V2O5 Nanospikes as a Cathode for Aqueous Zn-Based Batteries

V2O5 Nanospikes as a Cathode for Aqueous Zn-Based 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 Research Article V 2 O 5 Nanospikes as a Cathode for Aqueous Zn-Based Batteries Wu Jiandong, Jiao Yujie, Wei Hao, Lu Hui, Yang Shaolin, Ma Jinfu, and 2 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6892258/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract Vanadium oxides have been explored extensively as electroactive materials for aqueous Zn-ion batteries (ZIBs). In this study, V 2 O 5 nanospikes (VO-NS) were synthesized via thermal decomposition of dodecylamine from vanadium oxide nanotubes (VO-NTs), and its performance as cathode material for ZIBs was systematically investigated. The resulting VO-NS cathode exhibited substantially enhanced electronic conductivity and Zn 2+ transport kinetics compared to VO-NTs. Electrochemical tests revealed that VO-NS delivered a specific capacity of 355.2 mAh·g –1 at a current density of 0.5 A·g –1 and maintained 261.7 mAh·g –1 even at 5.0 A·g –1 , demonstrating an outstanding rate capability. Notably, the VO-NS cathode maintained 91.86% of its initial capacity (194.2 mAh·g –1 ) after 2000 cycle at 10.0 A·g –1 , highlighting the exceptional cyclic stability. Furthermore, it achieved a high value of energy density of 294.9 Wh·kg –1 at 0.5 A·g –1 and an exceptional power density of 6714 W·kg –1 at 10 A·g –1 , surpassing many previously reported vanadium-based ZIBs cathodes. These findings underscore the potential of VO-NS as an exceptional cathodic material for ZIBs. V2O5 Nanospikes Cathode Electrochemical performance Aqueous zinc-ion batteries Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 1. Introduction Grid-scale energy storage demands systems that are sustainable, safe, and cost-effective. Aqueous Zn-ion batteries (ZIBs) are considered future candidates for this application due to their low price, abundance, eco-friendliness, and high safety[ 1 , 2 ]. In general, manganese oxides[ 3 – 6 ], vanadium oxides[ 7 – 9 ], Prussian blue[ 10 ], and their derivatives[ 11 , 12 ] have been considered as cathode materials for ZIBs. Among these, layered vanadium oxides materials are particularly interesting owing to their high specific capacity, multiple oxidation numbers, open crystal structure, and abundant active sites[ 13 , 14 ]. Vanadium pentoxide (V 2 O 5 ) is the most extensively employed material owing to its structural stability, high abundance, and excellent theoretical capacity up to 589 mAh·g –1 [ 15 ]. However, the low ionic and electronic conductivity values of pure-phase V 2 O 5 hinder its practical applications[ 16 ]. Vanadium oxides containing mixed-valence vanadium species exhibit improved electrochemical properties when utilised as a cathode in ZIBs. For instance, V 4+ -V 2 O 5 ⸱3H 2 O pre-intercalated with PAN[ 17 ] demonstrates outstanding capacity retention of 133 mAh·g –1 following 1000 runs at 10 A·g –1 . Similarly, V 2 O 5 nanospheres comprising multiple vanadium oxidation numbers[ 18 ] deliver 140 mAh·g –1 over 1000 runs under the same conditions. Yang et al.[ 19 ] explored the electrochemical behaviour of vanadium oxide nanotubes (VO-NTs) incorporating mixed-valence vanadium ions. These VO-NTs exhibited a capacity of 314.6 mAh·g –1 at 0.1 A·g –1 . Also, they maintained 80.5% of their initial capacity after 950 cycles at a higher current density of 2.4 A·g –1 , suggesting remarkable cyclic efficiency. However, the capacity was limited to 87.8 mAh·g –1 at 9.6 A·g –1 . This was substantially lower in comparison to that observed for other V-based cathodes. This reduced performance could be associated with the high content of dodecylamine in VO-NTs, which has minimal contribution to charge storage. It is worth mentioning that Zhou et al. [ 20 ] removed dodecylamine from VO-NTs through thermal treatment, resulting in the formation of vanadium pentoxide nanospikes (VO-NS), which exhibited superior lithium-ion storage performance compared to VO-NTs. Building on this discovery, the Zn 2+ storage behavior of the VO-NS cathode was systematically investigated. The electrode delivered a notable specific capacity of 355.2 mAh·g –1 at 0.5 A·g –1 . Remarkably, it maintained 194.2 mAh·g –1 at 10 A·g –1 , with 178.4 mAh·g –1 retained after 2000 cycles—corresponding to a capacity retention of 91.86%, demonstrating exceptional long-term cycling stability and rate capability. 2. Experimental 2.1 Preparation of VO-NTs and VO-NS The synthesis process for vanadium pentoxide nanospikes (VO-NS) is presented in Fig. 1 . 0.76 g of V 2 O 5 was dispersed within 60 ml of deionised (DI) water with constant stirring for 10 min to achieve a uniform dispersion. Then, 0.72 g of dodecylamine was mixed with 5 mL of anhydrous C 2 H 5 OH and added to the vanadium oxide dispersion. After this, the dispersion was stirred continuously for 48 h. Thereafter, it was poured into a Teflon-lined stainless-steel autoclave and heated at 180 ℃ for 72 h. The solid product was thoroughly cleaned with DI water and ethyl alcohol upon cooling back to ambient temperature, after which it was dried at a temperature of 80°C overnight to yield VO-NTs. The VO-NTs were finally annealed under ambient conditions at 400°C to produce the desired VO-NS material. 2.2 Material analysis The crystal phases of the synthesised materials were investigated via XRD (SmartlabSE) equipped with a Cu Kα radiation source. Surface morphology and structural features were examined via FESEM (Zeiss, Sigma 500) and TEM (FEI, Talos F200X). The composition of the samples was determined via TGA. FTIR (Thermo Fisher Scientific Nicolet, iS20) was used to probe chemical structures and functional groups. Surface elemental composition and oxidation states were analysed using an ESCALAB 250XI XPS system from Thermo Fisher, utilising a monochromatic Al Kα source (1486.6 eV) under a pressure below 5×10 − 10 bar. 2.3 Electrochemical measurements A suspension of VO-NS/VO-NTs, carbon black, and PVDF, with a mass ratio of 7:2:1, was prepared in NMP as the solvent. This mixture was homogeneously coated onto Ti foil and dried in a vacuum oven at 120°C for a duration of 12 h to obtain the cathode. The electrochemical cell arrangement comprised glass fibre paper as the separator, Zn-metal foil as the anode, and 2.5 M zinc sulphate solution as the electrolyte. All electrochemical evaluations were carried out at ambient temperature. All electrochemical parameters were expressed relative to the mass of VO-NS/VO-NTs. galvanostatic charge-discharge (GCD) measurements and galvanostatic intermittent titration technique (GITT) tests were conducted utilising a Wuhan LAND CT2001A battery testing system. A CHI 660E electrochemical workstation was utilised to carry out the electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) analyses. 