that DMC mainly resides in the outer solvation layer. However, when the DMC fraction exceeds 25 vol%, the peak shifts to lower wavenumbers, indicating that excess DMC begins to coordinate directly with Zn²⁺ despite its weak donor ability. Similarly, the S = O stretching vibration (ν(S = O)) associated with DMSO coordination appears near 1010 cm⁻¹ (Fig. 3 b). The intensity of this peak increases with higher DMSO content, consistent with greater DMSO participation in Zn²⁺ solvation. Notably, when DMSO exceeds ~ 25 vol%, a broad shoulder emerges around 1055 cm⁻¹, which can be attributed to free (uncoordinated) DMSO molecules. This observation suggests that Zn²⁺ solvation becomes saturated with DMSO, and additional DMSO accumulates in the outer shell, potentially impeding ion transport and slowing charge transfer. To further probe Zn²⁺ coordination, XANES and Extended X-ray Absorption Fine Structure (EXAFS) spectra were collected for representative electrolytes (Fig. 3 c and d ). While the overall spectral features are similar, subtle but consistent trends emerge. In XANES, the absorption edge of 50M lies at the lowest energy with the highest edge jump, indicating weaker Zn–O coordination and a more ionic environment. In contrast, 1 M Zn(OTf)₂ shows the highest edge energy and lowest jump, suggesting stronger coordination and greater electron withdrawal by ligands such as water or OTf⁻. The spectra of 50 D and 25 D 25 M lie in between, implying moderate coordination strength dominated by DMSO. In EXAFS, the amplitude of the first coordination peak—related to coordination number (CN)—decreases in the order 1 M Zn(OTf)₂ > 50 M > 50 D ≈ 25 D 25 M, consistent with the replacement of smaller water molecules by bulkier organic species. The reduced CN in the dual-cosolvent system confirms a less crowded, more diverse solvation environment. To corroborate the experimental results, MD simulations were conducted for representative electrolyte compositions. The snapshots highlight well-dispersed Zn²⁺ solvation clusters in dual-cosolvent systems (Fig. 4a), in contrast to the aggregated structure of the water-rich electrolyte (Figure S7). In 25 D 25 M, a typical Zn²⁺ solvation shell consists of one DMSO, one OTf⁻, and four H₂O molecules in the primary solvation shell, while DMC occupies the outer solvation shell, possibly interacting with the inner species (Fig. 4b). The radial distribution functions (RDFs) and CNs confirm that DMSO serves as the dominant coordinating species, followed by OTf⁻ and DMC (Fig. 4c and Figure S7). The calculated interaction energies follow the order Zn–H₂O > Zn–DMSO > Zn–DMC, consistent with their respective solvation strengths and donor abilities (Fig. 4d). This reflects the distinct roles of water, strong (DMSO), and weak (DMC) cosolvents in constructing the solvation network. Notably, the dual-cosolvent electrolyte exhibits the lowest total interaction energy across all Zn–solvent and Zn–anion pairs, indicating more diverse yet weaker solvation environment that facilitates rapid desolvation. Furthermore, a weak attractive interaction (~ 9.5 kcal mol Zn ⁻¹) is identified between DMSO and DMC, supporting the hypothesis that outer-shell DMC interacts with inner-shell DMSO, collectively weakening Zn–solvent coordination and accelerating charge transfer. Figure 4. a) MD snapshot highlighting Zn²⁺ solvation clusters in dual-cosolvent electrolytes. b) Enlarged MD snapshot illustrating the interaction between outer-shell DMC and inner-shell DMSO molecules within a representative Zn²⁺ solvation structure. c) Radial distribution functions (RDFs) and corresponding coordination numbers (CNs) for Zn²⁺ in dual-cosolvent electrolytes. d) Interaction energies between solvent/anion species and Zn²⁺ ions in different electrolyte compositions. e) Schematic illustration of Zn²⁺ solvation structures evolving from a single strong-cosolvent system to a dual-cosolvent and finally to a single weak-cosolvent electrolyte, highlighting the contextual control of the dual-cosolvent design. Despite the relatively weak coordination ability of DMC, the 50 M electrolyte exhibits slower charge transfer kinetics from the previous analysis. This discrepancy suggests that, beyond the solvation structure, the interphase properties may also play a significant role in governing the overall electrochemical behavior. Therefore, we further investigated the Zn anode interphase formed in different electrolytes to elucidate its influence on charge transfer kinetics. Scanning electron microscopy (SEM) was performed on Zn electrodes after symmetric-cell cycling to examine the surface morphology (Figure S8). In the 1 M Zn(OTf)₂ electrolyte, the Zn surface is highly non-uniform, exhibiting extensive dendrites and byproducts from parasitic reactions. The 50 D electrolyte produces slightly more uniform deposits with fewer corrosion residues; however, the growth remains largely two-dimensional and susceptible to dendritic protrusion. In sharp contrast, the dual-cosolvent 25 D 25 M electrolyte yields uniform, planar Zn deposits indicative of homogeneous nucleation and guided growth. In the 50 M electrolyte, dense and thick deposits are observed, suggesting excessive interphase formation that may hinder ion transport. To further probe interphase chemistry, X-ray Photoelectron Spectroscopy (XPS) combined with Ar⁺ sputtering was used to characterize the SEI composition (Figure S9). The F 1s and C 1s spectra reveal both inorganic (e.g., ZnF₂) and organic (C–O, CO₃) constituents. ZnF₂ intensity increases with sputtering depth, confirming an inorganic-rich inner SEI. Organic carbonate species dominate the shallower regions, forming the organic-rich outer layer. While the overall SEI composition is broadly similar across strong-, dual-, and weak-cosolvent electrolytes, the 50 M system shows notably higher and deeper CO₃ signals, indicating substantial organic SEI accumulation. This can be attributed to possible DMC decomposition at elevated DMC concentrations as reported. 36 Time-of-flight secondary ion mass spectrometry (TOF-SIMS) (Figure S10) was further employed to resolve the spatial distribution of key SEI fragments (ZnO⁻, ZnF⁻, CO₃⁻). Consistent with SEM results, both the 1 M Zn(OTf)₂ and 50 D electrolytes generate thin and nonuniform interphases driven by dendritic growth and unstable surface reactions. In contrast, the dual-cosolvent 25 D 25 M electrolyte forms a uniform, moderately thick SEI with a well-defined organic-rich outer layer and inorganic-rich inner layer, providing a favorable balance of stability and ion transport. Meanwhile, the 50 M electrolyte produces a thicker SEI similar to the XPS results. Although a thick SEI may provide enhanced surface protection, an excessively thick—and especially organic-rich—layer hinders ion transport, impedes charge transfer, and ultimately deteriorates interfacial kinetics. Considering the solvation structure and interphase reconstruction, the mechanism underlying the enhanced kinetics of the dual-cosolvent system is summarized in Fig. 4e . In a strong-cosolvent electrolyte such as DMSO, the strong donor molecules directly participate in the Zn²⁺ primary solvation shell and effectively suppress water decomposition. However, their strong coordination with Zn²⁺ increases the desolvation barrier, leading to sluggish charge transfer kinetics and subsequently causes non-uniform interphase formation. When an excess amount of weak cosolvent is introduced, more weak molecules begin to coordinate directly with Zn²⁺. Although their coordination is weaker, decomposition of the weak cosolvent produces a thick, organic-rich SEI that hinders charge transfer kinetics. By mixing strong and weak cosolvents with sharply contrasting donor abilities, the dual-cosolvent electrolyte operates through a distinct mechanism. The strong cosolvent continues to dominate the primary Zn²⁺ solvation shell, while the weak cosolvent remains largely in the outer solvation layer, where it buffers the desolvation process and interacts with inner-shell species such as DMSO to moderate Zn²⁺ coordination strength. This regulated solvation context also guides the formation of a thin, uniform SEI. Together, these coupled solvation–interphase effects markedly accelerate charge transfer kinetics. This behavior exemplifies contextual control—a mechanism that regulates the surrounding context of the system rather than altering its core components. 37 In this case, kinetic enhancement is achieved by tuning the outer-shell solvation environment and the interphase, instead of modifying the intrinsic primary-shell coordination. 