Suppressing vertical aluminum growth via accelerated interfacial Cl⁻ dynamics for high-areal-capacity, long-life aluminum metal anodes

Abstract

Despite the high theoretical volumetric capacity of aluminum metal anodes (AMAs), their practical use in rechargeable aluminum batteries (RABs) is hindered by low capacity utilization and short-circuit-induced cell failure. Herein, we investigate the aluminum nucleation and growth behavior on a 2D electrode platform to uncover the origins of such failures, integrating experimental analysis with theoretical calculations. We find that the failure capacity is strongly dependent on separator thickness, irrespective of separator type. Short-circuiting arises from unfavorable multi-step reactions, where inefficient Cl⁻ removal promotes vertical Al growth due to localized accumulation of reaction products. Based on these insights, we design a 3D nanostructured graphitic carbon electrode (3D-GCE) to mitigate local AlCl₄⁻ buildup and enhance Al reversibility. Additionally, a Cl-doped polypropylene (Cl-PP) separator is employed to facilitate Cl⁻ transport via the Grotthuss mechanism. This integrated design achieves a record capacity of ~8.2 mAh cm⁻² and stable cycling over 500 cycles with a single thin PP separator.

Keywords

3D nanostructured graphitic carbon electrode / aluminum metal anode / aluminum nucleation and growth behavior / cell-failure mechanism / Cl-doped polypropylene separator / high volumetric energy density rechargeable aluminum batteries

References

[1] Bruce D, Kamath H, Tarascon J-M. Electrical energy storage for the grid: a battery of choices. Science. 2011; 334(6058): 928-935.

[2] Thackeray MM, Wolverton C, Isaacs ED. Electrical energy storage for transportation—approaching the limits of, and going beyond, lithium-ion batteries. Energ Environ Sci. 2012; 5(7): 7854.

[3] Cano ZP, Banham D, Ye S, et al. Batteries and fuel cells for emerging electric vehicle markets. Nat Energy. 2018; 3(4): 279-289.

[4] Manthiram A. A reflection on lithium-ion battery cathode chemistry. Nat Commun. 2020; 11(1):1550.

[5] Larcher D, Tarascon J-M. Towards greener and more sustainable batteries for electrical energy storage. Nat Chem. 2015; 7(1): 19-29.

[6] Wu F, Yushin G. Conversion cathodes for rechargeable lithium and lithium-ion batteries. Energ Environ Sci. 2017; 10(2): 435-459.

[7] Evarts EC. To the limits of lithium. Nature. 2015; 526(7575): S93-S95.

[8] Zubi G, D.-Lopez R, Carvalho M, Pasaoglu G. The lithium-ion battery: state of the art and future perspectives. Renew Sustain Energy Rev. 2018; 89: 292-308.

[9] Elia GA, Marquardt K, Hoeppner K, et al. An overview and future perspectives of aluminum batteries. Adv Mater. 2016; 28(35): 7564-7579.

[10] Lin M-C, Gong M, Lu B, et al. An ultrafast rechargeable aluminum-ion battery. Nature. 2015; 520(7547): 324-328.

[11] Zhang X, Tang Y, Zhang F, Lee C-S. A novel aluminum-graphite dual-ion battery. Adv Energy Mater. 2016; 6(11):1502588.

[12] Zheng J, Bock DC, Tang T, et al. Regulating electrodeposition morphology in high-capacity aluminium and zinc battery anodes using interfacial metal–substrate bonding. Nat Energy. 2021; 6(4): 398-406.

[13] Ng KL, Amrithraj B, Azimi G. Nonaqueous rechargeable aluminum batteries. Joule. 2022; 6(1): 134-170.

[14] Matsuda Y, Ouchi Y, Tamura H. Anodic polarization of aluminium in organic electrolytes. J Appl Electrochem. 1974; 4: 53-56.

[15] Wang H, Gu S, Bai Y, Wu F, Wu C. High-voltage and noncorrosive ionic liquid electrolyte used in rechargeable aluminum battery. ACS Appl Mater Interfaces. 2016; 8(41): 27444-27448.

[16] Loaiza LC, Lindahl N, Johansson P. Initial evolution of passivation layers in non-aqueous Aluminium batteries. J Electrochem Soc. 2023; 170(3):030512.

[17] Wilkes JS, Frye JS, Reynolds GF. ²⁷A1 and ¹³C NMR studies of aluminum chloride-Dialkylimidazolium chloride molten salts. Inorg Chem. 1983; 22(26): 3870-3872.