3. Results and discussion The thermal stability of VO-NTs was evaluated via TGA. As illustrated in Fig. 2 (a), an initial mass loss of 2.8% was recorded within the 30–110°C range as a result of the loss of physically adsorbed water. A more pronounced weight loss of 39.2% occurred between 110 and 400°C, associated with the release of structural water and the thermal degradation of the intercalated dodecylamine. The phase information of VO-NTs and VO-NS were examined using XRD, as depicted in Fig. 2 (b). The XRD profile of VO-NTs aligned well with the previous reports[ 20 , 21 ], confirming their successful synthesis. The diffraction peaks of VO-NTs located at 7.44°, 10.81°, 14.48°, 21.90°, 29.01°, 32.59°and 46.75° can be indexed to (002), (003), (100), (011), (200), (210) and (310) plane, respectively. According to the Bragg’s law, the interplanar distance of the (002) plane is calculated to be 1.18 nm, which further leads to the interplanar distance of the (001) plane being 2.36 nm. Following thermal treatment at 400°C, the characteristic peaks of VO-NTs disappeared, and new signals consistent with orthorhombic V 2 O 5 emerged, indicating a significant phase transformation. The diffraction peaks at 15.26°, 20.16°, 21.56°, 26.02°, 30.92°, 32.26°and 34.20° can be indexed to (200), (001), (101), (100), (301), (011) and (310) plane, respectively. To further investigate chemical bonding and functional groups of the as-synthesized VO-NTs and VO-NS, FTIR analysis was performed. As shown in Fig. 2 (c), the absorption band around 3460 and 1640 cm –1 were linked to the H-O stretching and H-O-H bending vibrational modes in H 2 O, while the peaks at 585 and 635 cm –1 was linked to the symmetric stretching vibrations of triply coordinated oxygen bonds [ 20 ]. Besides, peaks around 827 and 1020 cm –1 were assigned to the stretching vibrations of V = O and V-O-V, respectively[ 22 ]. It is worth noting that absorption bands at 741, 1460, 2850, and 2930 cm –1 , ascribed to the C-H vibrations of dodecylamine[ 23 ], were almost entirely eliminated after heat treatment, confirming the effective removal of the organic template. The oxidation states of V in VO-NTs and VO-NS were determined via XPS analysis (Fig. 2 (d)). The two fitted peaks at 516.4 and 517.6 eV were corresponded to the V 4+ 2p3/2 and V 5+ 2p3/2, respectively[ 24 , 25 ]. Quantitative analysis revealed that V 4+ comprised 67% of the vanadium in VO-NTs, which decreased to 19.4% in VO-NS, likely due to the partial oxidation of V 4+ to V 5+ during thermal treatment in an air atmosphere. As depicted by the SEM image in Fig. 3 (a), the synthesized VO-NTs display a well-defined tubular morphology, confirming the successful formation of nanotube structures. The TEM images provided in Figs. 3 (b) also revealed that the VO-NTs possess an open-ended, multi-walled tubular configuration. High-resolution TEM(HRTEM) analysis (Fig. 3 (c)) identified lattice planes having an interplanar spacing of 2.25 nm, which corresponded to the (001) crystallographic plane of VO-NTs, in agreement with the XRD data. Following annealing at 400 ℃, the VO-NTs undergo a significant morphological transformation from tubular form into nanospike architectures (Fig. 3 (d)) composed of smaller nanocrystalline grains (Fig. 3 (e)). HRTEM imaging (Fig. 3 (f)) reveals lattice planes with an interplanar spacing of 0.58 nm, which can be indexed to the (200) plane of V 2 O 5 . This transformation not only results in more channels for the transport of zinc ions but also enhances electrolyte penetration, thereby contributing to improved electrochemical performance. In summary, these results demonstrate that thermal annealing not only removes the organic dodecylamine but also induces a favourable reorganisation of the material. The rate performance of VO-NTs and VO-NS cathodes evaluated at 0.5, 0.7, 1, 3, and 5 A·g − 1 is presented in Fig. 4 (a). The VO-NS electrode delivered discharge capacities of 355.2, 337.7, 317.1, 284.4, and 261.7 mAh·g –1 at these rates, consistently outperforming VO-NTs. When the current density was returned to 0.5 A·g –1 , the VO-NS delivered a capacity of 327 mAh·g –1 , indicating excellent reversibility with a retention rate of 92.06%. Long-term cyclic stability at 10.0 A·g –1 is illustrated in Fig. 4 (b). After 2000 cycles, the VO-NS cathode retained a 178.4 mAh·g –1 , about 91.86% of its initial capacity (194.2 mAh·g –1 ), significantly higher than that of VO-NTs under identical conditions. Additionally, Fig. 4 (c) illustrates the cycling behaviour at 1 A·g –1 , where both materials exhibit an inactivation phase, characterised by a gradual increase in discharge capacity within the first 70 cycles. After 500 cycles, a slight decline is observed in both cases; however, The VO-NS retains 68.5% of its initial capacity, whereas VO-NTs maintain only 60.4%, further highlighting the improved cycling stability achieved by removing dodecylamine. Nyquist plots and equivalent circuits are presented in Fig. 4 (d). The VO-NS cathode exhibits a significantly smaller semicircle within the high-frequency region, implying a lower charge transfer resistance ( R ct ) compared to VO-NTs. Improved ion transport is further supported by the Warburg coefficient ( σ ω ​), derived from the Z' versus ω –1/2 plots in Fig. 4 (e). A significantly lower σ ω value of 3.66 was displayed by VO-NS compared to 18.57 for VO-NTs, suggesting faster Zn 2+ diffusion. Therefore, the removal of dodecylamine from VO-NTs not only reduces the charge transfer resistance but also enhances the Zn²⁺ diffusion coefficient, thereby improving its rate performance. The obtained GCD plots of VO-NS at 0.5 A·g –1 (Fig. 4 (f)) revealed two distinct discharge plateaus around 0.9 and 0.6 V, indicative of multistep Zn 2+ insertion. This is