2.3. Electrochemical Performance of Dual-Cosolvent Electrolyte on Zn Anode Understanding the unique kinetic enhancement of the dual-cosolvent electrolyte, we next evaluated the practical Zn-anode performance in various electrolyte systems. Plating/stripping tests were first conducted using Zn‖Zn symmetric cells at 1 mA cm⁻² and 1 mAh cm⁻². Among the dual-cosolvent electrolytes located in the mixed-ratio region that exhibited optimal kinetics in Fig. 2 a, three formulations—25 D 25 M, 30 D 20 M, and 20 D 30 M—were compared (Fig. 5 a). Although their electrochemical behaviors are broadly similar, 25 D 25 M consistently shows the lowest overpotential, particularly during long-term cycling. Therefore, 25 D 25 M was selected as the optimized dual-cosolvent formulation for subsequent investigations. Compared with the single-cosolvent electrolytes and the bare 1 M Zn(OTf)₂ aqueous electrolyte—both of which suffer from severe overpotential fluctuations and short cycling lifetimes due to dendrite formation—the 25 D 25 M electrolyte enables highly stable Zn plating/stripping for over 2000 hours with persistently low overpotential (Fig. 5 b). At a higher current density of 5 mA cm⁻² and 1 mAh cm⁻², the dual-cosolvent electrolyte again outperforms all other systems, maintaining over 1000 hours of cycling (Figure S11). Rate-capability tests further validate this enhancement. Across current densities from 0.5 to 5 mA cm⁻², 25 D 25 M exhibits consistently lower overpotential than the other electrolytes (Fig. 5 c). At 10 mA cm⁻², however, the overpotential of 25 D 25 M becomes slightly higher than that of pure 1 M Zn(OTf)₂ and comparable to that of 50 M, reflecting the onset of diffusion-limited behavior, where the low viscosity of the aqueous electrolyte provides a natural advantage. Closer inspection of the voltage profiles (Fig. 5 c, inset) reveals distinct characteristics of strong and weak cosolvents. Strong-cosolvent electrolytes exhibit a pronounced nucleation spike at the onset of plating, consistent with a high desolvation barrier, whereas weak-cosolvent electrolytes show elevated growth overpotential at later stages due to sluggish interfacial kinetics. The dual-cosolvent electrolyte effectively balances these two extremes, showing both a reduced nucleation overpotential and a minimized growth overpotential. Complementary chronoamperometry (CA) measurements further support this conclusion: the dual-cosolvent electrolyte transitions from 2D to 3D diffusion faster, as indicated by the dashed line where the current reaches a steady state (Fig. 5 d). This reflects more favorable Zn nucleation and growth behavior arising from the optimized charge transfer kinetics of the dual-cosolvent formulation. Next, the long-term Zn plating/stripping reversibility in terms of CE was evaluated in Cu‖Zn half cells. The baseline 1 M Zn(OTf)₂ electrolyte exhibits low CE from the onset and rapidly deteriorates due to extensive side reactions. Single-cosolvent electrolytes (50 M and 50 D) show relatively high initial CE but suffer from short cycling lifetimes, primarily attributed to dendrite formation. In contrast, the dual-cosolvent 25 D 25 M electrolyte delivers both high and stable reversibility, achieving 99.5% CE at 1 mA cm⁻² and 1 mAh cm⁻² (Figure S12) and 99.8% CE at 5 mA cm⁻² and 1 mAh cm⁻² (Fig. 5 e) over 1000 cycles. The low polarization observed in the voltage profiles (Fig. 5 e, inset) further corroborates its superior stability. To assess reversibility under harsher conditions, Aurbach’s reservoir method was employed by first plating 5 mA cm⁻² and 5 mAh cm⁻², followed by 200 plating/stripping cycles at 5 mA cm⁻² with a fixed DOD of 60%. Under these demanding conditions, both the bare aqueous electrolyte and the single-cosolvent systems failed within 200 cycles (Figure S13), whereas the dual-cosolvent electrolyte completed the full test with an average CE of 99.7% and consistently low polarization (Fig. 5 f). This exceptional reversibility arises not only from the maintained high thermodynamic stability of the mixed cosolvent environment but also from the improved Zn deposition behavior enabled by its optimized charge transfer kinetics. 2.4. Electrochemical Performance of Full Cells To evaluate the applicability of the dual-cosolvent electrolyte, we further tested its performance in full cells. A NaV₃O₈·1.5H₂O (NaVO) cathode was selected because layered vanadates possess high Zn²⁺ storage capacity, fast Zn²⁺ diffusion channels, and good structural stability, making them one of the most representative cathode systems in aqueous Zn batteries. 38 , 39 Full cells were first cycled at 0.2 A g⁻¹ (~ 0.8 C). As shown in Fig. 6a , the baseline 1 M Zn(OTf)₂ electrolyte exhibits rapid capacity decay due to severe vanadium dissolution and unstable cycling from dendrite growth. The 50 D electrolyte also shows fast capacity fading, consistent with the tendency of strong cosolvents such as DMSO to solubilize vanadium species, especially when excess free DMSO remains outside the primary solvation shell. The 50 M electrolyte, owing to its weak coordinating ability, suppresses vanadium dissolution and initially maintains high capacity; however, its sluggish interfacial kinetics lead to accelerated side reactions and early cell failure. The 25 D 25 M dual-cosolvent electrolyte provides a balanced solvation environment that does not promote vanadium dissolution—preserving the advantage of the weak cosolvent. This behavior was verified by inductively coupled plasma optical emission spectrometry (ICP-OES) on cycled electrolyte (Table S1 ): the vanadium dissolution in 25 D 25 M is less than 1/3 of that in the 50 D and bare aqueous electrolytes. Meanwhile, its optimized charge transfer kinetics ensure smooth Zn plating/stripping. Consequently, cells with 25 D 25 M exhibit stable cycling for over 500 cycles at 0.2 A g⁻¹, delivering an initial capacity of 275 mAh g⁻¹ and retaining 85% of this capacity. Figure 6. Cycling performance of Zn‖NaVO full cells with different electrolytes at a) 0.2 A g⁻¹ and b) 1 A g⁻¹. c) First-cycle voltage profiles of Zn‖NaVO full cells at 1 A g⁻¹ in cosolvent electrolytes. d) Rate performance of Zn‖NaVO full cells with different electrolytes at current densities ranging from 0.1 to 5 A g⁻¹. e) Cycling performance of the Zn‖NaVO full cell using the dual-cosolvent 25 D 25 M electrolyte. Under a higher current density of 1 A g⁻¹ (~ 5 C) (Fig. 6b), the performance differences become even more pronounced. Both 1 M Zn(OTf)₂ and 50 D fail rapidly, while 50 M again suffers from sluggish interfacial kinetics and premature cell death. In contrast, the dual-cosolvent electrolyte delivers > 200 mAh g⁻¹ with 83% capacity retention after 2000 cycles, demonstrating exceptional high-rate reversibility. Inspection of the first-cycle voltage profiles (Fig. 6c) shows a ~ 50% reduction in overpotential for 25 D 25 M compared with the single-cosolvent systems, consistent with the kinetic trends observed in symmetric cells. Such a markedly lower overpotential facilitates more uniform Zn deposition, suppresses side reactions, and improves the overall energy efficiency of the full cell. Rate testing from 0.1 to 5 A g⁻¹ (Fig. 6d) further confirms superior performance across all current densities. While the capacity difference among electrolytes is small at 0.1 A g⁻¹, the advantage of the dual-cosolvent system becomes increasingly prominent at higher rates due to its optimized charge transfer kinetics. Even at 5 A g⁻¹, the dual-cosolvent electrolyte still delivers 93 mAh g⁻¹, where the bare aqueous electrolyte exhibits comparable capacity at this high rate owing to its intrinsically lower viscosity and stronger diffusion contribution. Finally, pouch-cell tests validate the practical viability of the dual-cosolvent design (Fig. 6e). The 25 D 25 M electrolyte achieves ~ 300 mAh absolute capacity and maintains stable cycling over 50 cycles, demonstrating that the improved charge transfer kinetics are effectively translated into real-device operation. 3. Conclusion In this work, we demonstrate that pairing a strong cosolvent (DMSO) with a weak cosolvent (DMC) provides an effective route to engineer aqueous Zn electrolytes beyond the conventional, monotonic composition–property relationships. By systematically varying the strong-to-weak cosolvent ratio, we show that while thermodynamic stability remains similarly high across compositions, the charge transfer kinetics of Zn deposition exhibit a pronounced, nonlinear optimization that emerges exclusively in the dual-cosolvent regime. A mechanistic framework emerges when considering the dual-cosolvent system as a form of contextual control—a mechanism in which the electrolyte environment is regulated not by altering the core Zn²⁺ coordination motifs themselves, but by tuning the context surrounding them. In this system, outer-shell DMC imposes weak yet favorable interactions that modulate the Zn–ligand binding, buffer desolvation at the interface, and promote the reconstruction of a thin and uniform organic–inorganic SEI. Consequently, the optimized dual-cosolvent electrolyte supports highly efficient and stable Zn cycling and enables long-life, high-capacity NaVO full cells, further validated in pouch-cell configurations. More broadly, such strong–weak cosolvent synergy and contextual solvation control offers a versatile and generalizable principle for designing next-generation aqueous Zn electrolytes that not only preserves thermodynamic stability but also accelerates kinetics in aqueous Zn batteries. Declarations Acknowledgements The authors acknowledge the funding support from the ASTAR MTC programmatic project under grant no. 