Formamide-engineered VOPO₄ cathodes with high volumetric capacity and mass loading for aqueous zinc-ion batteries

Abstract

Aqueous zinc-ion batteries (AZIBs) have emerged as promising candidates for next-generation energy storage systems due to their inherent safety, cost-effectiveness, and high theoretical capacity. However, their practical application remains constrained by limited cycling stability and sluggish ion diffusion kinetics, particularly under high mass loading conditions. These limitations are primarily attributed to the restricted ion transport pathways within the electrode structure and structural degradation caused by repeated zinc-ion insertion and extraction in highly loaded electrodes. To address these challenges, formamide (FA)-inserted VOPO₄ (FA-VOPO₄) nanosheet cathodes were designed with expanded interlayer spacing (9.3 Å), where FA molecules partially replace interlayer water, thereby enhancing both structural stability and ion transport pathways. This unique structural modification, supported by synergistic hydrogen bonding between FA and residual water, significantly improves Zn²⁺ diffusion kinetics and charge transfer properties, as confirmed by electrochemical tests and theoretical analysis. Consequently, FA-VOPO₄ electrodes delivered a remarkable volumetric capacity of 733 mAh/cm³ at 40 mA/g, approximately 8 times higher than that of the VOPO₄·2H₂O electrode, and retained 82.1% of their capacity after 1000 cycles at 1 A/g with a mass loading of 10 mg/cm². Even at a high mass loading of 20 mg/cm² (4.4 mAh/cm²), the FA-VOPO₄ cathode maintained a volumetric capacity of 535 mAh/cm³. These findings provide valuable insights into electrode design strategies for high-performance AZIBs, contributing to the development of safer, more efficient energy storage technologies with potential applications in grid storage and portable electronics.

Graphical abstract

Keywords

high mass loading / aqueous zinc-ion battery / high volumetric capacity / FA-VOPO₄

References

[1] Fu Q, Zhang W, Liu X. . Dynamic imine chemistry enables paintable biogel electrolytes to shield on-body zinc-ion batteries from interfacial interference. Journal of the American Chemical Society, 2024, 146(50): 34950–34961

[2] Wu S, Hu Z, He P. . Crystallographic engineering of Zn anodes for aqueous batteries. eScience, 2023, 3(3): 100120

[3] Shang Y, Kundu D. A path forward for the translational development of aqueous zinc-ion batteries. Joule, 2023, 7(2): 244–250

[4] Xu Y, Li T, Zhang S. . Compact aqueous zinc–carbon capacitors with high capacity and ultra-long lifespan. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2024, 12(14): 8254–8261

[5] Liu M, Wang P, Zhang W. . Strategies for pH regulation in aqueous zinc ion batteries. Energy Storage Materials, 2024, 67: 103248

[6] Tang H, Chen W, Li N. . Layered MnO₂ nanodots as high-rate and stable cathode materials for aqueous zinc-ion storage. Energy Storage Materials, 2022, 48: 335–343

[7] Xu Y, Huang W, Liu J. . Promoting the reversibility of electrolytic MnO₂-Zn battery with high areal capacity by VOSO₄ mediator. Energy & Environmental Materials, 2024, 4(1): 400005

[8] Zhang F, Zhang W, Wexler D. . Recent progress and future advances on aqueous monovalent-ion batteries towards safe and high-power energy storage. Advanced Materials, 2022, 34(24): 2107965

[9] Zhang F L, Zhang W C, Wexler D. . Recent progress and future advances on aqueous monovalent-ion batteries towards safe and high-power energy storage. Advanced Materials, 2022, 34(24): 2107965

[10] Xu Y, Fan G, Sun P X. . Carbon nitride pillared vanadate via chemical pre-intercalation towards high-performance aqueous zinc-ion batteries. Angewandte Chemie International Edition, 2023, 62(26): e202303529

[11] Liang W, Rao D, Chen T. . Zn_0.52V₂O_5−a·1.8H₂O cathode stabilized by in situ phase transformation for aqueous zinc-ion batteries with ultra-long cyclability. Angewandte Chemie International Edition, 2022, 61(35): e202207779

[12] Li C, Jin S, Archer L A. . Toward practical aqueous zinc-ion batteries for electrochemical energy storage. Joule, 2022, 6(8): 1733–1738

[13] Zampardi G, La Mantia F. Open challenges and good experimental practices in the research field of aqueous Zn-ion batteries. Nature Communications, 2022, 13(1): 687