corroborated by the CV curves in Fig. 4 (g), which display two well-defined redox signals at 1.03/0.88 V and 0.76/0.61 V. The CV profiles also highlight excellent electrochemical reversibility. Finally, Fig. 4 (h) provides a comparison of the power density and energy density of VO-NS with other V-based aqueous ZIBs cathodes. VO-NS achieved an energy density of 294.9 Wh·kg –1 at 0.5 A·g − 1 and a power density of 6714 W·kg –1 at 10 A·g –1 , outperforming materials such as V 2 O 5 @PANI[ 26 ], H 2 V 3 O 8 [ 9 ], O V -ZVO[ 27 ], VO-NTs[ 21 ], and KVO[ 28 ]. These results collectively underscore the superior electronic conductivity and ion transport capability of the VO-NS cathode, which can be ascribed to the structural optimisation attained by the removal of dodecylamine. To develop a better understanding of the electrochemical kinetics of the VO-NS cathode, CV tests were carried out at various scan rates ( v ) ranging from 0.2 to 1.0 mV·s –1 , as presented in Fig. 5 (a). The oxidation signals moved to more positive potentials owing to the enhanced polarization effect at higher rates, while the reduction signals moved to more negative values. The peak current ( i ) and v are related to each other according to the equation given below[ 29 ]: $$\:i=a{v}^{b}$$ where a and b are tuneable parameters. The b -value offers insights into the charge storage mechanism: a value of 0.5 is typical of a diffusion-limited mechanism, whereas a value approaching 1.0 indicates surface-capacitive behaviour. From the linear plots of log( i ) against log( v ) (see Fig. 5 (b)), the b -values for the anodic and cathodic peaks were 0.84, 0.61, 0.65, and 0.77, respectively. This indicated that the redox process in VO-NS involved a combination of diffusion-limited and capacitive mechanisms. To quantify the contribution of capacitive behaviour, the current response was further separated using the relation[ 30 ]: $$\:i={\text{k}}_{1}\text{v}+{\text{k}}_{2}{\text{v}}^{1/2}$$ where the k 1 v corresponds to pseudocapacitive effects and k 2 v 1/2 to diffusion-limited contributions. The pseudocapacitive effects accounted for 88.23% of the overall current at v = 0.8 mV·s –1 (Fig. 5 (c)), clearly dominating the charge storage process. The pseudocapacitive contribution progressively rose as the scan rate was enhanced from 0.2 to 1.0 mV·s –1 , reaching up to 91% at 1.0 mV·s –1 (Fig. 5 (d)). These results confirmed that the electrochemical redox process of VO-NS at high current densities is predominantly governed by a pseudocapacitance-controlled mechanism, thereby promoting enhanced charge-transfer kinetics. In addition, GITT analysis was performed to assess Zn 2+ diffusion within the VO-NS electrode (Fig. 5 (e)). The diffusion coefficients (D Zn ) range from 10 –11 to 10 –9 cm 2 ·s –1 (Fig. 5 (f)), comparable to D Zn reported for other vanadium oxide-based cathodes[ 31 , 32 ]. The relatively high diffusivity is likely associated with the reduced grain size of the VO-NS structure, which provides shorter and more accessible ion transport pathways. 4. Conclusion In summary, VO-NS were successfully synthesised through thermal removal of dodecylamine from VO-NTs. When employed as a cathode in ZIBs, VO-NS exhibited improved electronic conductivity and Zn 2+ transport compared to VO-NTs. These advantages resulted in outstanding electrochemical performance, including a rate capability of 261.7 mAh·g –1 at 5.0 A·g –1 and a remarkable specific discharge capacity of 355.2 mAh·g –1 at 0.5 A·g –1 . Besides, the VO-NS cathode demonstrated excellent cycling durability, retaining 178.4 mAh·g –1 after 2000 cycles at 10.0 A·g –1 , which was 91.86% of its initial capacity. In addition, VO-NS also delivered high values of energy density and power density (294.9 Wh·kg –1 at 0.5 A·g –1 and 6714 W·kg –1 at 10 A·g –1 , respectively), exceeding the performance of most previously reported Vanadium oxides-based cathodes used for aqueous ZIBs. These findings underscore the significant potential of VO-NS as a high-efficiency cathode material for advanced aqueous ZIBs. Declarations Author Contribution Jiandong Wu : Investigation, Supervision, Writing –original draft, Formal analysis,Writing – review & editing. Jiao Yujie&Wei Hao: Validation, Data curation, Visualization. Lu Hui&Yang Shaolin: Data curation, Visualization. Ma Jinfu&Sheng Zhilin: Data curation. Hou Chunping: Formal analysis. Acknowledgement The authors greatly appreciate the financial support from Natural Science Foundation of Ningxia, China (No.2023AAC03290) and National Natural Science Foundation of China (No. 22169001, No. U22A20146). Data Availability The authors declare that the data supporting the findings of this study are available within the paper. If other formats of the original data files are required, they can be obtained from the corresponding author upon reasonable request. References Z.M. Zhao, J.W. Zhao, Z.L. Hu, J.D. Li, J.J. Li, Y.J. Zhang, C. Wang, G.L. Cui, Long-life and deeply rechargeable aqueous Zn anodes enabled by a multifunctional brightener-inspired interphase, Energy & Environmental Science 12 (2019) (6).1938–1949. W.A. Xu, X.N. Zhang, J.H. Li, X.B. Chen, L. Lan, J. Zhang, F.C.C. Ling, Q. Ru, Scaffolded hierarchical CeVO4/V2CTx-MXene cathode for flexible quasi-solid-state aqueous zinc-ion battery, Ionics 30 (2024) (3).1457–1467. Q. Zhao, X. Huang, M. Zhou, Z. Ju, X. Sun, Y. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-6892258","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":473216789,"identity":"cfb1e326-094b-48ea-bdda-ed0b2da037fe","order_by":0,"name":"Wu Jiandong","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA40lEQVRIiWNgGAWjYHCChAMMDMxAmvkAhH+AeC1sCURrAQGQFh4D4rQY3Eh4eODnDms5c/413x7dbGOQ47uRwPi5AL+WhIO9Z9KNLWe83W6c28ZgLHkjgVl6Bh4tZkAtB3jbDiduuHF2mzRQC5CRwMbMQ0DLwb9gLWeegbTUE6XlMNiW8z1sIC0JBoS02J95kHBYti3d2OAGm5l0zjkJw5lnHjZL49Mi2Z6T/PFtm7WcwfnDz6Rzymzk+Y4nH/yMTwswOhIgtASYlgBixga8GhgY2A9AaP4DBBSOglEwCkbBiAUArVBUkpW804sAAAAASUVORK5CYII=","orcid":"","institution":"North Minzu University","correspondingAuthor":true,"prefix":"","firstName":"Wu","middleName":"","lastName":"Jiandong","suffix":""},{"id":473216797,"identity":"96ead309-3f53-4bce-a89c-fd88575ef043","order_by":1,"name":"Jiao Yujie","email":"","orcid":"","institution":"North Minzu