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07:49:03","extension":"xml","order_by":18,"title":"","display":"","copyAsset":false,"role":"acdc-reference","size":137628,"visible":true,"origin":"","legend":"","description":"","filename":"NCOMMS25957930structuring.xml","url":"https://assets-eu.researchsquare.com/files/rs-8234367/v1/616170cd83feaeff8a307d6f.xml"},{"id":98490395,"identity":"88b15f02-2e44-4410-86e0-3ae1b4529ceb","added_by":"auto","created_at":"2025-12-18 07:49:03","extension":"html","order_by":19,"title":"","display":"","copyAsset":false,"role":"acdc-reference","size":149319,"visible":true,"origin":"","legend":"","description":"","filename":"earlyproof.html","url":"https://assets-eu.researchsquare.com/files/rs-8234367/v1/7c385bcbf0fbaff485b509ad.html"},{"id":98490375,"identity":"cf532a2c-ee0c-4c26-81c2-37535eb0994c","added_by":"auto","created_at":"2025-12-18 07:49:02","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":417845,"visible":true,"origin":"","legend":"\u003cp\u003ea) Schematic illustration of the two major challenges associated with the thermodynamic and kinetic aspects of the zinc anode in aqueous ZMBs. b) Plot of donor number (DN) versus dielectric constant (ε) for commonly used organic cosolvents in aqueous zinc electrolytes, with inset illustrating distinct solvation structures containing strong cosolvent and weak cosolvent. c) DFT calculated binding energies between Zn²⁺ ions and individual solvent molecules.\u003csup\u003e15,21\u003c/sup\u003e d) Average Coulombic efficiency (CE) of Cu||Zn half cells with electrolytes containing various amounts of cosolvent, error bars represent standard deviation over three measurements.\u003c/p\u003e","description":"","filename":"floatimage1.png","url":"https://assets-eu.researchsquare.com/files/rs-8234367/v1/b69d73d26d3463c36499c3e9.png"},{"id":98624393,"identity":"0fd701e0-5af6-4908-afc5-ec499c223fd0","added_by":"auto","created_at":"2025-12-19 17:08:23","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":349000,"visible":true,"origin":"","legend":"\u003cp\u003ea) Summary of kinetic performance for electrolytes with different cosolvent compositions, showing (from bottom to top), Marcus reorganization energy (λ), charge transfer resistance (R\u003csub\u003ect\u003c/sub\u003e), and the overpotential (η) in Zn‖Zn symmetric cells. Each data point represents the average value from three independent measurements, with error bars indicating the corresponding standard deviation. b) Marcus–Hush–Chidsey (MHC) model fitting of the linear sweep voltammetry (LSV) curves of Zn‖Zn symmetric cell with 50 D, used to extract reorganization energy. c) Arrhenius-type activation energy fitting for electrolytes with single and dual-cosolvents. d) Distribution of relaxation times (DRT) analysis comparing different cosolvent compositions.\u003c/p\u003e","description":"","filename":"floatimage2.png","url":"https://assets-eu.researchsquare.com/files/rs-8234367/v1/67ec33306ddb272374d20fb8.png"},{"id":98623875,"identity":"f3d76f0e-6acc-41e8-92f8-5e69aa3e87fd","added_by":"auto","created_at":"2025-12-19 17:07:43","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":492721,"visible":true,"origin":"","legend":"\u003cp\u003ea) ¹H NMR chemical shifts and b) FTIR spectra of electrolytes with different cosolvent compositions. c) XANES and d) EXAFS spectra of electrolytes containing single and dual-cosolvents.\u003c/p\u003e","description":"","filename":"floatimage3.png","url":"https://assets-eu.researchsquare.com/files/rs-8234367/v1/7614a828f826fb4ed3d55154.png"},{"id":98624590,"identity":"570b68e7-737c-4ec5-8260-659f52f69d5c","added_by":"auto","created_at":"2025-12-19 17:08:32","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":581400,"visible":true,"origin":"","legend":"\u003cp\u003ea) MD snapshot highlighting Zn²⁺ solvation clusters in dual-cosolvent electrolytes. b) Enlarged MD snapshot illustrating the interaction between outer-shell DMC and inner-shell DMSO molecules within a representative Zn²⁺ solvation structure. c) Radial distribution functions (RDFs) and corresponding coordination numbers (CNs) for Zn²⁺ in dual-cosolvent electrolytes. d) Interaction energies between solvent/anion species and Zn²⁺ ions in different electrolyte compositions. e) Schematic illustration of Zn²⁺ solvation structures evolving from a single strong-cosolvent system to a dual-cosolvent and finally to a single weak-cosolvent electrolyte, highlighting the contextual control of the dual-cosolvent design.\u003c/p\u003e","description":"","filename":"floatimage4.png","url":"https://assets-eu.researchsquare.com/files/rs-8234367/v1/9734f06ae9d3e81659705afb.png"},{"id":98490378,"identity":"471af493-292a-4446-a3df-40054021d2cf","added_by":"auto","created_at":"2025-12-18 07:49:02","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":292759,"visible":true,"origin":"","legend":"\u003cp\u003ea) Overpotential (η) profiles of Zn‖Zn symmetric cells at 1 mA cm⁻² and 1 mAh cm⁻², comparing optimized electrolyte compositions. b) Voltage profiles of Zn‖Zn symmetric cells at 1 mA cm⁻², 1 mAh cm⁻² for different electrolyte. c) Rate performance of Zn‖Zn symmetric cells cycled in different electrolytes. d) Chronoamperometry (CA) profiles of different electrolytes measured at –150 mV. e) CE of Cu‖Zn half cells of different electrolytes at 5 mA cm⁻² and 1 mAh cm⁻², with the inset showing voltage profiles. f) CE of Cu‖Zn half cells of dual-cosolvent electrolytes, measured by Aurbach’s reservoir method with a depth of discharge (DOD) of 60%.\u003c/p\u003e","description":"","filename":"floatimage5.png","url":"https://assets-eu.researchsquare.com/files/rs-8234367/v1/863a6eebd195c71f8c8b5502.png"},{"id":98490382,"identity":"3613c375-d599-426e-babe-64b2816069bb","added_by":"auto","created_at":"2025-12-18 07:49:03","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":395268,"visible":true,"origin":"","legend":"\u003cp\u003eCycling performance of Zn‖NaVO full cells with different electrolytes at a) 0.2 A g⁻¹ and b) 1 A g⁻¹. c) First-cycle voltage profiles of Zn‖NaVO full cells at 1 A g⁻¹ in cosolvent electrolytes. d) Rate performance of Zn‖NaVO full cells with different electrolytes at current densities ranging from 0.1 to 5 A g⁻¹. e) Cycling performance of the Zn‖NaVO full cell using the dual-cosolvent 25 D 25 M electrolyte.\u003c/p\u003e","description":"","filename":"floatimage6.png","url":"https://assets-eu.researchsquare.com/files/rs-8234367/v1/d99a5ef93cb3ea267dd82d65.png"},{"id":105903688,"identity":"4c1e1ff4-7525-4a62-b9dd-a36927019f1c","added_by":"auto","created_at":"2026-04-01 09:48:34","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2765069,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-8234367/v1/21a3d7d1-a5f0-4ee7-bb85-2f42669be129.pdf"},{"id":98624117,"identity":"1af3aee4-8e52-4e89-9c71-ca76754fbe8a","added_by":"auto","created_at":"2025-12-19 17:08:02","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":5447813,"visible":true,"origin":"","legend":"SUPPLEMENTARY INFO","description":"","filename":"SI.docx","url":"https://assets-eu.researchsquare.com/files/rs-8234367/v1/63cdee70806ef70b3e80e9b1.docx"},{"id":98624412,"identity":"0ca7c637-cbc0-43cb-b24d-3b7dcadd69c0","added_by":"auto","created_at":"2025-12-19 17:08:23","extension":"png","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":346590,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eTOC\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"floatimage7.png","url":"https://assets-eu.researchsquare.com/files/rs-8234367/v1/7e10ffd8fe6cba61562b45a5.png"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"Contextual Solvation Control for Nonlinear Kinetic Optimization in Dual-Cosolvent Electrolytes for Aqueous Zinc Metal Batteries","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eThe global transition toward renewable energy generation has highlighted the urgent need for safe, cost-effective, and sustainable energy storage systems.\u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e,\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e Among various candidates, aqueous zinc metal batteries (ZMBs) have attracted significant attention for large-scale grid applications owing to the intrinsic advantages of zinc metal\u0026mdash;low redox potential (\u0026ndash;0.76 V vs. SHE), high theoretical capacity (820 mAh g⁻\u0026sup1;), natural abundance, and water-compatible chemistry. These features make ZMBs a promising alternative to lithium-based technologies, especially for stationary storage where safety and cost are paramount.\u003csup\u003e\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e,\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003cp\u003eHowever, despite these merits, the zinc anode remains the bottleneck that hinders practical deployment. Two fundamental challenges dominate (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ea): (1) Side reactions, particularly the hydrogen evolution reaction (HER), which arise from water\u0026rsquo;s narrow electrochemical stability window and thermodynamic instability on the Zn surface; and (2) Uncontrolled zinc dendrite formation, associated with non-uniform nucleation and anisotropic Zn deposition, which closely relates to the kinetic aspect. These phenomena jointly deteriorate cycling life and threaten operational stability.\u003csup\u003e\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e,\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003cp\u003eTo address these challenges, extensive efforts have been directed toward engineering the anode\u0026ndash;electrolyte interfacial environment, including modifying the anode surface, tuning the separator chemistry, and\u0026mdash;most effectively\u0026mdash;optimizing the electrolyte composition.