High-performance Ag_0.333V₂O₅ nanowires as cathode materials for aqueous zinc-ion batteries

Abstract

Aqueous zinc-ion batteries (AZIBs) have attracted wide attention for large-scale energy storage owing to their low cost and intrinsic safety. However, the development of high-performance cathode materials remains a challenge. Herein, a nanowire-like Ag_0.333V₂O₅ was synthesized via a facile one-step hydrothermal method and systematically investigated as a cathode material for AZIBs. Benefiting from its one-dimensional nanowire architecture and Ag⁺ pre-intercalation, the as-prepared Ag_0.333V₂O₅ nanowires exhibit favorable electrochemical performance. They deliver a high specific capacity of 378 mAh g⁻¹ at a current density of 0.1 A g⁻¹, and an excellent cycling stability, retaining 92% of the initial capacity after 500 cycles at 2 A g⁻¹. These results demonstrate that the Ag_0.333V₂O₅ nanowires are promising cathode candidates for aqueous zinc-ion energy storage systems.

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Introduction

Rechargeable aqueous zinc-ion batteries (AZIBs) have recently emerged as a compelling alternative to lithium-ion batteries owing to their intrinsic safety, high theoretical capacity, low redox potential, and cost-effectiveness.^1,2 The use of aqueous electrolytes further improves operational safety and environmental sustainability, rendering AZIBs highly promising for large-scale energy storage applications. However, the practical implementation of AZIBs is still severely constrained by the lack of high-performance cathode materials that enable rapid and reversible Zn²⁺ (de)intercalation without significant structural collapse during prolonged cycling.^3,4

To date, various cathode materials have been explored for AZIBs, including manganese-based oxides, vanadium-based compounds, Prussian blue analogues, and organic frameworks.^5–10 Among these candidates, vanadium-based materials have attracted particular attention due to their multiple accessible oxidation states (V³⁺/V⁴⁺/V⁵⁺), diverse crystallographic structures, and high theoretical capacities, which enable multielectron redox reactions and flexible Zn²⁺ storage.¹¹ Nevertheless, most vanadium-based cathodes suffer from poor electronic conductivity, sluggish Zn²⁺ diffusion kinetics, and structural instability during cycling.^12,13 These issues arise primarily from strong electrostatic interactions between divalent Zn²⁺ ions and the host lattice, which induce lattice distortion, promote vanadium dissolution, and lead to capacity fading. To address these challenges, several modification strategies have been proposed: foreign-ion pre-intercalation to enlarge the interlayer spacing, nanostructure engineering to shorten the ion diffusion pathway, composites with conductive materials to increase electrical conductivity, and electrostatic screening to reduce the intercalation energy.^14,15 In particular, numerous studies have verified that pre-intercalation of metal ions (e.g., Na⁺, K⁺, Ca²⁺, and Al³⁺) is effective in enlarging the interlayer spacing, stabilizing the host framework, and facilitating Zn²⁺ transport.^16,17 For instance, CaVO nanoribbons synthesized by Niiu et al. delivered an initial discharge capacity of 300 mAh g⁻¹ at 0.1 A g⁻¹,¹⁸ while Co²⁺-substituted VO₂ reported by Zhang et al. exhibited suppressed vanadium dissolution and enhanced electronic conductivity and zinc ion mobility.¹⁹ He Lin et al. reported Al_0.34V₅O₁₂·2.4H₂O nanoribbons via the hydrothermal introduction of Al³⁺, which demonstrate excellent electrochemical performance of 407.8 mAh g⁻¹ at 0.2 A g⁻¹.²⁰ In parallel, Wang et al. design a hierarchical nanoflowers structure of Zn-vanadium oxide material, which provides abundant contact between electrode and electrolyte that facilitates fast electrochemical kinetics. As a result, the battery delivered a high specific capacity of 426 mAh g⁻¹ at 0.1 A g⁻¹.²¹