University","correspondingAuthor":false,"prefix":"","firstName":"Jiao","middleName":"","lastName":"Yujie","suffix":""},{"id":473216800,"identity":"3eee692c-c776-4465-9452-ff22f07cedc5","order_by":2,"name":"Wei Hao","email":"","orcid":"","institution":"North Minzu University","correspondingAuthor":false,"prefix":"","firstName":"Wei","middleName":"","lastName":"Hao","suffix":""},{"id":473216803,"identity":"7a92ad1f-966e-4304-a3d4-d1ca5907590b","order_by":3,"name":"Lu Hui","email":"","orcid":"","institution":"North Minzu University","correspondingAuthor":false,"prefix":"","firstName":"Lu","middleName":"","lastName":"Hui","suffix":""},{"id":473216805,"identity":"e3d5e281-8019-4e8a-819b-49c4d3c44db1","order_by":4,"name":"Yang Shaolin","email":"","orcid":"","institution":"North Minzu University","correspondingAuthor":false,"prefix":"","firstName":"Yang","middleName":"","lastName":"Shaolin","suffix":""},{"id":473216806,"identity":"b547bb18-103e-49df-a2f7-1e529df15841","order_by":5,"name":"Ma Jinfu","email":"","orcid":"","institution":"North Minzu University","correspondingAuthor":false,"prefix":"","firstName":"Ma","middleName":"","lastName":"Jinfu","suffix":""},{"id":473216807,"identity":"f17eb4d3-cacc-4e37-9391-4783b1b1909b","order_by":6,"name":"Sheng Zhilin","email":"","orcid":"","institution":"North Minzu University","correspondingAuthor":false,"prefix":"","firstName":"Sheng","middleName":"","lastName":"Zhilin","suffix":""},{"id":473216808,"identity":"1740b18c-6c65-4a14-832a-68a495a78554","order_by":7,"name":"Hou Chunping","email":"","orcid":"","institution":"North Minzu University","correspondingAuthor":false,"prefix":"","firstName":"Hou","middleName":"","lastName":"Chunping","suffix":""}],"badges":[],"createdAt":"2025-06-14 06:38:22","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-6892258/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-6892258/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":85074139,"identity":"6488001d-c6bf-422b-b98b-c634fbb23f2f","added_by":"auto","created_at":"2025-06-20 16:10:39","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":68864,"visible":true,"origin":"","legend":"\u003cp\u003eSchematic diagram illustrating the synthesis process for VO-NS\u003c/p\u003e","description":"","filename":"image1.png","url":"https://assets-eu.researchsquare.com/files/rs-6892258/v1/c1f134d859ce742c28238019.png"},{"id":85074386,"identity":"a64d4401-6a66-446f-81e1-7a048d6fa32e","added_by":"auto","created_at":"2025-06-20 16:18:39","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":85822,"visible":true,"origin":"","legend":"\u003cp\u003e(a) TG diagram of VO-NTs; (b) XRD spectra, (c) FTIR and (d) V 2p spectra of VO-NTs and VO-\u003c/p\u003e","description":"","filename":"image2.png","url":"https://assets-eu.researchsquare.com/files/rs-6892258/v1/bfb4f695b47e6ce703e5ee4d.png"},{"id":85074388,"identity":"d7a2583c-ed54-4de2-9933-b0d42465f312","added_by":"auto","created_at":"2025-06-20 16:18:39","extension":"jpeg","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":417126,"visible":true,"origin":"","legend":"\u003cp\u003e(a, d) SEM micrographs; (b, e) TEM images, (c, f) HRTEM images of VO-NTs and VO-NS\u003c/p\u003e","description":"","filename":"image3.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-6892258/v1/9a6a2a16cb4d4b7a2b41f11b.jpeg"},{"id":85074387,"identity":"2f0a80f3-a7a3-4d83-b1bd-2764d9a6ee2f","added_by":"auto","created_at":"2025-06-20 16:18:39","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":312279,"visible":true,"origin":"","legend":"\u003cp\u003e(a) Rate performance, (b-c) Cycling stability and (d) Nyquist plots of VO-NTs and VO-NS; (e) Z' vs. ω\u003csup\u003e–1/2 \u003c/sup\u003eplots; (f) GCD profiles and (g) CV curves of VO-NS after activation; (h) Ragone plot\u003c/p\u003e","description":"","filename":"image4.png","url":"https://assets-eu.researchsquare.com/files/rs-6892258/v1/5daa4372fc8cc26b9d00680e.png"},{"id":85074144,"identity":"601f832a-1827-43a0-acab-eb18ed52b26e","added_by":"auto","created_at":"2025-06-20 16:10:39","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":340715,"visible":true,"origin":"","legend":"\u003cp\u003e(a) The CV curves for VO-NS; (b) log(\u003cem\u003ei\u003c/em\u003e) vs log(\u003cem\u003ev\u003c/em\u003e) graphs; (c) The relative contribution of capacitive mechanism at 0.8 mV·s\u003csup\u003e–1\u003c/sup\u003e; (d) separation of diffusion-limited and pseudocapacitance-controlled mechanisms at various \u003cem\u003ev \u003c/em\u003evalues; (e) GITT profile of the VO-NS electrode; (f) calculated Zn²⁺ diffusion coefficients based on GITT.\u003c/p\u003e","description":"","filename":"image5.png","url":"https://assets-eu.researchsquare.com/files/rs-6892258/v1/61652c0d2e4df2b510ef4872.png"},{"id":88213845,"identity":"320cb3a3-ced7-4d6d-bcae-2077d2eb6449","added_by":"auto","created_at":"2025-08-04 06:18:23","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1620862,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6892258/v1/9acb2168-2dca-4fc9-a894-27525b9f415a.pdf"}],"financialInterests":"No competing interests reported.","formattedTitle":"\u003cp\u003eV\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e Nanospikes as a Cathode for Aqueous Zn-Based Batteries\u003c/p\u003e","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eGrid-scale energy storage demands systems that are sustainable, safe, and cost-effective. Aqueous Zn-ion batteries (ZIBs) are considered future candidates for this application due to their low price, abundance, eco-friendliness, and high safety[\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e, \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e]. In general, manganese oxides[\u003cspan additionalcitationids=\"CR4 CR5\" citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e], vanadium oxides[\u003cspan additionalcitationids=\"CR8\" citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e], Prussian blue[\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e], and their derivatives[\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e, \u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e] have been considered as cathode materials for ZIBs. Among these, layered vanadium oxides materials are particularly interesting owing to their high specific capacity, multiple oxidation numbers, open crystal structure, and abundant active