\u003csup\u003e\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e,\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e\u003c/sup\u003e Electrolyte engineering directly governs zinc-ion solvation structure, interfacial adsorption behavior, and the surrounding water network. In recent years, the cosolvent strategy\u0026mdash;introducing a controlled fraction of organic molecules into aqueous electrolytes\u0026mdash;has emerged as a simple yet versatile approach. By partially replacing water with organic components, such electrolytes combine the safety and ionic conductivity of aqueous media with the expanded electrochemical stability window and tunable solvation environment of organic systems (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ea).\u003csup\u003e\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e\u003c/sup\u003e Most early studies have concentrated on the thermodynamic aspect of cosolvent design, aiming primarily on adjusting the primary solvation shell to suppress HER and widen the Zn plating/stripping stability window.\u003csup\u003e\u003cspan additionalcitationids=\"CR11\" citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e\u003c/sup\u003e This focus is understandable, as establishing a stable thermodynamic environment is the prerequisite for enabling reversible Zn deposition.\u003c/p\u003e \u003cp\u003eHowever, as thermodynamic stabilization becomes better understood, attention has gradually shifted toward the kinetic dimension\u0026mdash;how electrolyte composition influences charge transfer dynamics. Electrochemical kinetics not only dictates the rate capability of ZMBs but also governs Zn nucleation behavior, growth morphology, and ultimately dendrite formation.\u003csup\u003e\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e,\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e\u003c/sup\u003e Several recent studies have begun to explore such effects in single-cosolvent systems. For example, Huang et al. selected ethylene carbonate (EC) with a highest dielectric constant and weakest ion-pair interactions to induce a kinetic compensation effect that enhances Zn\u0026sup2;⁺ transfer.\u003csup\u003e\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u003c/sup\u003e Chen et al. designed a medium-ion-association electrolyte with a moderate contact-ion-pair (CIP) ratio, achieving a balance between charge transfer kinetics and solid-electrolyte interphace (SEI) formation.\u003csup\u003e\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e\u003c/sup\u003e Nevertheless, single-cosolvent systems inherently offer limited tunability and often exhibit trade-offs between thermodynamics and kinetics.\u003c/p\u003e \u003cp\u003eTo overcome these limitations, multi-cosolvent systems have recently been proposed. For instance, dual-cosolvent electrolytes such as dimethyl sulfoxide (DMSO)\u0026ndash;acetonitrile (AN),\u003csup\u003e17\u003c/sup\u003e anthraquinone-1-sulfonate (AQS)- ethylene glycol (EG),\u003csup\u003e18\u003c/sup\u003e and high-entropy electrolytes\u003csup\u003e\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e,\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e\u003c/sup\u003e incorporating dual salts or dual strong cosolvents have been designed to suppress water activity and construct inorganic\u0026ndash;organic gradient SEI layers. Despite this growing interest, the interplay between different cosolvents remains poorly understood. In most reported systems, combining two strong cosolvents yields only a simple additive effect in restricting water decomposition. However, the reality is far more complex\u0026mdash;the interactions among water, salts, and two distinct cosolvents can fundamentally reshape solvation structures and ion-transport dynamics in ways that are not linearly predictable. Therefore, in this work, we present a systematic investigation of dual-cosolvent electrolytes, focusing on their coupled influence on both thermodynamic stability and, more importantly, the charge transfer kinetics of zinc deposition.\u003c/p\u003e \u003cp\u003eAs illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eb, commonly used cosolvents in ZMBs can be broadly categorized as \u003cem\u003estrong\u003c/em\u003e or \u003cem\u003eweak\u003c/em\u003e based on their donor number (DN) and dielectric constant (ε): a) Strong cosolvents possess high DN and ε, allowing them to coordinate directly with Zn\u0026sup2;⁺ in the primary solvation shell, thereby weakening the Zn\u0026ndash;H₂O interaction and suppressing parasitic reactions. b) Weak cosolvents with low DN and ε, contribute indirectly by modifying the outer solvation environment and potentially promoting CIPs through reduced ion dissociation.\u003csup\u003e\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e\u003c/sup\u003e In this study, we reveal how the contrasting characteristics of strong and weak cosolvents interplay to regulate Zn\u0026sup2;⁺ charge transfer kinetics. We elucidate a contextual control mechanism unique to the dual-cosolvent electrolyte\u0026mdash;one that does not fundamentally alter the primary Zn\u0026sup2;⁺ coordination motifs, but instead operates through weak, favorable interactions originating from the outer solvation shell and through the formation of a well-regulated interphase. These coupled, context-dependent effects give rise to a nonlinear kinetic response to the strong\u0026ndash;weak cosolvent ratio, with the dual-cosolvent formulation delivering the maximum enhancement and lowering the kinetic barrier by ~\u0026thinsp;40% relative to single-cosolvent systems. As a result, Zn‖Zn symmetric cells demonstrate stable cycling over 2000 hours with minimal overpotential, and Cu‖Zn half cells achieve an average Coulombic efficiency (CE) of 99.8% over 1000 cycles. Furthermore, a full cell using vanadium-based cathode achieved 83% capacity retention after 2000 cycles at 1 A g⁻\u0026sup1; and markedly improved rate performance. Overall, this study deepens the mechanistic understanding of multi-component effects in aqueous zinc systems and establishes a rational design framework for next-generation electrolytes that simultaneously optimize thermodynamic stability and electrochemical kinetics.\u003c/p\u003e"},{"header":"2. Results","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1. Thermodynamics and Kinetics of Cosolvent Electrolyte\u003c/h2\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFrom Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eb, we selected DMSO and dimethyl carbonate (DMC) as the focus of the current study. DMSO is a strongly coordinating, high-permittivity polar aprotic solvent with excellent solvating ability for a wide range of salts, and is one of the most extensively studied cosolvents for zinc batteries due to its capability to replace water molecules in the Zn\u0026sup2;⁺ solvation shell.\u003csup\u003e\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e,\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e,\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e\u003c/sup\u003e In contrast, DMC, a widely used organic carbonate solvent in lithium-ion battery (LIB) electrolytes, primarily serves as a low-viscosity diluent that enhances ionic conductivity and improves electrolyte fluidity.\u003csup\u003e\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e\u003c/sup\u003e The distinct physicochemical characteristics of these two solvents make them a representative pair of strong and weak cosolvents, enabling systematic investigation into their interactions and potential synergistic effects on electrolyte structure and electrochemical performance. According to density functional theory (DFT) calculations, the binding energies of DMSO, H₂O, and DMC toward Zn\u0026sup2;⁺ are \u0026minus;\u0026thinsp;1.27 eV, \u0026minus;\u0026thinsp;0.60 eV,\u003csup\u003e15\u003c/sup\u003e and \u0026minus;\u0026thinsp;0.40 eV,\u003csup\u003e21\u003c/sup\u003e respectively (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ec). These results clearly confirm the strongly coordinating nature of DMSO and the weak coordination ability of DMC relative to the reference solvent, water.\u003c/p\u003e \u003cp\u003eTo investigate the synergistic effect of dual cosolvents on zinc deposition\u0026mdash;which remains insufficiently understood due to limited prior research\u0026mdash; we examined the effects of varying the ratio between a strong (DMSO) and a weak (DMC) cosolvent on both the thermodynamics and kinetics of Zn\u0026sup2;⁺. We first evaluated the thermodynamic stability by measuring the CE of Cu‖Zn half cells containing electrolytes with different total cosolvent contents and various DMSO/DMC ratios (Figure \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e). The results are summarized in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ed, where DMSO and DMC are abbreviated as D and M, respectively, and the numbers preceding each letter indicate their volume percentage in the electrolyte. All electrolytes were formulated with 1 M Zn(OTf)₂, chosen for its favorable salting-in effect that facilitates dissolution in organic-rich systems. Each data point represents the average CE from three independent measurements, with error bars indicating the corresponding standard deviation. From left to right in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ed, the DMSO content increases gradually from 0 vol% to 50 vol%. It is evident that the CE improves significantly with increasing cosolvent concentration, demonstrating enhanced thermodynamic stability. However, when the total cosolvent content is fixed and the ratio between DMSO and DMC is varied, the CE remains relatively stable. This indicates that both strong and weak cosolvents contribute positively to suppressing parasitic reactions and enhancing thermodynamic stability.