[14] Liu Y, Li Q, Ma K. . Graphene oxide wrapped CuV₂O₆ nanobelts as high-capacity and long-life cathode materials of aqueous zinc-ion batteries. ACS Nano, 2019, 13(10): 12081–12089

[15] Wu F, Liu M, Li Y. . High-mass-loading electrodes for advanced secondary batteries and supercapacitors. Electrochemical Energy Reviews, 2021, 4(2): 382–446

[16] Yang L, Zhu Y J, Zeng F. . Synchronously promoting the electron and ion transport in high-loading Mn_2.5V₁₀O₂₄∙5.9H₂O cathodes for practical aqueous zinc-ion batteries. Energy Storage Materials, 2024, 65: 103162

[17] Dandan L, Ying-Jie Z, Long C. . A mxene modulator enabled high-loading iodine composite cathode for stable and high-energy-density Zn-I₂ battery. Advanced Energy Materials, 2024, 15(12): 2404426

[18] Ding Y, Peng Y, Chen S. . Hierarchical porous metallic V₂O₃@c for advanced aqueous zinc-ion batteries. ACS Applied Materials & Interfaces, 2019, 11(47): 44109–44117

[19] Javed M S, Lei H, Wang Z. . 2d V₂O₅ nanosheets as a binder-free high-energy cathode for ultrafast aqueous and flexible Zn-ion batteries. Nano Energy, 2020, 70: 104573

[20] Song Z, Zhao Y, Wang H. . Dual mechanism with graded energy storage in long-term aqueous zinc-ion batteries achieved using a polymer/vanadium dioxide cathode. Energy & Environmental Science, 2024, 17(18): 6666–6675

[21] Zhu K, Yang W. Vanadium-based cathodes for aqueous zinc-ion batteries: Mechanisms, challenges, and strategies. Accounts of Chemical Research, 2024, 57(19): 2887–2900

[22] Hu L, Wu Z, Lu C. . Principles of interlayer-spacing regulation of layered vanadium phosphates for superior zinc-ion batteries. Energy & Environmental Science, 2021, 14(7): 4095–4106

[23] Shi H Y, Jiang Q, Wu W. . Assisting Zn storage in layered vanadyl phosphate cathode by interactions with oligoaniline pillars for rechargeable aqueous zinc batteries. Chemical Engineering Journal, 2023, 454: 140323

[24] Wang L, Zhao M, Zhang X. . Novel high-voltage cathode for aqueous zinc ion batteries: Porous K_0.5VOPO₄·1.5H₂O with reversible solid-solution intercalation and conversion storage mechanism. Journal of Energy Chemistry, 2024, 93: 71–78

[25] Xiong P, Zhang F, Zhang X. . Strain engineering of two-dimensional multilayered heterostructures for beyond-lithium-based rechargeable batteries. Nature Communications, 2020, 11(1): 3297

[26] Jiang W, Zhu K, Yang W. Critical issues of vanadium-based cathodes towards practical aqueous Zn-ion batteries. Chemistry, 2023, 29(56): e202301769

[27] Verma V, Kumar S, Manalastas W Jr. . Undesired reactions in aqueous rechargeable zinc ion batteries. ACS Energy Letters, 2021, 6(5): 1773–1785

[28] Jia Z, Yang X, Shi H Y. . Stabilization of VOPO₄·2H₂O voltage and capacity retention in aqueous zinc batteries with a hydrogen bond regulator. Chemical Communications, 2022, 58(39): 5905–5908

[29] Shi H Y, Jiang Q, He T. . Uncovering and retrieving the internal vanadium migration caused voltage fade in vanadyl phosphate cathode for aqueous zinc batteries. ACS Energy Letters, 2023, 8(12): 5215–5220

[30] Wan F, Zhang Y, Zhang L. . Reversible oxygen redox chemistry in aqueous zinc-ion batteries. Angewandte Chemie International Edition, 2019, 58(21): 7062–7067

[31] Shi H Y, Jiang Q, Wu W. . Assisting Zn storage in layered vanadyl phosphate cathode by interactions with oligoaniline pillars for rechargeable aqueous zinc batteries. Chemical Engineering Journal, 2023, 454: 140323

[32] Verma V, Kumar S, Manalastas W Jr. . Layered VOPO₄ as a cathode material for rechargeable zinc-ion battery: Effect of polypyrrole intercalation in the host and water concentration in the electrolyte. ACS Applied Energy Materials, 2019, 2(12): 8667–8674

