Highly reversible and long-lived zinc anode assisted by polymer-based hydrophilic coating

Abstract

Rechargeable aqueous zinc-ion batteries (AZIBs) are the most promising candidates for the energy storage due to their high safety, rich resources, and large specific capacity. However, AZIBs using neutral or slightly acidic electrolytes still face side effects and zinc dendrites on the anode surface. To stabilize the Zn anode, a chemically stable and multi-functional coating of polyvinylidene fluoride (PVDF) and 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) was prepared on the Zn surface. The anhydride groups in 6FDA can improve the hydrophilicity, promoting the migration of zinc ions. Besides, PVDF is compatible with 6FDA because of the presence of organic F-containing groups, which can also effectively reduce the nucleation overpotential and exhibit the dendrite-free Zn deposition/stripping. The PVDF/6FDA@Zn symmetric cell can cycle for 5000 h at a current density of 0.5 mA·cm⁻², maintaining the extremely low polarization voltage and overpotential of 28 and 8 mV, respectively. The PVDF/6FDA@Zn||MnO₂ full cell can remain a specific capacity of ~90 mAh·g⁻¹ after 2000 cycles at 1.5 A·g⁻¹. This simple method achieves a reversible Zn anode, providing an inspiring strategy for ultra-long-cycle AZIBs.

Graphical abstract

Keywords

aqueous zinc ion battery / zinc anode / polyvinylidene fluoride / composite film

References

[1] Khalifa H, El-Safty S A, Reda A, . One-dimensional hierarchical anode/cathode materials engineering for high-performance lithium-ion batteries.Energy Storage Materials, 2021, 37: 363–377

[2] Zeng Y, Chalise D, Lubner S D, . A review of thermal physics and management inside lithium-ion batteries for high energy density and fast charging.Energy Storage Materials, 2021, 41: 264–288

[3] Chayambuka K, Mulder G, Danilov D L, . From Li-ion batteries toward Na-ion chemistries: challenges and opportunities.Advanced Energy Materials, 2020, 10(38): 2001310

[4] Zhang X, Sun Q, Zhen C, . Recent progress in flame-retardant separators for safe lithium-ion batteries.Energy Storage Materials, 2021, 37: 628–647

[5] Hosaka T, Kubota K, Hameed A S, . Research development on K-ion batteries.Chemical Reviews, 2020, 120(14): 6358–6466

[6] Liu Y, Li L, Ji X, . Scientific challenges and improvement strategies of Zn-based anodes for aqueous Zn-ion batteries.Chemical Record, 2022, 22(10): e202200114

[7] Wang F, Borodin O, Gao T, . Highly reversible zinc metal anode for aqueous batteries.Nature Materials, 2018, 17(6): 543–549

[8] Glatz H, Tervoort E, Kundu D . Unveiling critical insight into the Zn metal anode cyclability in mildly acidic aqueous electrolytes: implications for aqueous zinc batteries.ACS Applied Materials & Interfaces, 2020, 12(3): 3522–3530

[9] Jia H, Wang Z, Tawiah B, . Recent advances in zinc anodes for high-performance aqueous Zn-ion batteries.Nano Energy, 2020, 70: 104523

[10] Shang Y, Kundu D . Understanding and performance of the zinc anode cycling in aqueous zinc-ion batteries and a roadmap for the future.Batteries & Supercaps, 2022, 5(5): e202100394

[11] Yang Z, Lv C, Li W, . Revealing the two-dimensional surface diffusion mechanism for zinc dendrite formation on zinc anode.Small, 2022, 18(43): 2104148

[12] Yang Q, Li Q, Liu Z, . Dendrites in Zn-based batteries.Advanced Materials, 2020, 32(48): 2001854

[13] Yang J, Zhao R, Wang Y, . Insights on artificial interphases of Zn and electrolyte: protection mechanisms, constructing techniques, applicability, and prospective.Advanced Functional Materials, 2023, 33(14): 2213510

[14] Hu Y, Li Z, Wang Z, . Suppressing local dendrite hotspots via current density redistribution using a superlithiophilic membrane for stable lithium metal anode.Advanced Science, 2023, 10(12): 2206995

[15] Li D, Wei Z, Lei W, . In situ crosslinked hybrid aluminum polymer film for high-performance solid electrolyte interphase of lithium metal battery.Journal of Power Sources, 2023, 563: 232808

[16] Wang X, Sun C, Wu Z S . Recent progress of dendrite-free stable zinc anodes for advanced zinc-based rechargeable batteries: fundamentals, challenges, and perspectives.SusMat, 2023, 3(2): 180–206

[17] Zhou L F, Du T, Li J Y, . A strategy for anode modification for future zinc-based battery application.Materials Horizons, 2022, 9(11): 2722–2751

[18] Nie W, Cheng H, Sun Q, . Design strategies toward high-performance Zn metal anode.Small Methods, 2023, 7: 2201572