\u003c/p\u003e \u003cp\u003eHaving established that both DMSO and DMC enhance thermodynamic stability and that dual-cosolvent formulations maintain similarly high CE across composition, we then turned to how the cosolvent ratio modulates kinetics. In battery systems, overall electrochemical kinetics can be broadly divided into two regimes: diffusion kinetics and charge transfer kinetics. According to previous studies on aqueous ZMB,\u003csup\u003e25\u0026ndash;27\u003c/sup\u003e at low to moderate current densities, the charge transfer process typically dominates as the rate-determining step, whereas at very high current densities, ion diffusion through the electrolyte becomes the primary limitation. Since most practical operating conditions fall within the charge transfer-controlled regime, this study focuses on the charge transfer kinetics at the Zn anode/electrolyte interface.\u003c/p\u003e \u003cp\u003eTo comprehensively evaluate the kinetic behavior, three complementary descriptors were employed (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ea): (1) the intrinsic descriptor, Marcus reorganization energy (λ), which reflects the fundamental electron-transfer barrier; (2) the extrinsic descriptor, charge transfer resistance (Rct); and (3) the macroscopic performance indicator, the overpotential (η) observed during Zn‖Zn symmetric cell cycling.\u003c/p\u003e \u003cp\u003eThe Marcus reorganization energy (λ) serves as a fundamental parameter describing electron-transfer kinetics, originating from Marcus theory.\u003csup\u003e\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e\u003c/sup\u003e It represents the energy required to reorganize the solvation environment of both the redox species and surrounding solvent molecules during electron transfer. A smaller λ indicates a lower degree of structural rearrangement and therefore a faster charge transfer process. Unlike empirical kinetic descriptors such as the exchange current density (i₀) obtained from the Butler\u0026ndash;Volmer (B\u0026ndash;V) model, λ provides a mechanistic and physically meaningful insight into the interfacial electron-transfer barrier, directly linked to solvation structure and molecular reorganization at the interface.\u003csup\u003e\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e\u003c/sup\u003e In this work, λ was quantified using the Marcus\u0026ndash;Hush\u0026ndash;Chidsey (MHC) model\u003csup\u003e\u003cspan additionalcitationids=\"CR30\" citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e\u003c/sup\u003e fitted to linear sweep voltammetry (LSV) data.\u003csup\u003e\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e\u003c/sup\u003e As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eb and Figure S2, the MHC fitting of the LSV curves exhibits high R\u0026sup2; values, validating the robustness of this approach in describing the Zn\u0026sup2;⁺ charge transfer process.\u003c/p\u003e \u003cp\u003eAs summarized in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ea, λ exhibits a clear nonlinear U-shaped trend with varying strong/weak cosolvent ratios. Upon decreasing the fraction of DMSO and increasing that of DMC, the reorganization energy initially decreases, reaching a minimum in the mixed-cosolvent regime, and then increases again as the weak cosolvent becomes dominant. This observation clearly demonstrates that the cosolvent synergy is not a simple additive effect, but rather arises from a nonlinear interplay between the distinct solvation characteristics and inter-cosolvent interactions.\u003c/p\u003e \u003cp\u003eTo verify whether this intrinsic trend is reflected at the electrochemical interface, we further examined the Rct obtained from EIS measurements (Figure S3). Consistent with λ, R\u003csub\u003ect\u003c/sub\u003e also decreases in the mixed-cosolvent region and increases again toward both single-cosolvent extremes. Because Rct reflects the extrinsic response under practical measurement conditions\u0026mdash;incorporating contributions from the solvation, local ion transport, and interfacial structure\u0026mdash;the parallel trend with λ strongly suggests that the dual-cosolvent system indeed provides a more favorable environment for Zn\u0026sup2;⁺ charge transfer.\u003c/p\u003e \u003cp\u003eFinally, these kinetic advantages are directly manifested in the overpotential (η) measured during Zn‖Zn symmetric cycling. The overpotential follows the same U-shaped dependence as λ and Rct, with the lowest η observed in the mixed-cosolvent formulation. Since η integrates both intrinsic desolvation kinetics and practical deposition behavior, this agreement confirms that the improved kinetics are not limited to fundamental electron transfer, but are fully translated into real performance under operational cycling conditions.\u003c/p\u003e \u003cp\u003eCollectively, the excellent correspondence across intrinsic (λ), extrinsic (Rct), and macroscopic (η) descriptors demonstrates that optimal kinetic performance emerges uniquely in the dual-cosolvent regime, and validates the robustness of the multi-level kinetic evaluation framework employed in this study.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eTo further validate the conclusions, the activation energy (Eₐ)\u0026mdash;a key descriptor of the desolvation barrier\u0026mdash;was calculated using the Arrhenius relationship between charge transfer rate and temperature.\u003csup\u003e\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e\u003c/sup\u003e As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ec, the extracted activation energies for the single-cosolvent systems\u0026mdash;50 D and 50 M\u0026mdash;were 56.06 kJ mol⁻\u0026sup1; and 50.31 kJ mol⁻\u0026sup1;, respectively. In contrast, the representative dual-cosolvent electrolyte (25 D 25 M) exhibited a markedly lower Eₐ of 30.33 kJ mol⁻\u0026sup1;, corresponding to an approximately 40% reduction in the kinetic barrier. This substantial decrease confirms that the synergistic solvation environment in the mixed electrolyte greatly facilitates ion desolvation and accelerates charge transfer kinetics at the Zn interface.\u003c/p\u003e \u003cp\u003eTo gain further insight into the interfacial processes, we analyzed the distribution of relaxation times (DRT), which was derived from the EIS spectra to deconvolute overlapping electrochemical processes in the frequency domain. DRT analysis enables separation of different resistive and capacitive contributions\u003csup\u003e\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e,\u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e\u003c/sup\u003e\u0026mdash;such as diffusion, charge transfer, and interphase\u0026mdash;without relying on an assumed equivalent circuit (Figure S4). As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ed, the dual-cosolvent electrolyte displays significantly reduced relaxation peaks in both the charge transfer (~\u0026thinsp;10\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e s) and interphase regions (~\u0026thinsp;10\u003csup\u003e\u0026minus;\u0026thinsp;3\u003c/sup\u003e s) compared with single-cosolvent systems, indicating minimized charge transfer resistance and enhanced mobility at interphase.\u003c/p\u003e \u003cp\u003eTaken together, these results demonstrate that the dual-cosolvent electrolyte\u0026mdash;comprising strongly coordinating DMSO and weakly interacting DMC\u0026mdash;achieves a unique balance between thermodynamic stability and fast charge transfer kinetics, a combination rarely accessible in single-cosolvent systems that follow more linear compositional trends. Although electrolytes with the same total cosolvent content display similarly high CE independent of the strong\u0026ndash;weak cosolvent ratio, their kinetic behavior shows a pronounced nonlinear optimization. This dual regulation of stability and kinetics ultimately underpins the superior zinc-deposition performance observed in the dual-cosolvent electrolyte.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2. Mechanistic Insights into Solvation and Interphase Regulation\u003c/h2\u003e \u003cp\u003eTo elucidate the mechanistic origin of the unique kinetic optimization achieved in the dual-cosolvent electrolyte, a series of spectroscopic characterizations were conducted, such as Nuclear Magnetic Resonance (NMR), Fourier Transform Infrared Spectroscopy (FTIR), and X-ray absorption fine structure (XAFS). These techniques collectively provide complementary insights into the solvation structure and molecular interactions governing Zn\u0026sup2;⁺ coordination and interfacial charge transfer.