Simultaneous Construction of Hydrophobic Environment and Optimized Ion Channels in V₂O₅ for Zinc Ion Batteries

Abstract

Vanadium-based oxides are commonly used as cathode materials for aqueous zinc ion batteries (AZIBs), offering the advantages of open crystalline structure and high theoretical capacity. However, vanadium-based oxides are limited in further application development by poor structural stability and uncontrollable dissolution. Here, the hexamethylenediammonium (HMA²⁺) preintercalated V₂O₅ cathode (HVOH) is constructed to enhance the comprehensive performance of AZIBs. In terms of active material stability, the lamellar structure is stabilized with the existence of interlayer pillar HMA²⁺, and the cathodic hydrophobicity is enhanced by long alkyl chains to inhibit vanadium dissolution and water-related side reactions. Besides, the interlayer spacing (13 Å) is widened, and new active sites are introduced due to the preintercalated HMA²⁺, realizing higher capacity performance. Specifically, the insertion of ions into the low-voltage area is significantly increased. The electrostatic interaction between the V₂O₅ layer and Zn²⁺ is weakened thanks to the positive electrical properties of HMA²⁺. Thus, accelerated diffusion rates and electrochemical kinetics are obtained. As a result, the assembled Zn||Zn(CF₃SO₃)₂||HVOH cell obtains a high specific capacity of 431.7 mAh g⁻¹ at 0.2 A g⁻¹ and achieves an improved cycling performance at 10 A g⁻¹ (137.5 mAh g⁻¹ after 3000 cycles). This strategy provides a perspective for the optimization of layered vanadium oxides by organic cationic preintercalation.

Keywords

cathodes / hydrophobic functional groups / preintercalation / vanadium oxides / zinc ion batteries

References

[1] J. H. Williams, A. DeBenedictis, R. Ghanadan, et al., “The Technology Path to Deep Greenhouse Gas Emissions Cuts by 2050: The Pivotal Role of Electricity,” Science 335, no. 6064 (2012): 53–59.

[2] J. B. Goodenough, “Electrochemical Energy Storage in a Sustainable Modern Society,” Energy & Environmental Science 7, no. 1 (2014): 14–18.

[3] Z. Zhu, T. Jiang, M. Ali, et al., “Rechargeable Batteries for Grid Scale Energy Storage,” Chemical Reviews 122, no. 22 (2022): 16610–16751.

[4] Y. Liang and Y. Yao, “Designing Modern Aqueous Batteries,” Nature Reviews Materials 8, no. 2 (2023): 109–122.

[5] T. Jiang, D. Shen, Z. Zhang, et al., “Battery Technologies for Grid-Scale Energy Storage,” Nature Reviews Clean Technology 1, no. 7 (2025): 474–492.

[6] X. Zhang, J. P. Hu, N. Fu, et al., “Comprehensive Review Onzinc-Ionbattery Anode: Challenges and Strategies,” InfoMat 4, no. 7 (2022): e12306.

[7] Y. Xu, G. Zhang, J. Liu, et al., “Recent Advances on Challenges and Strategies of Manganese Dioxide Cathodes for Aqueous Zinc-Ion Batteries,” Energy & Environmental Materials 6, no. 6 (2023): e12575.

[8] T. Lv, Y. Peng, G. Zhang, et al., “How About Vanadium-Based Compounds as Cathode Materials for Aqueous Zinc Ion Batteries?,” Advanced Science 10, no. 12 (2023): 2206907.

[9] G. Zampardi and F. La Mantia, “Prussian Blue Analogues as Aqueous Zn-Ion Batteries Electrodes: Current Challenges and Future Perspectives,” Current Opinion in Electrochemistry 21 (2020): 84–92.

[10] Z. Li, J. Tan, Y. Wang, et al., “Building Better Aqueous Zn-Organic Batteries,” Energy & Environmental Science 16, no. 6 (2023): 2398–2431.

[11] Y. Bai, Y. Qin, J. Hao, H. Zhang, and C. M. Li, “Advances and Perspectives of Ion-Intercalated Vanadium Oxide Cathodes for High-Performance Aqueous Zinc Ion Battery,” Advanced Functional Materials 34, no. 11 (2023): 2310393.

[12] Y. Guo, H. Jiang, B. Liu, et al., “Better Engineering Layered Vanadium Oxides for Aqueous Zinc-Ion Batteries: Going Beyond Widening the Interlayer Spacing,” SmartMat 5, no. 1 (2023): e1231.

[13] T. Zhou and G. Gao, “V₂O₅-Based Cathodes for Aqueous Zinc Ion Batteries: Mechanisms, Preparations, Modifications, and Electrochemistry,” Nano Energy 127 (2024): 109691.

[14] A. Guo, Z. Wang, L. Chen, et al., “A Comprehensive Review of the Mechanism and Modification Strategies of V₂O₅ Cathodes for Aqueous Zinc-Ion Batteries,” ACS Nano 18, no. 40 (2024): 27261–27286.