[19] Ren Q, Tang X, Zhao X, . A zincophilic interface coating for the suppression of dendrite growth in zinc anodes.Nano Energy, 2023, 109: 108306

[20] Guo W, Cong Z, Guo Z, . Dendrite-free Zn anode with dual channel 3D porous frameworks for rechargeable Zn batteries.Energy Storage Materials, 2020, 30: 104–112

[21] Chladil L, Cech O, Smejkal J, . Study of zinc deposited in the presence of organic additives for zinc-based secondary batteries.Journal of Energy Storage, 2019, 21: 295–300

[22] Mitha A, Mi H, Dong W, . Thixotropic gel electrolyte containing poly (ethylene glycol) with high zinc ion concentration for the secondary aqueous Zn/LiMn₂O₄ battery.Journal of Electroanalytical Chemistry, 2019, 836: 1–6

[23] Yang X, Liu S, Tang J, . Effective inhibition of zinc dendrites during electrodeposition using thiourea derivatives as additives.Journal of Materials Science, 2019, 54(4): 3536–3546

[24] Naveed A, Yang H, Yang J, . Highly reversible and rechargeable safe Zn batteries based on a triethyl phosphate electrolyte.Angewandte Chemie International Edition, 2019, 58(9): 2760–2764

[25] Wang F, Borodin O, Gao T, . Highly reversible zinc metal anode for aqueous batteries.Nature Materials, 2018, 17(6): 543–549

[26] Zhao Z, Zhao J, Hu Z, . Long-life and deeply rechargeable aqueous Zn anodes enabled by a multifunctional brightener-inspired interphase.Energy & Environmental Science, 2019, 12(6): 1938–1949

[27] Zhao J, Zhang J, Yang W, . “Water-in-deep eutectic solvent” electrolytes enable zinc metal anodes for rechargeable aqueous batteries.Nano Energy, 2019, 57: 625–634

[28] Chen P, Yuan X, Xia Y, . An artificial polyacrylonitrile coating layer confining zinc dendrite growth for highly reversible aqueous zinc-based batteries.Advanced Science, 2021, 8(11): 2100309

[29] Zeng X, Xie K, Liu S, . Bio-inspired design of an in situ multifunctional polymeric solid–electrolyte interphase for Zn metal anode cycling at 30 mA·cm⁻² and 30 mAh·cm⁻².Energy & Environmental Science, 2021, 14(11): 5947–5957

[30] Niu B, Li Z, Cai S, . Robust Zn anode enabled by a hydrophilic adhesive coating for long-life zinc-ion hybrid supercapacitors.Chemical Engineering Journal, 2022, 442: 136217

[31] Hieu L T, So S, Kim I T, . Zn anode with flexible β-PVDF coating for aqueous Zn-ion batteries with long cycle life.Chemical Engineering Journal, 2021, 411: 128584

[32] Wang X, Wang X, Zhou Y, . In-situ construction of multifunctional protection interface for ultra-stable zinc anodes.Journal of Alloys and Compounds, 2023, 947: 169510

[33] Wei T, Zhang X, Ren Y, . Reconstructing anode/electrolyte interface and solvation structure towards high stable zinc anode.Chemical Engineering Journal, 2023, 457: 141272

[34] Tao F, Feng K, Liu Y, . Suppressing interfacial side reactions of zinc metal anode via isolation effect toward high-performance aqueous zinc-ion batteries.Nano Research, 2023, 16(5): 6789–6797

[35] Hao J, Li X, Zhang S, . Designing dendrite-free zinc anodes for advanced aqueous zinc batteries.Advanced Functional Materials, 2020, 30(30): 2001263

[36] Ge X, Zhang W, Song F, . Single-ion-functionalized nanocellulose membranes enable lean-electrolyte and deeply cycled aqueous zinc-metal batteries.Advanced Functional Materials, 2022, 32(26): 2200429

[37] Zhang Z, Wang R, Hu J, . An in situ self-assembled 3D zincophilic heterogeneous metal layer on a zinc metal surface for dendrite-free aqueous zinc-ion batteries.Sustainable Energy & Fuels, 2021, 5(22): 5843–5850

[38] Xie C, Li Y, Wang Q, . Issues and solutions toward zinc anode in aqueous zinc-ion batteries: a mini review.Carbon Energy, 2020, 2(4): 540–560

[39] Lee S, Song G, Kim S, . Ion-selective and chemical-protective elastic block copolymer interphase for durable zinc metal anode.Cell Reports Physical Science, 2022, 3(10): 101070

[40] Zhao R, Yang J, Han X, . Stabilizing Zn metal anodes via cation/anion regulation toward high energy density Zn-ion batteries.Advanced Energy Materials, 2023, 13(8): 2203542

RIGHTS & PERMISSIONS

Higher Education Press