sites[\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e, \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e]. Vanadium pentoxide (V\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e) is the most extensively employed material owing to its structural stability, high abundance, and excellent theoretical capacity up to 589 mAh\u0026middot;g\u003csup\u003e\u0026ndash;1\u003c/sup\u003e[\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e]. However, the low ionic and electronic conductivity values of pure-phase V\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e hinder its practical applications[\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eVanadium oxides containing mixed-valence vanadium species exhibit improved electrochemical properties when utilised as a cathode in ZIBs. For instance, V\u003csup\u003e4+\u003c/sup\u003e-V\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e⸱3H\u003csub\u003e2\u003c/sub\u003eO pre-intercalated with PAN[\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e] demonstrates outstanding capacity retention of 133 mAh\u0026middot;g\u003csup\u003e\u0026ndash;1\u003c/sup\u003e following 1000 runs at 10 A\u0026middot;g\u003csup\u003e\u0026ndash;1\u003c/sup\u003e. Similarly, V\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e nanospheres comprising multiple vanadium oxidation numbers[\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e] deliver 140 mAh\u0026middot;g\u003csup\u003e\u0026ndash;1\u003c/sup\u003e over 1000 runs under the same conditions. Yang et al.[\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e] explored the electrochemical behaviour of vanadium oxide nanotubes (VO-NTs) incorporating mixed-valence vanadium ions. These VO-NTs exhibited a capacity of 314.6 mAh\u0026middot;g\u003csup\u003e\u0026ndash;1\u003c/sup\u003e at 0.1 A\u0026middot;g\u003csup\u003e\u0026ndash;1\u003c/sup\u003e. Also, they maintained 80.5% of their initial capacity after 950 cycles at a higher current density of 2.4 A\u0026middot;g\u003csup\u003e\u0026ndash;1\u003c/sup\u003e, suggesting remarkable cyclic efficiency. However, the capacity was limited to 87.8 mAh\u0026middot;g\u003csup\u003e\u0026ndash;1\u003c/sup\u003e at 9.6 A\u0026middot;g\u003csup\u003e\u0026ndash;1\u003c/sup\u003e. This was substantially lower in comparison to that observed for other V-based cathodes. This reduced performance could be associated with the high content of dodecylamine in VO-NTs, which has minimal contribution to charge storage. It is worth mentioning that Zhou et al. [\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e] removed dodecylamine from VO-NTs through thermal treatment, resulting in the formation of vanadium pentoxide nanospikes (VO-NS), which exhibited superior lithium-ion storage performance compared to VO-NTs.\u003c/p\u003e \u003cp\u003eBuilding on this discovery, the Zn\u003csup\u003e2+\u003c/sup\u003e storage behavior of the VO-NS cathode was systematically investigated. The electrode delivered a notable specific capacity of 355.2 mAh\u0026middot;g\u003csup\u003e\u0026ndash;1\u003c/sup\u003e at 0.5 A\u0026middot;g\u003csup\u003e\u0026ndash;1\u003c/sup\u003e. Remarkably, it maintained 194.2 mAh\u0026middot;g\u003csup\u003e\u0026ndash;1\u003c/sup\u003e at 10 A\u0026middot;g\u003csup\u003e\u0026ndash;1\u003c/sup\u003e, with 178.4 mAh\u0026middot;g\u003csup\u003e\u0026ndash;1\u003c/sup\u003e retained after 2000 cycles\u0026mdash;corresponding to a capacity retention of 91.86%, demonstrating exceptional long-term cycling stability and rate capability.\u003c/p\u003e"},{"header":"2. Experimental","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1 Preparation of VO-NTs and VO-NS\u003c/h2\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe synthesis process for vanadium pentoxide nanospikes (VO-NS) is presented in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e. 0.76 g of V\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e was dispersed within 60 ml of deionised (DI) water with constant stirring for 10 min to achieve a uniform dispersion. Then, 0.72 g of dodecylamine was mixed with 5 mL of anhydrous C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e5\u003c/sub\u003eOH and added to the vanadium oxide dispersion. After this, the dispersion was stirred continuously for 48 h. Thereafter, it was poured into a Teflon-lined stainless-steel autoclave and heated at 180 ℃ for 72 h. The solid product was thoroughly cleaned with DI water and ethyl alcohol upon cooling back to ambient temperature, after which it was dried at a temperature of 80\u0026deg;C overnight to yield VO-NTs. The VO-NTs were finally annealed under ambient conditions at 400\u0026deg;C to produce the desired VO-NS material.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2\u003c/b\u003e Material analysis\u003c/h2\u003e \u003cp\u003eThe crystal phases of the synthesised materials were investigated via XRD (SmartlabSE) equipped with a Cu Kα radiation source. Surface morphology and structural features were examined via FESEM (Zeiss, Sigma 500) and TEM (FEI, Talos F200X). The composition of the samples was determined via TGA. FTIR (Thermo Fisher Scientific Nicolet, iS20) was used to probe chemical structures and functional groups. Surface elemental composition and oxidation states were analysed using an ESCALAB 250XI XPS system from Thermo Fisher, utilising a monochromatic Al Kα source (1486.6 eV) under a pressure below 5\u0026times;10\u003csup\u003e\u0026minus;\u0026thinsp;10\u003c/sup\u003e bar.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e2.3 Electrochemical measurements\u003c/h2\u003e \u003cp\u003eA suspension of VO-NS/VO-NTs, carbon black, and PVDF, with a mass ratio of 7:2:1, was prepared in NMP as the solvent. This mixture was homogeneously coated onto Ti foil and dried in a vacuum oven at 120\u0026deg;C for a duration of 12 h to obtain the cathode. The electrochemical cell arrangement comprised glass fibre paper as the separator, Zn-metal foil as the anode, and 2.5 M zinc sulphate solution as the electrolyte. All electrochemical evaluations were carried out at ambient temperature. All electrochemical parameters were expressed relative to the mass of VO-NS/VO-NTs. galvanostatic charge-discharge (GCD) measurements and galvanostatic intermittent titration technique (GITT) tests were conducted utilising a Wuhan LAND CT2001A battery testing system. A CHI 660E electrochemical workstation was utilised to carry out the electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) analyses.