[15] C. Guo, S. Yi, R. Si, et al., “Advances on Defect Engineering of Vanadium-Based Compounds for High-Energy Aqueous Zinc–Ion Batteries,” Advanced Energy Materials 12, no. 40 (2022): 202202039.

[16] X. Zeng, Z. Gong, C. Wang, P. J. Cullen, and Z. Pei, “Vanadium-Based Cathodes Modification via Defect Engineering: Strategies to Support the Leap From Lab to Commercialization of Aqueous Zinc-Ion Batteries,” Advanced Energy Materials 14, no. 31 (2024): 202401704.

[17] X. Dai, F. Wan, L. Zhang, H. Cao, and Z. Niu, “Freestanding Graphene/VO₂ Composite Films for Highly Stable Aqueous Zn-Ion Batteries With Superior Rate Performance,” Energy Storage Materials 17 (2019): 143–150.

[18] G. Yoo, B.-R. Koo, and H. An, “Nano-Sized Split V₂O₅ With H₂O-Intercalated Interfaces as a Stable Cathode for Zinc Ion Batteries Without an Aging Process,” Chemical Engineering Journal 434 (2022): 134738.

[19] L. Xing, C. Zhang, M. Li, et al., “Revealing Excess Al³⁺ Preinsertion on Altering Diffusion Paths of Aluminum Vanadate for Zinc-Ion Batteries,” Energy Storage Materials 52 (2022): 291–298.

[20] Y. Liu, Y. Liu, X. Wu, and Y. R. Cho, “High Performance Aqueous Zinc Battery Enabled by Potassium Ion Stabilization,” Journal of Colloid and Interface Science 628 (2022): 33–40.

[21] J. Guo, B. He, W. Gong, et al., “Emerging Amorphous to Crystalline Conversion Chemistry in Ca-Doped VO₂ Cathodes for High-Capacity and Long-Term Wearable Aqueous Zinc-Ion Batteries,” Advanced Materials 36, no. 11 (2024): e2303906.

[22] Y.-H. Du, X.-Y. Liu, X.-Y. Wang, et al., “Freestanding Strontium Vanadate/Carbon Nanotube Films for Long-Life Aqueous Zinc-Ion Batteries,” Rare Metals 41, no. 2 (2021): 415–424.

[23] W. Liu, X. Liu, F. Ning, et al., “Fabrication of a Heterovalent Dual-Cation Pre-Embedded Hydrated Vanadium Oxide Cathode for High-Performance Zinc Ion Storage,” Journal of Materials Chemistry A 12 (2024): 11883–11894.

[24] Y. Liu, C. Lu, Y. Yang, et al., “Multiple Cations Nanoconfinement in Ultrathin V₂O₅ Nanosheets Enables Ultrafast Ion Diffusion Kinetics Toward High-Performance Zinc Ion Battery,” Advanced Materials 36, no. 18 (2024): 2312982.

[25] L. Ma, N. Li, C. Long, et al., “Achieving Both High Voltage and High Capacity in Aqueous Zinc-Ion Battery for Record High Energy Density,” Advanced Functional Materials 29, no. 46 (2019): 1906142.

[26] Z. Chen, H. Liu, S. Fan, et al., “Inhibition of Vanadium Cathode Dissolution in Zinc-Ion Batteries on Thermodynamics and Kinetics by Guest Pre-Intercalation,” Advanced Energy Materials 14, no. 25 (2024): 2400977.

[27] A. Wang, D. H. Liu, L. Yang, et al., “Building Stabilized Cu_0.17Mn_0.03V₂O_5−□·2.16H₂O Cathode Enables an Outstanding Room-/Low-Temperature Aqueous Zn-Ion Batteries,” Carbon Energy 6, no. 8 (2024): e512.

[28] Q. Wang, J. Wu, M. Wang, H. Yu, X. Qiu, and W. Chen, “Vanadate-Based Fibrous Electrode Materials for High Performance Aqueous Zinc Ion Batteries,” Advanced Science 11, no. 11 (2024): 2307872.

[29] Y. S. Joe, M. S. Kang, G. Jang, et al., “Intercalation of Bilayered V₂O₅ by Electronically Coupled PEDOT for Greatly Improved Kinetic Performance of Magnesium Ion Battery Cathodes,” Chemical Engineering Journal 460 (2023): 141706.

[30] Y. Tong, Y. Zang, S. Su, et al., “Methylene Blue Intercalated Vanadium Oxide With Synergistic Energy Storage Mechanism for Highly Efficient Aqueous Zinc Ion Batteries,” Journal of Energy Chemistry 77 (2023): 269–279.

[31] M. Zhu, I. Ullah, X. Zhang, et al., “Phenolphthalein-Modified Multivalent Vanadium Oxide: Harnessing Oxygen Vacancies and Hydrophobicity for Improved Aqueous Zinc-Ion Battery Performance,” ACS Sustainable Chemistry & Engineering 12, no. 10 (2024): 4255–4263.