Silver vanadium oxides (SVOs) are essential functional inorganic materials that have found applications in various electrochemical storage devices. Ag_0.33V₂O₅ has been reported as a promising cathode material with high capacity and stability for lithium-ion, aqueous zinc-ion, and manganese batteries.^22–24 The pre-intercalation Ag⁺ ion was reported to improve the ion diffusion rate, modulate the layered structure, and enhance structural stability.²⁵ However, a clear understanding of the electrochemical behavior of Ag_0.33V₂O₅ within aqueous multivalent-ion systems remains elusive, particularly regarding the reversibility of the Ag species and structural evolution during cycling. Lan et al. attributed the outstanding performance of Ag_0.33V₂O₅ to enhanced conductivity of pre-intercalated Ag⁺ and a vacancy-exchange mechanism of Zn²⁺/Ag⁺.²⁶ Guo et al. proposed that Ag_0.33V₂O₅ exhibits a high reversible combination displacement/intercalation mechanism: Ag⁰ nanoparticles are generated upon Zn²⁺ intercalation and are highly reversibly oxidized to Ag⁺ upon Zn²⁺ de-intercalation.²⁷ Wang et al. reported an in situ phase transformation to Zn₃(OH)₂V₂O₇·2H₂O, which will gradually replace the pristine material during cycling, accompanied by Zn²⁺/Ag⁺ exchange and metallic Ag formation.²⁸ These differing observations indicate that the Zn²⁺ storage mechanism in Ag_0.33V₂O₅ remains under debate. Moreover, the strong electrostatic interaction between divalent Zn²⁺ and the host lattice in vanadium oxides generally leads to sluggish diffusion kinetics, underscoring the need for structural regulation strategies,²⁹ and enhance structural stability. Thereby, making it challenging to achieve both fast kinetics and stable cycling performance in a single system.

In this work, we report a facile one-step hydrothermal synthesis of Ag_0.333V₂O₅ nanowires as a high-performance cathode material for aqueous zinc-ion batteries. The incorporation of Ag⁺ pre-intercalation and a one-dimensional nanowire architecture are excepted to enhanced electronic conductivity, shorten Zn²⁺ diffusion pathways, and mitigate structural strain during cycling. As a result, the Ag_0.333V₂O₅ nanowires deliver a high specific capacity of 378 mAh g⁻¹ at 0.1 A g⁻¹, and excellent cycling stability with 90% capacity retention after 500 cycles at 2 A g⁻¹.

Experimental

Synthesis of Ag_0.333V₂O₅ nanowires

The Ag_0.333V₂O₅ nanowires were synthesized via a one-step hydrothermal method with tartaric acid employed as a mild reducing agent. Typically, 0.468 g of NH₄VO₃ and 0.3 g of tartaric acid were dissolved in 100 mL of distilled water while stirring at 50 °C. Next, 3.5 mL of 3 M of HNO₃ solution was added dropwise to adjust the pH of the suspension until a clear, blue solution formed. After that, 0.1698 g of AgNO₃ was added with further stirring. The pH value of the final solution is approximately 2.5. The resulting homogeneous solution was transferred into a 150 mL Teflon-lined autoclave and heated at 180 °C for 24 h in a dry oven. After naturally cooling to room temperature, the precipitate was collected by filtration, rinsed with ethanol and water, and dried in a vacuum oven at 80 °C for 12 h.

Characterization

The prepared samples were characterized using an X-ray diffractometer (XRD, Rigaku Ultima IV) with Cu Kα radiation. The elemental composition of the sample was analyzed by X-ray photoelectron spectroscopy (XPS; Thermo Scientific ESCALAB 250Xi). The morphology, structure, and size were obtained by scanning electron microscopy (SEM, Hitachi SU8010) and scanning transmission electron microscopy (STEM, FEI Talos F200S G2). The surface area was measured by nitrogen adsorption using the Brunauer–Emmett–Teller (BET) method on a Quantachrome Nova analyzer at 77 K.

Electrochemical measurements

The electrochemical performance of the as-prepared Ag_0.333V₂O₅ as ZIBs cathode material was tested in an assembled 2032-type coin half-cell. The working electrode was fabricated by coating a slurry composed of 70 wt% active material, 20 wt% Super P conducting additive, and 10 wt% polyvinylidene fluoride (PVDF) binder in N-methyl-2-pyrrolidine (NMP) onto a titanium foil. The zinc foil was used as the counter electrode, and a Whatman GF/A glass fiber filter served as the separator. 3 M Zn(CF₃SO₃)₂ aqueous solution was employed as the electrolyte. The mass loading of active material ranges 2.2 to 2.8 mg per electrode, corresponding to an areal mass loading of approximately 1.95–2.48 mg cm⁻² on a circular titanium foil.

