Vanadium oxide cathode pillared by Al³⁺ and H₂O for high-performance aqueous zinc-ion batteries

Abstract

Aqueous zinc-ion batteries (AZBs) are considered safer and potential substitutes for large-scale energy storage and conversion devices. The conventional vanadium pentoxide (V₂O₅) cathode material has attracted widespread attention duo to its typical layered structure and high theoretical capacity. Unfortunately, it still suffers from severe structural collapse, sluggish diffusion dynamics, and fast capacity fading. Herein, we rationally designed and prepared trivalent Al³⁺ and H₂O co-intercalated V₂O₅ (AlVO), in which Al³⁺ plays a “pillar” role and forms strong Al−O bonds, while H₂O acts as the “lubricant”, synergistically maintaining the structural stability and accelerating the diffusion of zinc ions. The Zn//AlVO battery is found to possess not only an impressive reversible capacity of 390.7 mAh·g⁻¹ at 0.5 A·g⁻¹, 5.13 times that of Zn//c-V₂O₅, but also excellent rate capability and long-term cycling performance (with the residual capacity of 138.2 mAh·g⁻¹ over 10000 cycles at 10 A·g⁻¹).

Graphical abstract

Keywords

aqueous zinc battery / vanadium oxide cathode / intercalation / cycling performance / aluminum

References

[1] Jiang L, Lu Y, Zhao C, . Building aqueous K-ion batteries for energy storage.Nature Energy, 2019, 4(6): 495–503

[2] Lang J, Jiang C, Fang Y, . Room-temperature rechargeable Ca-ion based hybrid batteries with high rate capability and long-term cycling life.Advanced Energy Materials, 2019, 9(29): 1901099

[3] Yuan Y, Bin D, Dong X, . Intercalation pseudocapacitive nanoscale nickel hexacyanoferrate@carbon nanotubes as a high-rate cathode material for aqueous sodium-ion battery.ACS Sustainable Chemistry & Engineering, 2020, 8(9): 3655–3663

[4] Zhang B Y, Zhang W Y, Jin H X, . Research progress of cathode materials for rechargeable aluminum batteries in AlCl₃/[EMIm]Cl and other electrolyte systems.ChemistrySelect, 2023, 8(10): e202204575

[5] Yan L, Qi Y E, Dong X L, . Ammonium-ion batteries with a wide operating temperature window from −40 to 80 °C.eScience, 2021, 1(2): 212–218

[6] Kundu D, Adams B D, Duffort V, . A high-capacity and long-life aqueous rechargeable zinc battery using a metal oxide intercalation cathode.Nature Energy, 2016, 1(10): 16119

[7] Song W J, Lee S, Song G, . Stretchable aqueous batteries: progress and prospects.ACS Energy Letters, 2019, 4(1): 177–186

[8] Wu J, Yang L, Wang S, . Zinc ion modulation of hydrated vanadium pentoxide for high-performance aqueous zinc ion batteries.Journal of Power Sources, 2024, 595: 234057

[9] Liu Z, Huang Y, Huang Y, . Voltage issue of aqueous rechargeable metal-ion batteries.Chemical Society Reviews, 2020, 49(1): 180–232

[10] Yuan W, Qu X, Wang Y, . Polycationic polymer functionalized separator to stabilize aqueous zinc-iodine batteries.Energy Storage Materials, 2025, 76: 104130

[11] Lv T, Peng Y, Zhang G, . How about vanadium-based compounds as cathode materials for aqueous zinc ion batteries.Advanced Science, 2023, 10(12): 2206907

[12] Zhang N, Dong Y, Jia M, . Rechargeable aqueous Zn-V₂O₅ battery with high energy density and long cycle life.ACS Energy Letters, 2018, 3(6): 1366–1372

[13] Wan F, Niu Z . Design strategies for vanadium-based aqueous zinc-ion batteries.Angewandte Chemie International Edition, 2019, 58(46): 16358–16367

[14] Wang T, Li S, Weng X, . Ultrafast 3D hybrid-ion transport in porous V₂O₅ cathodes for superior-rate rechargeable aqueous zinc batteries.Advanced Energy Materials, 2023, 13(18): 2204358

[15] Zhang Y F, Li Q, Feng W C, , . Valence engineering via polyoxometalate-induced on vanadium centers for efficient aqueous zinc-ion batteries. Angewandte Chemie Interational Edition, 2025, 64(19): e202501728