\u003c/p\u003e \u003c/div\u003e"},{"header":"3. Results and discussion","content":"\u003cp\u003eThe thermal stability of VO-NTs was evaluated via TGA. As illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e(a), an initial mass loss of 2.8% was recorded within the 30–110°C range as a result of the loss of physically adsorbed water. A more pronounced weight loss of 39.2% occurred between 110 and 400°C, associated with the release of structural water and the thermal degradation of the intercalated dodecylamine. The phase information of VO-NTs and VO-NS were examined using XRD, as depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e(b). The XRD profile of VO-NTs aligned well with the previous reports[\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e, \u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e], confirming their successful synthesis. The diffraction peaks of VO-NTs located at 7.44°, 10.81°, 14.48°, 21.90°, 29.01°, 32.59°and 46.75° can be indexed to (002), (003), (100), (011), (200), (210) and (310) plane, respectively. According to the Bragg’s law, the interplanar distance of the (002) plane is calculated to be 1.18 nm, which further leads to the interplanar distance of the (001) plane being 2.36 nm. Following thermal treatment at 400°C, the characteristic peaks of VO-NTs disappeared, and new signals consistent with orthorhombic V\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e emerged, indicating a significant phase transformation. The diffraction peaks at 15.26°, 20.16°, 21.56°, 26.02°, 30.92°, 32.26°and 34.20° can be indexed to (200), (001), (101), (100), (301), (011) and (310) plane, respectively. To further investigate chemical bonding and functional groups of the as-synthesized VO-NTs and VO-NS, FTIR analysis was performed. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e(c), the absorption band around 3460 and 1640 cm\u003csup\u003e–1\u003c/sup\u003e were linked to the H-O stretching and H-O-H bending vibrational modes in H\u003csub\u003e2\u003c/sub\u003eO, while the peaks at 585 and 635 cm\u003csup\u003e–1\u003c/sup\u003e was linked to the symmetric stretching vibrations of triply coordinated oxygen bonds [\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e]. Besides, peaks around 827 and 1020 cm\u003csup\u003e–1\u003c/sup\u003e were assigned to the stretching vibrations of V = O and V-O-V, respectively[\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e]. It is worth noting that absorption bands at 741, 1460, 2850, and 2930 cm\u003csup\u003e–1\u003c/sup\u003e, ascribed to the C-H vibrations of dodecylamine[\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e], were almost entirely eliminated after heat treatment, confirming the effective removal of the organic template. The oxidation states of V in VO-NTs and VO-NS were determined via XPS analysis (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e(d)). The two fitted peaks at 516.4 and 517.6 eV were corresponded to the V\u003csup\u003e4+\u003c/sup\u003e 2p3/2 and V\u003csup\u003e5+\u003c/sup\u003e 2p3/2, respectively[\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e, \u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e]. Quantitative analysis revealed that V\u003csup\u003e4+\u003c/sup\u003e comprised 67% of the vanadium in VO-NTs, which decreased to 19.4% in VO-NS, likely due to the partial oxidation of V\u003csup\u003e4+\u003c/sup\u003e to V\u003csup\u003e5+\u003c/sup\u003e during thermal treatment in an air atmosphere.\u003c/p\u003e \u003cp\u003eAs depicted by the SEM image in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e(a), the synthesized VO-NTs display a well-defined tubular morphology, confirming the successful formation of nanotube structures. The TEM images provided in Figs.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e(b) also revealed that the VO-NTs possess an open-ended, multi-walled tubular configuration. High-resolution TEM(HRTEM) analysis (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e(c)) identified lattice planes having an interplanar spacing of 2.25 nm, which corresponded to the (001) crystallographic plane of VO-NTs, in agreement with the XRD data. Following annealing at 400 ℃, the VO-NTs undergo a significant morphological transformation from tubular form into nanospike architectures (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e (d)) composed of smaller nanocrystalline grains (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e (e)). HRTEM imaging (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e(f)) reveals lattice planes with an interplanar spacing of 0.58 nm, which can be indexed to the (200) plane of V\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e. This transformation not only results in more channels for the transport of zinc ions but also enhances electrolyte penetration, thereby contributing to improved electrochemical performance. In summary, these results demonstrate that thermal annealing not only removes the organic dodecylamine but also induces a favourable reorganisation of the material.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe rate performance of VO-NTs and VO-NS cathodes evaluated at 0.5, 0.7, 1, 3, and 5 A·g\u003csup\u003e− 1\u003c/sup\u003e is presented in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e (a). The VO-NS electrode delivered discharge capacities of 355.2, 337.7, 317.1, 284.4, and 261.7 mAh·g\u003csup\u003e–1\u003c/sup\u003e at these rates, consistently outperforming VO-NTs. When the current density was returned to 0.5 A·g\u003csup\u003e–1\u003c/sup\u003e, the VO-NS delivered a capacity of 327 mAh·g\u003csup\u003e–1\u003c/sup\u003e, indicating excellent reversibility with a retention rate of 92.06%. Long-term cyclic stability at 10.0 A·g\u003csup\u003e–1\u003c/sup\u003e is illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e(b). After 2000 cycles, the VO-NS cathode retained a 178.4 mAh·g\u003csup\u003e–1\u003c/sup\u003e, about 91.86% of its initial capacity (194.2 mAh·g\u003csup\u003e–1\u003c/sup\u003e), significantly higher than that of VO-NTs under identical conditions. Additionally, Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e(c) illustrates