Galvanostatic charge and discharge tests and Galvanostatic Intermittent Titration Technique (GITT) experiments on the testing system (LAND CT2001A, Wuhan, China) over a voltage window of 0.2–1.6 V vs. Zn/Zn²⁺ at various current densities. Cyclic voltammetry (CV) between 0.2 and 1.6 V at different scan rates was performed on the electrochemical workstation (CHI660E, Shanghai Chenhua Co., Ltd, China).

Results and discussion

Various Ag/V precursor ratios was systematically explored, and the target phase was successfully obtained at an Ag/V ratio of 1 : 4 (Fig. S1). The crystal structure of the as-prepared sample was investigated by X-ray diffraction (XRD). As shown in Fig. 1a, all diffraction peaks can be well indexed to the standard diffraction peaks of monoclinic Ag_0.333V₂O₅ (PDF No. 81-1740),³⁰ confirming the formation of the target phase. The main peaks at 12.32, 18.72, 23.26, 26.42, 27.92, 29.32, 30.68, and 32.92° are assigned to the (200), (002), (4̄01), (1̄11), (111), (401), (4̄03) and (3̄12) crystal planes, respectively. No impurity phase was detected, indicating the high purity of the synthesized Ag_0.333V₂O₅.

Fig. 1 Structural characterizations of the samples. (a) XRD pattern. (b) XPS survey spectrum. (c) Ag 3d. (d) V 2p. (e) O 1s.

X-ray photoelectron spectroscopy (XPS) was performed to elucidate the chemical states of the constituent elements (Fig. 1b–e). The Ag 3d XPS spectrum exhibits two characteristic peaks located at binding energies of 367.5 eV and 373.5 eV, assignable to Ag 3d_5/2 and Ag 3d_3/2 of monovalent Ag⁺ species rather than metallic Ag⁰. In the V 2p spectrum, peaks located at 524.2 eV and 516.9 eV correspond to the V 2p_1/2 and V 2p_3/2, respectively. The V 2p spectrum can be deconvoluted into contirbutions from V⁵⁺ and V⁴⁺ peaks within both regions, suggesting the coexistence of mixed valence states. The presence of V⁴⁺ is attributed to a reduction of V₂O₅ during synthesis, while the introduction of Ag⁺ serves as a charge-compensating species to maintain overall electroneutrality.²⁸ The O 1s spectrum in Fig. 1e can be fitted into two components located at 529.6 eV and 530.6 eV, corresponding to M=O and O-defects.²⁰ Oxygen vacancies were reported to provide additional active sites, enhance the conductivity, and promote the intercalation pseudocapacitive behavior.³¹ Collectively, XRD and XPS results confirm the successful synthesis of phase-pure Ag_0.333V₂O₅ with the intercalation of Ag⁺ into the vanadium structure.

Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) are utilized to observe the morphologies of the as-prepared samples. Fig. 2a, b and c (SEM) and (TEM) images reveal an intertwined and uniform nanowire morphology. The individual nanowire exhibits an average diameter of approximately 50 nm, forming a well-connected network. Form the elemental mapping analysis (Fig. S2), the atomic ratio of Ag to V is determined to be approximately 1 : 6, which is consistent with the stoichiometry of Ag_0.333V₂O₅, further supporting the successful formation of the target phase. High-resolution TEM (HRTEM) image (Fig. 2d) exhibits clear lattice fringes with an interplanar spacing of 3.38 Å, which can be indexed to the (1̄11) crystal plane of monoclinic Ag_0.333V₂O₅, indicative of high crystallinity of the nanowires. Furthermore, high-angle annular dark-field scanning TEM (HAADF-STEM) elemental mapping images (Fig. 2e–h) demonstrate a homogeneous distribution of Ag, V, and O throughout the nanowires, confirming the compositional uniformity of the material. The specific surface area was evaluated by nitrogen adsorption using the Brunauer–Emmett–Teller (BET) method. The surface area of the sample is 32.5 m² g⁻¹, which is expected to provide sufficient electrode–electrolyte interface.

Fig. 2 (a and b) SEM images. (c and d) HRTEM images. (e–h) HAADF-STEM element mapping images.