\u003c/p\u003e \u003cp\u003eThe \u0026sup1;H NMR spectra were collected to probe the local hydrogen environment in both water molecules and the methyl groups of DMSO and DMC. The raw spectra are shown in Figure S5, and the extracted chemical shifts are summarized in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea. From the bare 1 M Zn(OTf)₂ aqueous electrolyte to the cosolvent-containing systems, a clear downfield shift of the water proton signal was observed, indicating a more restricted water environment caused by cosolvent incorporation. This shift reflects the reduction in water activity and the strengthening of hydrogen bonding within the reorganized solvation structure. When the overall cosolvent content was fixed but the ratio between DMSO and DMC was varied, only a slight additional downfield shift was detected. This minor shift likely arises from the deshielding effect of DMC, which possesses a low dielectric constant. Overall, both the strong cosolvent (DMSO) and weak cosolvent (DMC) suppress water activity by reconstructing the hydrogen-bonding framework and improving thermodynamic stability.\u003c/p\u003e \u003cp\u003eFor the methyl protons of DMC, an intriguing upfield\u0026ndash;downfield trend was observed as the DMC content increased. At low DMC concentrations, DMC molecules are likely restricted by DMSO, leading to electron withdrawal and a downfield shift. At intermediate DMC content\u0026mdash;within the dual-cosolvent regime\u0026mdash;DMC experiences the freest solvation environment, where the DMSO\u0026ndash;DMC interaction reaches an optimal balance, leading to an upfield shift. At higher DMC contents, however, more DMC molecules enter the Zn\u0026sup2;⁺ solvation shell, lowering the local electron density and resulting in a downfield shift once again. This evolution demonstrates that a moderate DMC fraction allows for weakly binded DMC molecules in the outer solvation shell, which may act as a dynamic buffer during Zn\u0026sup2;⁺ desolvation. Such species can facilitate solvent exchange and lower the reorganization energy (λ), consistent with the kinetic trends observed earlier. The methyl protons of DMSO show a similar overall shift pattern to that of water but with a larger magnitude, reflecting its direct participation in the Zn\u0026sup2;⁺ primary solvation shell. The increased DMC content further induces a deshielding effect on DMSO, possibly due to interactions between primary-shell DMSO and outer-shell DMC molecules, which reduce the overall electron density around the DMSO hydrogen atoms.\u003c/p\u003e \u003cp\u003eTo complement the NMR results, FTIR spectroscopy was employed to examine the evolution of key vibrational modes related to solvent coordination. The O\u0026ndash;H stretching vibration of water near 3500 cm⁻\u0026sup1; exhibits a progressive red shift with increasing DMSO content (Figure S6), signifying the formation of stronger hydrogen-bond networks and restricted water dynamics as DMSO participates in solvation. The C\u0026thinsp;=\u0026thinsp;O stretching mode (ν(C\u0026thinsp;=\u0026thinsp;O)) of DMC (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eb), centered around 1750 cm⁻\u0026sup1;, remains largely unchanged when the DMC content is below 25 vol%, suggesting that DMC mainly resides in the outer solvation layer. However, when the DMC fraction exceeds 25 vol%, the peak shifts to lower wavenumbers, indicating that excess DMC begins to coordinate directly with Zn\u0026sup2;⁺ despite its weak donor ability. Similarly, the S\u0026thinsp;=\u0026thinsp;O stretching vibration (ν(S\u0026thinsp;=\u0026thinsp;O)) associated with DMSO coordination appears near 1010 cm⁻\u0026sup1; (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eb). The intensity of this peak increases with higher DMSO content, consistent with greater DMSO participation in Zn\u0026sup2;⁺ solvation. Notably, when DMSO exceeds\u0026thinsp;~\u0026thinsp;25 vol%, a broad shoulder emerges around 1055 cm⁻\u0026sup1;, which can be attributed to free (uncoordinated) DMSO molecules. This observation suggests that Zn\u0026sup2;⁺ solvation becomes saturated with DMSO, and additional DMSO accumulates in the outer shell, potentially impeding ion transport and slowing charge transfer.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eTo further probe Zn\u0026sup2;⁺ coordination, XANES and Extended X-ray Absorption Fine Structure (EXAFS) spectra were collected for representative electrolytes (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ec \u003cb\u003eand d\u003c/b\u003e). While the overall spectral features are similar, subtle but consistent trends emerge. In XANES, the absorption edge of 50M lies at the lowest energy with the highest edge jump, indicating weaker Zn\u0026ndash;O coordination and a more ionic environment. In contrast, 1 M Zn(OTf)₂ shows the highest edge energy and lowest jump, suggesting stronger coordination and greater electron withdrawal by ligands such as water or OTf⁻. The spectra of 50 D and 25 D 25 M lie in between, implying moderate coordination strength dominated by DMSO. In EXAFS, the amplitude of the first coordination peak\u0026mdash;related to coordination number (CN)\u0026mdash;decreases in the order 1 M Zn(OTf)₂ \u0026gt; 50 M\u0026thinsp;\u0026gt;\u0026thinsp;50 D\u0026thinsp;\u0026asymp;\u0026thinsp;25 D 25 M, consistent with the replacement of smaller water molecules by bulkier organic species. The reduced CN in the dual-cosolvent system confirms a less crowded, more diverse solvation environment.\u003c/p\u003e \u003cp\u003eTo corroborate the experimental results, MD simulations were conducted for representative electrolyte compositions. The snapshots highlight well-dispersed Zn\u0026sup2;⁺ solvation clusters in dual-cosolvent systems (Fig.\u0026nbsp;4a), in contrast to the aggregated structure of the water-rich electrolyte (Figure S7). In 25 D 25 M, a typical Zn\u0026sup2;⁺ solvation shell consists of one DMSO, one OTf⁻, and four H₂O molecules in the primary solvation shell, while DMC occupies the outer solvation shell, possibly interacting with the inner species (Fig.\u0026nbsp;4b).\u003c/p\u003e \u003cp\u003eThe radial distribution functions (RDFs) and CNs confirm that DMSO serves as the dominant coordinating species, followed by OTf⁻ and DMC (Fig.\u0026nbsp;4c and Figure S7). The calculated interaction energies follow the order Zn\u0026ndash;H₂O\u0026thinsp;\u0026gt;\u0026thinsp;Zn\u0026ndash;DMSO\u0026thinsp;\u0026gt;\u0026thinsp;Zn\u0026ndash;DMC, consistent with their respective solvation strengths and donor abilities (Fig.\u0026nbsp;4d). This reflects the distinct roles of water, strong (DMSO), and weak (DMC) cosolvents in constructing the solvation network. Notably, the dual-cosolvent electrolyte exhibits the lowest total interaction energy across all Zn\u0026ndash;solvent and Zn\u0026ndash;anion pairs, indicating more diverse yet weaker solvation environment that facilitates rapid desolvation. Furthermore, a weak attractive interaction (~\u0026thinsp;9.5 kcal mol\u003csub\u003eZn\u003c/sub\u003e⁻\u0026sup1;) is identified between DMSO and DMC, supporting the hypothesis that outer-shell DMC interacts with inner-shell DMSO, collectively weakening Zn\u0026ndash;solvent coordination and accelerating charge transfer.\u003cb\u003eFigure 4.\u003c/b\u003e a) MD snapshot highlighting Zn\u0026sup2;⁺ solvation clusters in dual-cosolvent electrolytes. b) Enlarged MD snapshot illustrating the interaction between outer-shell DMC and inner-shell DMSO molecules within a representative Zn\u0026sup2;⁺ solvation structure. c) Radial distribution functions (RDFs) and corresponding coordination numbers (CNs) for Zn\u0026sup2;⁺ in dual-cosolvent electrolytes. d) Interaction energies between solvent/anion species and Zn\u0026sup2;⁺ ions in different electrolyte compositions. e) Schematic illustration of Zn\u0026sup2;⁺ solvation structures evolving from a single strong-cosolvent system to a dual-cosolvent and finally to a single weak-cosolvent electrolyte, highlighting the contextual control of the dual-cosolvent design.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eDespite the relatively weak coordination ability of DMC, the 50 M electrolyte exhibits slower charge transfer kinetics from the previous analysis. This discrepancy suggests that, beyond the solvation structure, the interphase properties may also play a significant role in governing the overall electrochemical behavior. Therefore, we further investigated the Zn anode interphase formed in different electrolytes to elucidate its influence on charge transfer kinetics.\u003c/p\u003e \u003cp\u003eScanning electron microscopy (SEM) was performed on Zn electrodes after symmetric-cell cycling to examine the surface morphology (Figure S8). In the 1 M Zn(OTf)₂ electrolyte, the Zn surface is highly non-uniform, exhibiting extensive dendrites and byproducts from parasitic reactions. The 50 D electrolyte produces slightly more uniform deposits with fewer corrosion residues; however, the growth remains largely two-dimensional and susceptible to dendritic protrusion. In sharp contrast, the dual-cosolvent 25 D 25 M electrolyte yields uniform, planar Zn deposits indicative of homogeneous nucleation and guided growth. In the 50 M electrolyte, dense and thick deposits are observed, suggesting excessive interphase formation that may hinder ion transport.