[16] Li R, Zhang H, Zheng Q, . Porous V₂O₅ yolk–shell microspheres for zinc ion battery cathodes: activation responsible for enhanced capacity and rate performance.Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2020, 8(10): 5186–5193

[17] He P, Zhang G, Liao X, . Sodium ion stabilized vanadium oxide nanowire cathode for high-performance zinc-ion batteries.Advanced Energy Materials, 2018, 8(10): 1702463

[18] Ming F, Liang H, Lei Y, . Layered Mg_xV₂O₅·nH₂O as cathode material for high-performance aqueous zinc ion batteries.ACS Energy Letters, 2018, 3(10): 2602–2609

[19] Xia C, Guo J, Li P, . Highly stable aqueous zinc-ion storage using a layered calcium vanadium oxide bronze cathode.Angewandte Chemie International Edition, 2018, 57(15): 3943–3948

[20] 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

[21] Zhang D, Cao J, Yue Y, . Two birds with one stone: boosting zinc-ion insertion/extraction kinetics and suppressing vanadium dissolution of V₂O₅ via La³⁺ incorporation enable advanced zinc-ion batteries.ACS Applied Materials & Interfaces, 2021, 13(32): 38416–38424

[22] Jiang H, Zhang Y, Xu L, . Fabrication of (NH₄)₂V₃O₈ nanoparticles encapsulated in amorphous carbon for high capacity electrodes in aqueous zinc ion batteries.Chemical Engineering Journal, 2020, 382: 122844

[23] Yan M, He P, Chen Y, . Water-lubricated intercalation in V₂O₅·nH₂O for high-capacity and high-rate aqueous rechargeable zinc batteries.Advanced Materials, 2018, 30(1): 1703725

[24] Zhao D, Wang X, Zhang W, . Unlocking the capacity of vanadium oxide by atomically thin graphene-analogous V₂O₅·nH₂O in aqueous zinc-ion batteries.Advanced Functional Materials, 2023, 33(13): 2211412

[25] Sun J, Zhao Y, Liu Y, . “Three-in-one” strategy that ensures V₂O₅·nH₂O with superior Zn²⁺ storage by simultaneous protonated polyaniline intercalation and encapsulation.Small Structures, 2022, 3(4): 2100212

[26] Qi Y, Liao M, Xie Y, . Long-life vanadium oxide cathode for zinc battery enabled by polypyrrole intercalation and concentrated electrolyte.Chemical Engineering Journal, 2023, 470: 143971

[27] Chen S, Li K, Hui K S, . Regulation of lamellar structure of vanadium oxide via polyaniline intercalation for high-performance aqueous zinc-ion battery.Advanced Functional Materials, 2020, 30(43): 2003890

[28] Yang Y, Tang Y, Fang G, . Li⁺ intercalated V₂O₅·nH₂O with enlarged layer spacing and fast ion diffusion as an aqueous zinc-ion battery cathode.Energy & Environmental Science, 2018, 11(11): 3157–3162

[29] Tian M, Liu C, Zheng J, . Structural engineering of hydrated vanadium oxide cathode by K⁺ incorporation for high-capacity and long-cycling aqueous zinc ion batteries.Energy Storage Materials, 2020, 29: 9–16

[30] Qi Y, Huang J, Yan L, . Towards high-performance aqueous zinc-ion battery via cesium ion intercalated vanadium oxide nanorods.Chemical Engineering Journal, 2022, 442: 136349

[31] Liu Y, Xiao X, Liu X, . Aluminium vanadate with unsaturated coordinated V centers and oxygen vacancies: surface migration and partial phase transformation mechanism in high performance zinc-ion batteries.Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2022, 10(2): 912–927

[32] Luo Y R. Comprehensive Handbook of Chemical Bond Energies. Boca Raton, USA: CRC Press, 2007

[33] Zhang W, Liang S, Fang G, . Ultra-high mass-loading cathode for aqueous zinc-ion battery based on graphene-rapped aluminum vanadate nanobelts.Nano-Micro Letters, 2019, 11(1): 69

[34] Wei T, Liu Y, Yang G, . Aluminum vanadate hollow spheres as zero-strain cathode material for highly reversible and durable aqueous zinc-ion batteries.Energy Storage Materials, 2020, 30: 130–137