Comprehensive structure characterization confirms the successful formation of phase-pure Ag_0.333V₂O₅. The interconnected one-dimensional nanowire is expected to shorten the Zn²⁺ diffusion pathway. Thus, the synergistic effects of Ag⁺ intercalation, oxygen defects and nanowires architecture are anticipated to enhance electronic conductivity, accelerated Zn²⁺ transport kinetics, and deliver a superior electrochemical performance, which will be further investigated in the following study.

The electrochemical properties of Ag_0.333V₂O₅ were assessed in CR2032-type coin cells using metallic zinc as the anode and 3 M aqueous Zn(CF₃SO₃)₂ solution as the electrolyte. Fig. 3a presents the cyclic voltammetry (CV) pattern within a voltage window of 0.2–1.6 V (versus Zn/Zn²⁺) at a scan rate of 0.1 mV s⁻¹. A dominant reduction peak emerges at 0.58 V, accompanied by additional features at 0.39 V, 0.51 V, and 0.73 V, which can be attributed to stepwise Zn²⁺ insertion into the host framework.²⁶ In the reverse scan, two oxidation peaks emerge at 1.1 V and 0.75 V, corresponding to the reversible de-intercalation of Zn²⁺ ions from the host structure. It is notable that distinct differences between the first cycle and the subsequent cycles, which can be commonly observed in vanadium-based oxide cathodes.³¹ In our system, the presence of oxygen defects, as revealed by XPS analysis, suggests that vacancy filling and defect stabilization process. It is reported that oxygen vacancies may undergo migration or refilling during the initial cycles, which can lead to partially irreversible processes.³² To gain deeper insight into the redox processes, differential capacity (dQ/dV) curves were derived from the initial galvanostatic charge–discharge (GCD) profile (Fig. 3d). Two apparent peaks are observed at approximately 0.43 and 0.62 V, indicating two discharge platforms during the ion intercalation process and further confirming the stepwise storage behavior of zinc ions.

Fig. 3 (a) CV curves at 0.1 mV s⁻¹. (b) GCD curves of SVO at 0.1 A g⁻¹, (c) GCD curves of SVO at different current densities, (d) differential capacity (dQ/dV) curves of the initial discharge curve, (e) rate cycle performance, (f) long cycle performance of SVO at 2 A g⁻¹.

Galvanostatic charge–discharge tests demonstrate the excellent electrochemical performance of the Ag_0.333V₂O₅ cathode. As shown in Fig. 3b, the electrode delivers a highest specific capacity of 378 mAh g⁻¹ at a current density of 0.1 A g⁻¹ and presents a good reversibility. The rate performance of the electrode at various current densityies is shown in Fig. 3c, e and S4. It demonstrates favourable rate capability with discharge capacities of 345, 332, 304, 271, and 230 mAh g⁻¹ at current densities of 0.1, 0.2, 0.5, 1, and 2 A g⁻¹, respectively. The electrode also exhibits stable cycling performance, retaining discharge capacities of 237 and 226 mAh g⁻¹ after 100 cycles at 0.5 and 1 A g⁻¹, respectively. A comparison of zinc-ion storage performance with previously reported cathode materials is summarized in Table 1.^33–41 The electrochemical performance in this work is highly competitive compared among silver vanadium oxide cathodes.

Table 1 The electrochemical performance of silver vanadium oxides electrodes reported for AZIBs

Materials	Morphology	Discharge capacity (mAh g^−1/A g^−1)	Cycling stability (mAh g^−1/A g^−1/cycles)	Voltage window (V)	Ref.
V2O5	Nanofibers	265/0.02	116/0.588/500	0.5–1.5	33
V2O5	Nanowires	317/0.2	97.4/2000/1	0.2–1.6	34
V2O5	Hollow spheres	280/0.2	108/6200/10	0.2–1.6	35
Ag0.33V2O5	Nanorods	∼150/0.5	70/3/700	0.2–1.6	26
Ag0.33V2O5	Nanorods	∼210/0.5	144/2/500	0.1–1.6	25
Ag0.33V2O5	Nanobelts	∼300/0.1	150/2/3000	0.4–1.4	28
Ag2V4O11	Micro-rods	∼221/0.5	117/3/1000	0.3–1.3	36
Ag1.2V3O8	Nanorods	∼150/1	—	0.4–1.4	27
Ag0.4V2O5	Nanobelts	237/0.5	216/5/1000	0.4–1.4	37
K0.23V2O5	—	284/0.1	103/2/500	0.1–1.7	38
ZnxV2O5·nH2O	Flower-like	324/0.1	200/5/2000	0–1.5	39
Na0.13(NH4)0.5V2O5·5H2O	Nanorod	267/1	245/5/2000	0.4–1.6	40
Cu0.4V2O5	Nanoflake	358.3/0.1	128/2/1000	0.2–1.4	41
Ag0.333V2O5	Nanowires	∼332/0.2	180/2/500	0.2–1.6	This work