[32] M. Du, C. Liu, F. Zhang, et al., “Tunable Layered (Na,Mn)V₈O₂₀·nH₂O Cathode Material for High-Performance Aqueous Zinc Ion Batteries,” Advanced Science 7, no. 13 (2020): 2000083.

[33] H. Liu, X. Hou, T. Fang, et al., “Boosting Zinc-Ion Storage in Hydrated Vanadium Oxides via Migration Regulation,” Energy Storage Materials 55 (2023): 279–288.

[34] P. Shvets, O. Dikaya, K. Maksimova, and A. Goikhman, “A Review of Raman Spectroscopy of Vanadium Oxides,” Journal of Raman Spectroscopy 50, no. 8 (2019): 1226–1244.

[35] J. R. Sohn, J. S. Han, and J. S. Lim, “Spectroscopic Study of V₂O₅ Supported on Zirconia and Modified With MoO₃,” Materials Chemistry and Physics 91 (2005): 558–566.

[36] B. H. Kim, H. Y. Yu, W. G. Hong, et al., “Hydrogen Spillover in Pd-Doped V₂O₅ Nanowires at Room Temperature,” Chemistry – An Asian Journal 7, no. 4 (2012): 684–687.

[37] J. Krzystek, A. Ozarowski, J. Telser, and D. C. Crans, “High-Frequency and -Field Electron Paramagnetic Resonance of Vanadium(IV, III, and II) Complexes,” Coordination Chemistry Reviews 301–302, no. SI (2015): 123–133.

[38] C. Wang, J. Wang, S. Zhang, et al., “Insights Into the Energy Storage Differences of Zinc and Calcium Ions With Layered Vanadium Oxide as a Model Material,” Advanced Energy Materials 13, no. 41 (2023): 2302683.

[39] C. Lee, Y. Hong, D. Kim, Y. Lim, J. W. Choi, and S. Y. Chung, “Metal Ions Versus Protons: Tracking of Charge-Carrier Insertion Into a Cathode Oxide in Aqueous Rechargeable Batteries,” Advanced Functional Materials 33, no. 44 (2023): 2303763.

[40] F. Zhang, X. Sun, M. Du, et al., “Weaker Interactions in Zn²⁺ and Organic Ion-Pre-Intercalated Vanadium Oxide Toward Highly Reversible Zinc-Ion Batteries,” Energy & Environmental Materials 4, no. 4 (2020): 620–630.

[41] T. Liu, L. Chen, X. Wang, Y. Huang, M. Wang, and Y. Zhang, “Polypyrrole-Coated V₂O₅ Nanobelts Arrays on Carbon Cloth for High Performance Zinc Energy Storage,” Electrochimica Acta 441 (2023): 141806.

[42] L. Fan, L. Cao, S. Xiong, Y. Wu, Z. Li, and F. Gu, “Enhanced Zinc Ions Storage Performance by Calcium Ion Induction/Anchoring of Vanadium-Based Nanobelts at Low Temperature,” Materials Today Sustainability 19 (2022): 100160.

[43] X. Xu, Y. Qian, C. Wang, et al., “Enhanced Charge Transfer and Reaction Kinetics of Vanadium Pentoxide for Zinc Storage via Nitrogen Interstitial Doping,” Chemical Engineering Journal 451 (2023): 138770.

[44] H. Liu, X. Hou, T. Fang, et al., “Fast Zinc-Ion Storage Enabled by Hydrophobic Alkyl Chains via Reducing Dual Diffusion Barriers,” Energy Storage Materials 65 (2024): 103092.

[45] R. Frech and W. Huang, “Anion-Solvent and Anion-Cation Interactions in Lithium and Tetrabutylammonium Trifluoromethanesulfonate Solutions,” Journal of Solution Chemistry 23 (1994): 469–481.

[46] T. Wei, Y. Liu, G. Yang, and C. Wang, “Aluminum Vanadate Hollow Spheres as Zero-Strain Cathode Material for Highly Reversible and Durable Aqueous Zinc-Ion Batteries,” Energy Storage Materials 30 (2020): 130–137.

[47] G. Kresse and J. Furthmüller, “Efficient Iterative Schemes for Ab Initio Total-Energy Calculations Using a Plane-Wave Basis Set,” Physical Review B 54, no. 16 (1996): 11169–11186.

[48] P. E. Blöchl, “Projector Augmented-Wave Method,” Physical Review B 50, no. 24 (1994): 17953–17979.

[49] J. P. Perdew, K. Burke, and M. Ernzerhof, “Generalized Gradient Approximation Made Simple,” Physical Review Letters 77, no. 18 (1996): 3865–3868.

RIGHTS & PERMISSIONS

2025 The Author(s). Carbon Energy published by Wenzhou University and John Wiley & Sons Australia, Ltd.