\u003c/p\u003e \u003cp\u003eTo further probe interphase chemistry, X-ray Photoelectron Spectroscopy (XPS) combined with Ar⁺ sputtering was used to characterize the SEI composition (Figure S9). The F 1s and C 1s spectra reveal both inorganic (e.g., ZnF₂) and organic (C\u0026ndash;O, CO₃) constituents. ZnF₂ intensity increases with sputtering depth, confirming an inorganic-rich inner SEI. Organic carbonate species dominate the shallower regions, forming the organic-rich outer layer. While the overall SEI composition is broadly similar across strong-, dual-, and weak-cosolvent electrolytes, the 50 M system shows notably higher and deeper CO₃ signals, indicating substantial organic SEI accumulation. This can be attributed to possible DMC decomposition at elevated DMC concentrations as reported.\u003csup\u003e\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003cp\u003eTime-of-flight secondary ion mass spectrometry (TOF-SIMS) (Figure S10) was further employed to resolve the spatial distribution of key SEI fragments (ZnO⁻, ZnF⁻, CO₃⁻). Consistent with SEM results, both the 1 M Zn(OTf)₂ and 50 D electrolytes generate thin and nonuniform interphases driven by dendritic growth and unstable surface reactions. In contrast, the dual-cosolvent 25 D 25 M electrolyte forms a uniform, moderately thick SEI with a well-defined organic-rich outer layer and inorganic-rich inner layer, providing a favorable balance of stability and ion transport. Meanwhile, the 50 M electrolyte produces a thicker SEI similar to the XPS results. Although a thick SEI may provide enhanced surface protection, an excessively thick\u0026mdash;and especially organic-rich\u0026mdash;layer hinders ion transport, impedes charge transfer, and ultimately deteriorates interfacial kinetics.\u003c/p\u003e \u003cp\u003eConsidering the solvation structure and interphase reconstruction, the mechanism underlying the enhanced kinetics of the dual-cosolvent system is summarized in \u003cb\u003eFig.\u0026nbsp;4e\u003c/b\u003e. In a strong-cosolvent electrolyte such as DMSO, the strong donor molecules directly participate in the Zn\u0026sup2;⁺ primary solvation shell and effectively suppress water decomposition. However, their strong coordination with Zn\u0026sup2;⁺ increases the desolvation barrier, leading to sluggish charge transfer kinetics and subsequently causes non-uniform interphase formation. When an excess amount of weak cosolvent is introduced, more weak molecules begin to coordinate directly with Zn\u0026sup2;⁺. Although their coordination is weaker, decomposition of the weak cosolvent produces a thick, organic-rich SEI that hinders charge transfer kinetics.\u003c/p\u003e \u003cp\u003eBy mixing strong and weak cosolvents with sharply contrasting donor abilities, the dual-cosolvent electrolyte operates through a distinct mechanism. The strong cosolvent continues to dominate the primary Zn\u0026sup2;⁺ solvation shell, while the weak cosolvent remains largely in the outer solvation layer, where it buffers the desolvation process and interacts with inner-shell species such as DMSO to moderate Zn\u0026sup2;⁺ coordination strength. This regulated solvation context also guides the formation of a thin, uniform SEI. Together, these coupled solvation\u0026ndash;interphase effects markedly accelerate charge transfer kinetics. This behavior exemplifies contextual control\u0026mdash;a mechanism that regulates the surrounding context of the system rather than altering its core components.\u003csup\u003e\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e\u003c/sup\u003e In this case, kinetic enhancement is achieved by tuning the outer-shell solvation environment and the interphase, instead of modifying the intrinsic primary-shell coordination.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e2.3. Electrochemical Performance of Dual-Cosolvent Electrolyte on Zn Anode\u003c/h2\u003e \u003cp\u003eUnderstanding the unique kinetic enhancement of the dual-cosolvent electrolyte, we next evaluated the practical Zn-anode performance in various electrolyte systems. Plating/stripping tests were first conducted using Zn‖Zn symmetric cells at 1 mA cm⁻\u0026sup2; and 1 mAh cm⁻\u0026sup2;. Among the dual-cosolvent electrolytes located in the mixed-ratio region that exhibited optimal kinetics in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ea, three formulations\u0026mdash;25 D 25 M, 30 D 20 M, and 20 D 30 M\u0026mdash;were compared (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e5\u003c/span\u003ea). Although their electrochemical behaviors are broadly similar, 25 D 25 M consistently shows the lowest overpotential, particularly during long-term cycling. Therefore, 25 D 25 M was selected as the optimized dual-cosolvent formulation for subsequent investigations.\u003c/p\u003e \u003cp\u003eCompared with the single-cosolvent electrolytes and the bare 1 M Zn(OTf)₂ aqueous electrolyte\u0026mdash;both of which suffer from severe overpotential fluctuations and short cycling lifetimes due to dendrite formation\u0026mdash;the 25 D 25 M electrolyte enables highly stable Zn plating/stripping for over 2000 hours with persistently low overpotential (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e5\u003c/span\u003eb). At a higher current density of 5 mA cm⁻\u0026sup2; and 1 mAh cm⁻\u0026sup2;, the dual-cosolvent electrolyte again outperforms all other systems, maintaining over 1000 hours of cycling (Figure S11).\u003c/p\u003e \u003cp\u003eRate-capability tests further validate this enhancement. Across current densities from 0.5 to 5 mA cm⁻\u0026sup2;, 25 D 25 M exhibits consistently lower overpotential than the other electrolytes (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e5\u003c/span\u003ec). At 10 mA cm⁻\u0026sup2;, however, the overpotential of 25 D 25 M becomes slightly higher than that of pure 1 M Zn(OTf)₂ and comparable to that of 50 M, reflecting the onset of diffusion-limited behavior, where the low viscosity of the aqueous electrolyte provides a natural advantage.\u003c/p\u003e \u003cp\u003eCloser inspection of the voltage profiles (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e5\u003c/span\u003ec, inset) reveals distinct characteristics of strong and weak cosolvents. Strong-cosolvent electrolytes exhibit a pronounced nucleation spike at the onset of plating, consistent with a high desolvation barrier, whereas weak-cosolvent electrolytes show elevated growth overpotential at later stages due to sluggish interfacial kinetics. The dual-cosolvent electrolyte effectively balances these two extremes, showing both a reduced nucleation overpotential and a minimized growth overpotential. Complementary chronoamperometry (CA) measurements further support this conclusion: the dual-cosolvent electrolyte transitions from 2D to 3D diffusion faster, as indicated by the dashed line where the current reaches a steady state (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e5\u003c/span\u003ed). This reflects more favorable Zn nucleation and growth behavior arising from the optimized charge transfer kinetics of the dual-cosolvent formulation.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eNext, the long-term Zn plating/stripping reversibility in terms of CE was evaluated in Cu‖Zn half cells. The baseline 1 M Zn(OTf)₂ electrolyte exhibits low CE from the onset and rapidly deteriorates due to extensive side reactions. Single-cosolvent electrolytes (50 M and 50 D) show relatively high initial CE but suffer from short cycling lifetimes, primarily attributed to dendrite formation. In contrast, the dual-cosolvent 25 D 25 M electrolyte delivers both high and stable reversibility, achieving 99.5% CE at 1 mA cm⁻\u0026sup2; and 1 mAh cm⁻\u0026sup2; (Figure S12) and 99.8% CE at 5 mA cm⁻\u0026sup2; and 1 mAh cm⁻\u0026sup2; (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e5\u003c/span\u003ee) over 1000 cycles. The low polarization observed in the voltage profiles (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e5\u003c/span\u003ee, inset) further corroborates its superior stability.\u003c/p\u003e \u003cp\u003eTo assess reversibility under harsher conditions, Aurbach\u0026rsquo;s reservoir method was employed by first plating 5 mA cm⁻\u0026sup2; and 5 mAh cm⁻\u0026sup2;, followed by 200 plating/stripping cycles at 5 mA cm⁻\u0026sup2; with a fixed DOD of 60%. Under these demanding conditions, both the bare aqueous electrolyte and the single-cosolvent systems failed within 200 cycles (Figure S13), whereas the dual-cosolvent electrolyte completed the full test with an average CE of 99.7% and consistently low polarization (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e5\u003c/span\u003ef).\u003c/p\u003e \u003cp\u003eThis exceptional reversibility arises not only from the maintained high thermodynamic stability of the mixed cosolvent environment but also from the improved Zn deposition behavior enabled by its optimized charge transfer kinetics.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003e2.4. Electrochemical Performance of Full Cells\u003c/h2\u003e \u003cp\u003eTo evaluate the applicability of the dual-cosolvent electrolyte, we further tested its performance in full cells. A NaV₃O₈\u0026middot;1.5H₂O (NaVO) cathode was selected because layered vanadates possess high Zn\u0026sup2;⁺ storage capacity, fast Zn\u0026sup2;⁺ diffusion channels, and good structural stability, making them one of the most representative cathode systems in aqueous Zn batteries.