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Notably, a gradual capacity increment is observed in the initial stages of cycling. The increment trend can be attributed to an activation process associated with improved the electrolyte penetration and enhanced utilization of active sites within the entangled nanowire structure.⁴² For long-term cycling assessment, the Ag_0.333V₂O₅ cathode was tested at a current density of 2 A g⁻¹. As shown in Fig. 3f, it displays a high discharge specific capacity of 250 mAh g⁻¹ and retains 92% of its initial capacity after 500 cycles, demonstrating exceptional long-term cycling stability.

To further investigate the electrochemical kinetics of Ag_0.333V₂O₅, CV measurements were conducted at scan rates ranging from 0.1 to 0.5 mV s⁻¹. As shown in Fig. 4a, with increasing scan rate, the anodic peaks shift slightly toward higher potentials and the cathodic peaks move toward lower potentials, while the overall CV curves remain well preserved, suggesting low polarization and good reversibility. The kinetic behavior was analyzed based on the relationship between the peak current (i) and scan rate (v), expressed as:

i = av^b

where a and b are regulable values.⁴³ The b-value can be obtained from the slope of the linear fitting of log(i) versus log(v). In general, a b-value close to 1 indicates a surface-controlled process, whereas a b-value close to 0.5 corresponds to diffusion-limited behavior. As illustrated in Fig. 4b, the b-value of peaks 1–4 are calculated to be 0.804, 0.973, 0.893, and 0.843, respectively. All fitted values exhibit correlation coefficients (R² > 0.99), indicating excellent linearity and reliability of the fitting. The intermediate b-values reveal that Zn²⁺ storage in Ag_0.333V₂O₅ follows a mixed mechanism, with a dominant contribution from surface-controlled processes.

Fig. 4 (a) CV curves of the SVO at scan rates from 0.1 to 0.5 mV s⁻¹. (b) Fitting plots of log(i) versus log(v) at specific peak currents. (c) CV curve and calculated capacitive contribution at 0.3 mV s⁻¹. (d) Capacitive contribution ratios at various scan rates. (e–g) Discharge and charge GITT curves at 0.1 A g⁻¹ and corresponding Zn²⁺ diffusion coefficient.

Additionally, the relative contributions of capacitive and diffusion-controlled processer were quantitatively analysed via Dunn's method based on the equation:

i = k₁v + k₂v^1/2

where k₁v represents the capacitive-controlled contribution and k₂v^1/2 corresponds to the diffusion-controlled contribution.^44,45 The capacitive contribution was obtained by integrating the k₁v component over the entire potential window.

As shown in Fig. 4c, the orange region represents the capacitive contribution, accounting for 80.9% at a scan rate of 0.3 mV s⁻¹. The capacitive contribution with scan rate increased from 0.1–0.5 mV s⁻¹ is summarized in Fig. 4d. The capacitive contributions are 78.9%, 79.0%, 80.9%, 85.0% and 89.9%, demonstrating in Fig. S3, confirming the predominance of fast surface-controlled kinetics, in good agreement with the b-value analysis discussed above. The high capacitive contributions can be partly attributed to the presence of oxygen defects which are considered to provide additional active sites and facilitate fast surface-controlled Zn²⁺ storage.³¹ Moreover, the interconnected nanowire network further promotes efficient charge transfer and ion transport, collectively contributing to enhanced pseudocapacitive behaviour.

The Zn²⁺ diffusion kinetics were further examined by galvanostatic intermittent titration technique (GITT) measurements. The Zn²⁺ diffusion coefficient (D_Zn²⁺) was calculated based on the standard the equation:

where τ is the pulse duration, M_B and V_M denote the molar mass and the molar mass of the material, m_B is the mass of the active material, and S is the electrode/electrolyte contact area.²⁰ ΔE_s and ΔE_t can be obtained from the GITT curves (Fig. 4f).