the cycling behaviour at 1 A·g\u003csup\u003e–1\u003c/sup\u003e, where both materials exhibit an inactivation phase, characterised by a gradual increase in discharge capacity within the first 70 cycles. After 500 cycles, a slight decline is observed in both cases; however, The VO-NS retains 68.5% of its initial capacity, whereas VO-NTs maintain only 60.4%, further highlighting the improved cycling stability achieved by removing dodecylamine. Nyquist plots and equivalent circuits are presented in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e(d). The VO-NS cathode exhibits a significantly smaller semicircle within the high-frequency region, implying a lower charge transfer resistance (\u003cem\u003eR\u003c/em\u003e\u003csub\u003ect\u003c/sub\u003e) compared to VO-NTs. Improved ion transport is further supported by the Warburg coefficient (\u003cem\u003eσ\u003c/em\u003e\u003csub\u003eω\u003c/sub\u003e​), derived from the Z' versus ω\u003csup\u003e–1/2\u003c/sup\u003e plots in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e(e). A significantly lower \u003cem\u003eσ\u003c/em\u003e\u003csub\u003eω\u003c/sub\u003e value of 3.66 was displayed by VO-NS compared to 18.57 for VO-NTs, suggesting faster Zn\u003csup\u003e2+\u003c/sup\u003e diffusion. Therefore, the removal of dodecylamine from VO-NTs not only reduces the charge transfer resistance but also enhances the Zn²⁺ diffusion coefficient, thereby improving its rate performance. The obtained GCD plots of VO-NS at 0.5 A·g\u003csup\u003e–1\u003c/sup\u003e (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e(f)) revealed two distinct discharge plateaus around 0.9 and 0.6 V, indicative of multistep Zn\u003csup\u003e2+\u003c/sup\u003e insertion. This is corroborated by the CV curves in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e(g), which display two well-defined redox signals at 1.03/0.88 V and 0.76/0.61 V. The CV profiles also highlight excellent electrochemical reversibility. Finally, Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e(h) provides a comparison of the power density and energy density of VO-NS with other V-based aqueous ZIBs cathodes. VO-NS achieved an energy density of 294.9 Wh·kg\u003csup\u003e–1\u003c/sup\u003e at 0.5 A·g\u003csup\u003e− 1\u003c/sup\u003e and a power density of 6714 W·kg\u003csup\u003e–1\u003c/sup\u003e at 10 A·g\u003csup\u003e–1\u003c/sup\u003e, outperforming materials such as V\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e@PANI[\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e], H\u003csub\u003e2\u003c/sub\u003eV\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e8\u003c/sub\u003e[\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e], O\u003csub\u003eV\u003c/sub\u003e-ZVO[\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e], VO-NTs[\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e], and KVO[\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e]. These results collectively underscore the superior electronic conductivity and ion transport capability of the VO-NS cathode, which can be ascribed to the structural optimisation attained by the removal of dodecylamine.\u003c/p\u003e \u003cp\u003eTo develop a better understanding of the electrochemical kinetics of the VO-NS cathode, CV tests were carried out at various scan rates (\u003cem\u003ev\u003c/em\u003e) ranging from 0.2 to 1.0 mV·s\u003csup\u003e–1\u003c/sup\u003e, as presented in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e(a). The oxidation signals moved to more positive potentials owing to the enhanced polarization effect at higher rates, while the reduction signals moved to more negative values. The peak current (\u003cem\u003ei\u003c/em\u003e) and \u003cem\u003ev\u003c/em\u003e are related to each other according to the equation given below[\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e]:\u003c/p\u003e\u003cdiv id=\"Equa\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equa\" name=\"EquationSource\"\u003e\n$$\\:i=a{v}^{b}$$\u003c/div\u003e\u003c/div\u003e\u003cp\u003e\u003c/p\u003e \u003cp\u003ewhere a and b are tuneable parameters. The \u003cem\u003eb\u003c/em\u003e-value offers insights into the charge storage mechanism: a value of 0.5 is typical of a diffusion-limited mechanism, whereas a value approaching 1.0 indicates surface-capacitive behaviour. From the linear plots of log(\u003cem\u003ei\u003c/em\u003e) against log(\u003cem\u003ev\u003c/em\u003e) (see Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e(b)), the \u003cem\u003eb\u003c/em\u003e-values for the anodic and cathodic peaks were 0.84, 0.61, 0.65, and 0.77, respectively. This indicated that the redox process in VO-NS involved a combination of diffusion-limited and capacitive mechanisms. To quantify the contribution of capacitive behaviour, the current response was further separated using the relation[\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e]:\u003c/p\u003e\u003cdiv id=\"Equb\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equb\" name=\"EquationSource\"\u003e\n$$\\:i={\\text{k}}_{1}\\text{v}+{\\text{k}}_{2}{\\text{v}}^{1/2}$$\u003c/div\u003e\u003c/div\u003e\u003cp\u003e\u003c/p\u003e \u003cp\u003ewhere the k\u003csub\u003e1\u003c/sub\u003ev corresponds to pseudocapacitive effects and k\u003csub\u003e2\u003c/sub\u003ev\u003csup\u003e1/2\u003c/sup\u003e to diffusion-limited contributions. The pseudocapacitive effects accounted for 88.23% of the overall current at \u003cem\u003ev\u003c/em\u003e = 0.8 mV·s\u003csup\u003e–1\u003c/sup\u003e (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e(c)), clearly dominating the charge storage process. The pseudocapacitive contribution progressively rose as the scan rate was enhanced from 0.2 to 1.0 mV·s\u003csup\u003e–1\u003c/sup\u003e, reaching up to 91% at 1.0 mV·s\u003csup\u003e–1\u003c/sup\u003e (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e(d)). These results confirmed that the electrochemical redox process of VO-NS at high current densities is predominantly governed by a pseudocapacitance-controlled mechanism, thereby promoting enhanced charge-transfer kinetics. In addition, GITT analysis was performed to assess Zn\u003csup\u003e2+\u003c/sup\u003e diffusion within the VO-NS electrode (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e(e)). The diffusion coefficients (D\u003csub\u003eZn\u003c/sub\u003e) range from 10\u003csup\u003e–11\u003c/sup\u003e to 10\u003csup\u003e–9\u003c/sup\u003e cm\u003csup\u003e2\u003c/sup\u003e·s\u003csup\u003e–1\u003c/sup\u003e (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e(f)), comparable to D\u003csub\u003eZn\u003c/sub\u003e reported for other vanadium oxide-based cathodes[\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e, \u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e]. The relatively high diffusivity is likely associated with the reduced grain size of the VO-NS structure, which provides shorter and more accessible ion transport pathways.