[33] Ran Y, Ren J, Kong Y. . Electrochemical zinc and hydrogen co-intercalation in Li₃ (V₆O₁₆): A high-capacity aqueous zinc-ion battery cathode. Electrochimica Acta, 2022, 412: 140120

[34] Zhang W, Tang C, Lan B. . K_0.23V₂O₅ as a promising cathode material for rechargeable aqueous zinc ion batteries with excellent performance. Journal of Alloys and Compounds, 2020, 819: 152971

[35] Dilwale S, Ghosh M, Vijayakumar V. . Electrodeposited layered sodium vanadyl phosphate (Na_xVOPO₄·nH₂O) as cathode material for aqueous rechargeable zinc metal batteries. Energy & Fuels, 2022, 36(12): 6520–6531

[36] Wu Y, Zong Q, Liu C. . Sodium-ion substituted water molecule in layered vanadyl phosphate enhancing electrochemical kinetics and stability of zinc ion storage. Small, 2023, 19(40): 2303227

[37] Jiang Y, Wu Z, Ye F. . Spontaneous knitting behavior of 6.7-nm thin (NH₄)_0.38V₂O₅ nano-ribbons for binder-free zinc-ion batteries. Energy Storage Materials, 2021, 42: 286–294

[38] Wu Z, Lu C, Ye F. . Bilayered VOPO₄·2H₂O nanosheets with high-concentration oxygen vacancies for high-performance aqueous zinc-ion batteries. Advanced Functional Materials, 2021, 31(45): 2106816

[39] Du Y, Wang X, Zhang Y. . High mass loading CaV₄O₉ microflowers with amorphous phase transformation as cathode for aqueous zinc-ion battery. Chemical Engineering Journal, 2022, 434: 134642

[40] Chen S, Ji D, Chen Q. . Coordination modulation of hydrated zinc ions to enhance redox reversibility of zinc batteries. Nature Communications, 2023, 14(1): 3526

[41] Jian Q, Wang T, Sun J. . Hydrated solvation suppression of zinc ions for highly reversible zinc anodes. Chemical Engineering Journal, 2023, 466: 143189

[42] Jin Y Q, Chen H, Peng L. . Interfacial polarization triggered by glutamate accelerates dehydration of hydrated zinc ions for zinc-ion batteries. Chemical Engineering Journal, 2021, 416: 127704

[43] Li M, Wang X, Meng J. . Comprehensive understandings of hydrogen bond chemistry in aqueous batteries. Advanced Materials, 2024, 36(3): 2308628

[44] Tian Z, Guo W, Shi Z. . The role of hydrogen bonding in aqueous batteries: Correlating molecular-scale interactions with battery performance. ACS Energy Letters, 2024, 9(10): 5179–5205

[45] Feng Z, Zhang Y, Jiang H. . On the origin of enhanced electrochemical kinetics in guest-ions pre-intercalated layered vanadium oxides: Interlayer spacing vs lattice distortion. Energy Storage Materials, 2024, 71: 103552

[46] Räsänen M. A matrix infrared study of monomeric formamide. Journal of Molecular Structure, 1983, 101(3–4): 275–286

[47] Urso R G, Scirè C, Baratta G A. . Infrared study on the thermal evolution of solid state formamide. Physical Chemistry Chemical Physics, 2017, 19(32): 21759–21768

[48] Golczak S, Kanciurzewska A, Fahlman M. . Comparative xps surface study of polyaniline thin films. Solid State Ionics, 2008, 179(39): 2234–2239

[49] Huang H, Xia X, Yun J. . Interfacial engineering of hydrated vanadate to promote the fast and highly reversible H⁺/Zn²⁺ co-insertion processes for high-performance aqueous rechargeable batteries. Energy Storage Materials, 2022, 52: 473–484

[50] Zhang Z, Xi B, Wang X. . Oxygen defects engineering of VO₂·xH₂O nanosheets via in situ polypyrrole polymerization for efficient aqueous zinc ion storage. Advanced Functional Materials, 2021, 31(34): 2103070

[51] Zhu Q, Cai D, Lan X. . Design of multidimensional nanocomposite material to realize the application both in energy storage and electrocatalysis. Science Bulletin, 2018, 63(3): 152–154

[52] Singh S B, Tran D T, Jeong K U. . A flexible and transparent zinc-nanofiber network electrode for wearable electrochromic, rechargeable Zn-ion battery. Small, 2022, 18(5): 2104462

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