Typically, the coin cell was subjected to a constant current density of 0.1 A g⁻¹ for 600 s, followed by a shelved process for 1 h. The calculated zinc ion diffusion coefficients of SVO in Fig. 4g fall in the range of 10⁻¹¹ to 10⁻¹⁰ cm² s⁻¹ throughout the charge–discharge process. These values are higher than those reported for pristine V₂O₅ cathodes (10⁻¹² to 10⁻¹¹ cm² s⁻¹),⁴⁶ suggesting improved Zn²⁺ transport kinetics in the present system. The enhancement is reasonably associated with Ag⁺ pre-intercalation and one-dimensional nanowire architecture, which together may facilitate ion diffusion and charge transfer during repeated cycling.

Ex situ XRD measurements were carried out to monitor the structural evolution of Ag_0.333V₂O₅ during electrochemical cycling (Fig. 5a–c). Throughout the charge–discharge process, the characteristic diffraction peaks are well preserved, while a slight shift of the diffraction peak from 29.32° to 29.1° and peak broadening are observed, implying reversible interlayer expansion associated with ion insertion.⁴⁷ Such peak evolution is characteristic of lattice breathing in layered structures, where guest-ion insertion/extraction induces reversible lattice distortion without losing crystallinity.⁴⁸ Importantly, no new diffraction peaks emerge during cycling, excluding the formation of irreversible phases. Although the diffraction intensities decrease at the fully discharged and charged states, the characteristic reflections remain identifiable and recover at intermediate states. This behavior suggests that preserved structural integrity rather than framework collapse. Overall, the ex situ XRD results demonstrate that the Ag_0.333V₂O₅ framework maintains it structural integrity during repeated Zn²⁺ insertion and extraction. The pre-intercalated Ag⁺ ions is likely beneficial for stabilizing the V–O framework and enabling reversible lattice breathing, which is consistent with the excellent cycling electrochemical performance.

Fig. 5 (a) The second discharge–charge curves at 0.1 A g⁻¹. (b and c) Ex situ XRD patterns of the Ag_0.333V₂O₅ cathode at different states during the discharge–charge process.

Conclusions

In summary, one-dimensional Ag_0.333V₂O₅ nanowires were successfully synthesized via a facile one-step hydrothermal method and demonstrated effective Zn²⁺ storage behavior in aqueous zinc-ion batteries. The enhanced electrochemical performance can be attributed to a synergistic effect of structure and electronic factors: (i) pre-intercalation Ag⁺ help maintain the structure and improve electronic conductivity; (ii) the one-dimensional nanowire architecture shortens Zn²⁺ diffusion pathways and enhances electrolyte accessibility. (iii) the presence of oxygen defects, as revealed by XPS analysis, provides abundant active sites and promotes surface-controlled charge storage. The synergistic effects enable fast Zn²⁺ storage reaction kinetics, improved Zn²⁺ ion diffusion, and robust structural stability. As a result, the Ag_0.333V₂O₅ cathode delivers a high specific capacity, excellent rate capability and long-term cycling stability. This work highlights the effectiveness of Ag⁺ pillars in stabilizing vanadium-based frameworks and provides a generalizable design strategy for developing high-performance cathode materials for vanadium-based cathodes in aqueous zinc-ion batteries.

Author contributions

Yimeng Xu: conceptualization, data curation, formal analysis, visualization and writing—original draft and review. Junyu Qu: material preparation and characterization. Xunna Ke and Hongrui Jiang: electrochemical performance inverstigation. Ali Bahadui: supervision and writing—review and editing.

Conflicts of interest

There are no conflicts to declare.

Data availability

The data supporting the finding of this study are available within the article and its accompanying supplementary information (SI). Supplementary information: additional XRD, Dunn analysis, SEM-EDS, and electrochemical data. See DOI: https://doi.org/10.1039/d6ra01786j.

Acknowledgements

We thank Public Technology Service Center of the Wenzhou Institute. UCAS for instrument availability that supported this work. We are grateful for the financial support from the Zhejiang Provincial Education Department General Program (No. Y202147286), Wenzhou Science and Technology Program (No. GC20250037), and the International Collaborative Research Program (No. ICRP2023008).

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