\u003c/p\u003e "},{"header":"4. Conclusion","content":"\u003cp\u003eIn summary, VO-NS were successfully synthesised through thermal removal of dodecylamine from VO-NTs. When employed as a cathode in ZIBs, VO-NS exhibited improved electronic conductivity and Zn\u003csup\u003e2+\u003c/sup\u003e transport compared to VO-NTs. These advantages resulted in outstanding electrochemical performance, including a rate capability of 261.7 mAh·g\u003csup\u003e–1\u003c/sup\u003e at 5.0 A·g\u003csup\u003e–1\u003c/sup\u003e and a remarkable specific discharge capacity of 355.2 mAh·g\u003csup\u003e–1\u003c/sup\u003e at 0.5 A·g\u003csup\u003e–1\u003c/sup\u003e. Besides, the VO-NS cathode demonstrated excellent cycling durability, retaining 178.4 mAh·g\u003csup\u003e–1\u003c/sup\u003e after 2000 cycles at 10.0 A·g\u003csup\u003e–1\u003c/sup\u003e, which was 91.86% of its initial capacity. In addition, VO-NS also delivered high values of energy density and power density (294.9 Wh·kg\u003csup\u003e–1\u003c/sup\u003e at 0.5 A·g\u003csup\u003e–1\u003c/sup\u003e and 6714 W·kg\u003csup\u003e–1\u003c/sup\u003e at 10 A·g\u003csup\u003e–1\u003c/sup\u003e, respectively), exceeding the performance of most previously reported Vanadium oxides-based cathodes used for aqueous ZIBs. These findings underscore the significant potential of VO-NS as a high-efficiency cathode material for advanced aqueous ZIBs.\u003c/p\u003e"},{"header":"Declarations","content":"\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003eJiandong Wu : Investigation, Supervision, Writing \u0026ndash;original draft, Formal analysis,Writing \u0026ndash; review \u0026amp; editing. Jiao Yujie\u0026amp;Wei Hao: Validation, Data curation, Visualization. Lu Hui\u0026amp;Yang Shaolin: Data curation, Visualization. Ma Jinfu\u0026amp;Sheng Zhilin: Data curation. Hou Chunping: Formal analysis.\u003c/p\u003e\u003ch2\u003eAcknowledgement\u003c/h2\u003e\u003cp\u003eThe authors greatly appreciate the financial support from Natural Science Foundation of Ningxia, China (No.2023AAC03290) and National Natural Science Foundation of China (No. 22169001, No. U22A20146).\u003c/p\u003e\u003ch2\u003eData Availability\u003c/h2\u003e\u003cp\u003eThe authors declare that the data supporting the findings of this study are available within the paper. If other formats of the original data files are required, they can be obtained from the corresponding author upon reasonable request.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eZ.M. Zhao, J.W. Zhao, Z.L. Hu, J.D. Li, J.J. Li, Y.J. Zhang, C. Wang, G.L. 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Sun, Vanadium Pentoxide Nanosheets in-Situ Spaced with Acetylene Black as Cathodes for High-Performance Zinc-lon Batteries, \u003cem\u003eACS APPL MATER INTER\u003c/em\u003e 11 (2019) (44).41297\u0026ndash;41303.\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":true,"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":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"V2O5, Nanospikes, Cathode, Electrochemical performance, Aqueous zinc-ion batteries","lastPublishedDoi":"10.21203/rs.3.rs-6892258/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-6892258/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eVanadium oxides have been explored extensively as electroactive materials for aqueous Zn-ion batteries (ZIBs). In this study, V\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e nanospikes (VO-NS) were synthesized via thermal decomposition of dodecylamine from vanadium oxide nanotubes (VO-NTs), and its performance as cathode material for ZIBs was systematically investigated. The resulting VO-NS cathode exhibited substantially enhanced electronic conductivity and Zn\u003csup\u003e2+\u003c/sup\u003e transport kinetics compared to VO-NTs. Electrochemical tests revealed that VO-NS delivered a specific capacity of 355.2 mAh\u0026middot;g\u003csup\u003e\u0026ndash;1\u003c/sup\u003e at a current density of 0.5 A\u0026middot;g\u003csup\u003e\u0026ndash;1\u003c/sup\u003e and maintained 261.7 mAh\u0026middot;g\u003csup\u003e\u0026ndash;1\u003c/sup\u003e even at 5.0 A\u0026middot;g\u003csup\u003e\u0026ndash;1\u003c/sup\u003e, demonstrating an outstanding rate capability. Notably, the VO-NS cathode maintained 91.86% of its initial capacity (194.2 mAh\u0026middot;g\u003csup\u003e\u0026ndash;1\u003c/sup\u003e) after 2000 cycle at 10.0 A\u0026middot;g\u003csup\u003e\u0026ndash;1\u003c/sup\u003e, highlighting the exceptional cyclic stability. Furthermore, it achieved a high value of energy density of 294.9 Wh\u0026middot;kg\u003csup\u003e\u0026ndash;1\u003c/sup\u003e at 0.5 A\u0026middot;g\u003csup\u003e\u0026ndash;1\u003c/sup\u003e and an exceptional power density of 6714 W\u0026middot;kg\u003csup\u003e\u0026ndash;1\u003c/sup\u003e at 10 A\u0026middot;g\u003csup\u003e\u0026ndash;1\u003c/sup\u003e, surpassing many previously reported vanadium-based ZIBs cathodes. These findings underscore the potential of VO-NS as an exceptional cathodic material for ZIBs.\u003c/p\u003e","manuscriptTitle":"V2O5 Nanospikes as a Cathode for Aqueous Zn-Based Batteries","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-06-20 16:10:35","doi":"10.21203/rs.3.rs-6892258/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"7bcef845-448b-49fb-949b-a50ffc52e3c6","owner":[],"postedDate":"June 20th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2025-08-04T06:10:12+00:00","versionOfRecord":[],"versionCreatedAt":"2025-06-20 16:10:35","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-6892258","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-6892258","identity":"rs-6892258","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}