[35] Chen H D, Huang J J, Tian S H, . Interlayer modification of pseudocapacitive vanadium oxide and Zn(H₂O)_n²⁺ migration regulation for ultrahigh rate and durable aqueous zinc-ion batteries.Advanced Science, 2021, 8(14): 2004924

[36] Zheng J, Liu C, Tian M, . Fast and reversible zinc ion intercalation in Al-ion modified hydrated vanadate.Nano Energy, 2020, 70: 104519

[37] Zong Q, Du W, Liu C, . Enhanced reversible zinc ion intercalation in deficient ammonium vanadate for high-performance aqueous zinc-ion battery.Nano-Micro Letters, 2021, 13(1): 116

[38] Li K, Gong Y, Lin J . Benzoquinone-intercalated vanadium oxide in the electrolyte with Al³⁺ for zinc-ion storage: dual-pillar effect and reversible disorder–order conversion.Chemical Engineering Journal, 2023, 452: 139621

[39] He W, Fan Z, Huang Z, . A Li⁺ and PANI co-intercalation strategy for hydrated V₂O₅ to enhance zinc ion storage performance.Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2022, 10(36): 18962–18971

[40] Feng Z, Sun J, Liu Y, . Engineering interlayer space of vanadium oxide by pyridinesulfonic acid-assisted intercalation of polypyrrole enables enhanced aqueous zinc-ion storage.ACS Applied Materials & Interfaces, 2021, 13(51): 61154–61165

[41] Song H, Liu C, Zhang C, . Self-doped V⁴⁺-V₂O₅ nanoflake for 2 Li-ion intercalation with enhanced rate and cycling performance.Nano Energy, 2016, 22: 1–10

[42] Liu F, Chen Z, Fang G, . V₂O₅ nanospheres with mixed vanadium valences as high electrochemically active aqueous zinc-ion battery cathode.Nano-Micro Letters, 2019, 11(1): 25

[43] Qian W T, Chen Z, Chen L, . Mixed-valence vanadium oxides with ultra-high rates and long cycles for aqueous zinc ion batteries.Applied Surface Science, 2025, 684: 161981

[44] Li J, Luo N, Wan F, . Defected vanadium bronzes as superb cathodes in aqueous zinc-ion batteries.Nanoscale, 2020, 12(40): 20638–20648

[45] Hu P, Zhu T, Ma J, . Porous V₂O₅ microspheres: a high-capacity cathode material for aqueous zinc-ion batteries.Chemical Communications, 2019, 55(58): 8486–8489

[46] Ma G, Yuan W, Li X, . Organic cations texture zinc metal anodes for deep cycling aqueous zinc batteries.Advanced Materials, 2024, 36(35): 2408287

[47] Zheng S S, Sun Y, Xue H G, . Dual-ligand and hard-soft-acid-base strategies to optimize metal‒organic framework nanocrystals for stable electrochemical cycling performance.National Science Review, 2022, 9(7): nwab197

[48] Lindström H, Södergren S, Solbrand A, . Li⁺ ion insertion in TiO₂ (Anatase).2. Voltammetry on nanoporous films. The Journal of Physical Chemistry B, 1997, 101(39): 7717–7722

[49] Guo X, Fang G, Zhang W, . Mechanistic insights of Zn²⁺ storage in sodium vanadates.Advanced Energy Materials, 2018, 8(27): 1801819

[50] Zhang Y, Wan F, Huang S, . A chemically self-charging aqueous zinc-ion battery.Nature Communications, 2020, 11(1): 2199

[51] Su Y C, Yuan G Q, Hu J L, . Thiosalicylic-acid-mediated coordination structure of nickel center via thermodynamic modulation for aqueous Ni–Zn batteries.Advanced Materials, 2024, 36(32): 2406094

[52] Sun Q C, Cheng H W, Yuan Y F, . Uncovering the fundamental role of interlayer water in charge storage for bilayered V₂O₅·nH₂O xerogel cathode materials.Advanced Energy Materials, 2023, 13(3): 2202515

[53] Zhang G, Wu T, Zhou H, . Rich alkali ions preintercalated vanadium oxides for durable and fast zinc-ion storage.ACS Energy Letters, 2021, 6(6): 2111–2120

RIGHTS & PERMISSIONS

Higher Education Press