\u003csup\u003e\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e,\u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003cp\u003eFull cells were first cycled at 0.2 A g⁻\u0026sup1; (~\u0026thinsp;0.8 C). As shown in \u003cb\u003eFig.\u0026nbsp;6a\u003c/b\u003e, the baseline 1 M Zn(OTf)₂ electrolyte exhibits rapid capacity decay due to severe vanadium dissolution and unstable cycling from dendrite growth. The 50 D electrolyte also shows fast capacity fading, consistent with the tendency of strong cosolvents such as DMSO to solubilize vanadium species, especially when excess free DMSO remains outside the primary solvation shell. The 50 M electrolyte, owing to its weak coordinating ability, suppresses vanadium dissolution and initially maintains high capacity; however, its sluggish interfacial kinetics lead to accelerated side reactions and early cell failure. The 25 D 25 M dual-cosolvent electrolyte provides a balanced solvation environment that does not promote vanadium dissolution\u0026mdash;preserving the advantage of the weak cosolvent. This behavior was verified by inductively coupled plasma optical emission spectrometry (ICP-OES) on cycled electrolyte (Table \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e): the vanadium dissolution in 25 D 25 M is less than 1/3 of that in the 50 D and bare aqueous electrolytes. Meanwhile, its optimized charge transfer kinetics ensure smooth Zn plating/stripping. Consequently, cells with 25 D 25 M exhibit stable cycling for over 500 cycles at 0.2 A g⁻\u0026sup1;, delivering an initial capacity of 275 mAh g⁻\u0026sup1; and retaining 85% of this capacity.\u003cb\u003eFigure 6.\u003c/b\u003e Cycling performance of Zn‖NaVO full cells with different electrolytes at a) 0.2 A g⁻\u0026sup1; and b) 1 A g⁻\u0026sup1;. c) First-cycle voltage profiles of Zn‖NaVO full cells at 1 A g⁻\u0026sup1; in cosolvent electrolytes. d) Rate performance of Zn‖NaVO full cells with different electrolytes at current densities ranging from 0.1 to 5 A g⁻\u0026sup1;. e) Cycling performance of the Zn‖NaVO full cell using the dual-cosolvent 25 D 25 M electrolyte.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eUnder a higher current density of 1 A g⁻\u0026sup1; (~\u0026thinsp;5 C) (Fig.\u0026nbsp;6b), the performance differences become even more pronounced. Both 1 M Zn(OTf)₂ and 50 D fail rapidly, while 50 M again suffers from sluggish interfacial kinetics and premature cell death. In contrast, the dual-cosolvent electrolyte delivers\u0026thinsp;\u0026gt;\u0026thinsp;200 mAh g⁻\u0026sup1; with 83% capacity retention after 2000 cycles, demonstrating exceptional high-rate reversibility. Inspection of the first-cycle voltage profiles (Fig.\u0026nbsp;6c) shows a\u0026thinsp;~\u0026thinsp;50% reduction in overpotential for 25 D 25 M compared with the single-cosolvent systems, consistent with the kinetic trends observed in symmetric cells. Such a markedly lower overpotential facilitates more uniform Zn deposition, suppresses side reactions, and improves the overall energy efficiency of the full cell.\u003c/p\u003e \u003cp\u003eRate testing from 0.1 to 5 A g⁻\u0026sup1; (Fig.\u0026nbsp;6d) further confirms superior performance across all current densities. While the capacity difference among electrolytes is small at 0.1 A g⁻\u0026sup1;, the advantage of the dual-cosolvent system becomes increasingly prominent at higher rates due to its optimized charge transfer kinetics. Even at 5 A g⁻\u0026sup1;, the dual-cosolvent electrolyte still delivers 93 mAh g⁻\u0026sup1;, where the bare aqueous electrolyte exhibits comparable capacity at this high rate owing to its intrinsically lower viscosity and stronger diffusion contribution. Finally, pouch-cell tests validate the practical viability of the dual-cosolvent design (Fig.\u0026nbsp;6e). The 25 D 25 M electrolyte achieves\u0026thinsp;~\u0026thinsp;300 mAh absolute capacity and maintains stable cycling over 50 cycles, demonstrating that the improved charge transfer kinetics are effectively translated into real-device operation.\u003c/p\u003e \u003c/div\u003e"},{"header":"3. Conclusion","content":"\u003cp\u003eIn this work, we demonstrate that pairing a strong cosolvent (DMSO) with a weak cosolvent (DMC) provides an effective route to engineer aqueous Zn electrolytes beyond the conventional, monotonic composition\u0026ndash;property relationships. By systematically varying the strong-to-weak cosolvent ratio, we show that while thermodynamic stability remains similarly high across compositions, the charge transfer kinetics of Zn deposition exhibit a pronounced, nonlinear optimization that emerges exclusively in the dual-cosolvent regime.\u003c/p\u003e \u003cp\u003eA mechanistic framework emerges when considering the dual-cosolvent system as a form of contextual control\u0026mdash;a mechanism in which the electrolyte environment is regulated not by altering the core Zn\u0026sup2;⁺ coordination motifs themselves, but by tuning the context surrounding them. In this system, outer-shell DMC imposes weak yet favorable interactions that modulate the Zn\u0026ndash;ligand binding, buffer desolvation at the interface, and promote the reconstruction of a thin and uniform organic\u0026ndash;inorganic SEI.\u003c/p\u003e \u003cp\u003eConsequently, the optimized dual-cosolvent electrolyte supports highly efficient and stable Zn cycling and enables long-life, high-capacity NaVO full cells, further validated in pouch-cell configurations. More broadly, such strong\u0026ndash;weak cosolvent synergy and contextual solvation control offers a versatile and generalizable principle for designing next-generation aqueous Zn electrolytes that not only preserves thermodynamic stability but also accelerates kinetics in aqueous Zn batteries.\u003c/p\u003e"},{"header":"Declarations","content":"\u003ch2\u003eAcknowledgements\u003c/h2\u003e \u003cp\u003eThe authors acknowledge the funding support from the ASTAR MTC programmatic project under grant no. 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Angew Chem Int Ed 58(46):16358\u0026ndash;16367. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1002/anie.201903941\u003c/span\u003e\u003cspan address=\"10.1002/anie.201903941\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \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":"[email protected]","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":"aqueous zinc batteries, zinc metal anode, cosolvent engineering, kinetics optimization, dual-cosolvent electrolyte","lastPublishedDoi":"10.21203/rs.3.rs-8234367/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-8234367/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eCosolvent engineering for aqueous Zn metal batteries has traditionally emphasized thermodynamic stabilization, whereas the kinetic dimension of Zn\u0026sup2;⁺ charge transfer\u0026mdash;particularly in multi-cosolvent systems\u0026mdash;remains far less understood. Here, we uncover a contextual solvation control mechanism in a dual-cosolvent electrolyte pairing a strong cosolvent (dimethyl sulfoxide, DMSO) with a weak cosolvent (dimethyl carbonate, DMC). Mechanistically, the outer-shell weak cosolvent imposes mild yet favorable interactions that modulate Zn\u0026ndash;ligand binding and facilitate solvent exchange, while simultaneously promoting the formation of a thin, well-regulated SEI that accelerates interfacial charge transfer kinetics. This contextual regulation preserves thermodynamic stability while, more importantly, enabling a nonlinear kinetic optimization that emerges exclusively at specific strong-to-weak cosolvent ratios. Using a multi-descriptor kinetic framework, we show that the dual-cosolvent regime lowers the reorganization energy and charge-transfer barrier by ~\u0026thinsp;40% relative to single-cosolvent systems. As a result, the electrolyte supports stable Zn plating/stripping for over 2000 hours with suppressed dendrite formation. Full cells paired with vanadium-based cathodes further exhibit enhanced capacity retention, long-term cycling stability, and markedly improved rate performance.\u003c/p\u003e","manuscriptTitle":"Contextual Solvation Control for Nonlinear Kinetic Optimization in Dual-Cosolvent Electrolytes for Aqueous Zinc Metal Batteries","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-12-18 07:48:58","doi":"10.21203/rs.3.rs-8234367/v1","editorialEvents":[],"status":"published","journal":{"display":true,"email":"[email protected]","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":"bbc515d1-7646-439b-a360-2022d8424730","owner":[],"postedDate":"December 18th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"under-review","subjectAreas":[{"id":59788472,"name":"Physical sciences/Energy science and technology/Energy storage/Batteries"},{"id":59788473,"name":"Physical sciences/Materials science/Materials for energy and catalysis/Batteries"},{"id":59788474,"name":"Physical sciences/Materials science/Materials for energy and catalysis/Electrochemistry"}],"tags":[],"updatedAt":"2026-04-10T05:05:30+00:00","versionOfRecord":[],"versionCreatedAt":"2025-12-18 07:48:58","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-8234367","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-8234367","identity":"rs-8234367","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}