[18] Wilkes JS, Levisky JA, Wilson RA, Hussey CL. Dialkylimidazolium Chloroaluminate melts: a new class of room-temperature ionic liquids for electrochemistry, spectroscopy, and synthesis. Inorg Chem. 1982; 21(3): 1263-1264.

[19] Armand A, Fannin J, King LA, Levisky JA, Wilkes JS. Properties of 1,3-Dialkyiimidazolium chloride-aluminum chloride ionic liquids. 1. Ion interactions by nuclear magnetic resonance spectroscopy. J Phys Chem. 1984; 88(12): 2609-2614.

[20] Böttcher R, Mai S, Ispas A, Bund A. Aluminum deposition and dissolution in [EMIm]Cl-based ionic liquids–kinetics of charge–transfer and the rate–determining step. J Electrochem Soc. 2020; 167(10):102516.

[21] Shen X, Sun T, Yang L, et al. Ultra-fast charging in aluminum-ion batteries: electric double layers on active anode. Nat Commun. 2021; 12(1):820.

[22] Wang S, Guo Y, Du X, et al. Space limited growth strategy for ultra-high areal capacity rechargeable aluminum batteries. Energy Storage Mater. 2023; 60:102826.

[23] Wang S, Guo Y, Du X, et al. Bottom growth strategy for high areal capacity rechargeable aluminum batteries. Nano Energy. 2023; 114:108626.

[24] Long Y, Li H, Ye M, et al. Suppressing Al dendrite growth towards a long-life Al-metal battery. Energy Storage Mater. 2021; 34: 194-202.

[25] Wang S, Guo Y, Du X, et al. Preferred crystal plane electrodeposition of aluminum anode with high lattice-matching for long-life aluminum batteries. Nat Commun. 2024; 15(1):6476.

[26] Gu S, Nie W, Meng Q, et al. Stabilizing the aluminum metal anode through polymer coating-enabled regulation of exchange current. Energ Environ Sci. 2025; 18(3): 1477-1488.

[27] Lv A, Wang M, Shi H, Lu S, Zhang J, Jiao S. A carbon aerogel lightweight Al battery for fast storage of fluctuating energy. Adv Mater. 2023; 35(35):2303943.

[28] Meng Y, Wang J, Wang M, et al. Anode-free aluminum electrode with ultralong cycle life and high coulombic efficiency exceeding 99.92% enabled by a lattice-matching layer. Adv Energy Mater. 2023; 13(30):2301322.

[29] Rakov DA, Ahmed N, Kong Y, et al. Exploring the impact of in situ-formed solid–electrolyte interphase on the cycling performance of aluminum metal anodes. ACS Nano. 2024; 18(41): 28456-28468.

[30] Yao L, Ju S, Xia G, Sun D, Yu X. Dynamic Al–O interactions enable uniform Al deposition toward high energy-density and practical Al metal batteries. ACS Energy Lett. 2024; 9(1): 253-261.

[31] Lindahl N, Bitenc J, Dominko R, Johansson P. Aluminum metal–organic batteries with integrated 3D thin film anodes. Adv Funct Mater. 2020; 30(51):2004573.

[32] Li J, Hui KS, Ji S, et al. Electrodeposition of a dendrite-free 3D Al anode for improving cycling of an aluminum–graphite battery. Carbon Energy. 2022; 4(2): 155-169.

[33] Xu C, Diemant T, Liu X, Passerini S. Locally concentrated deep eutectic liquids electrolytes for low-polarization aluminum metal batteries. Adv Mater. 2024; 36(24):2400263.

[34] Ha S, Hyun JC, Kwak JH, et al. Waste-induced pyrolytic carbon nanotube forest as a catalytic host electrode for high-performance aluminum metal anodes. Chem Eng J. 2022; 437:135416.

[35] Yoon J, Moon S, Ha S, Lim H-K, Jin H-J, Yun YS. Nanoconfinement effect of nanoporous carbon electrodes for ionic liquid-based aluminum metal anode. J Energy Chem. 2022; 74(11): 121-127.

[36] Heo YH, Lee J, Ha S, et al. 3D-structured bifunctional MXene paper electrodes for protection and activation of Al metal anodes. J Mater Chem A. 2023; 11(26): 14380-14389.

[37] Chen J, Zhu Q, Jiang L, et al. Rechargeable aqueous aluminum organic batteries. Angew Chem Int Ed. 2020; 60(11): 5794-5799.

[38] Liu X, Zhu Q, Jiang A, et al. Realizing a wide-temperature aluminum-foil-anode-based lithium-ion battery. Adv Funct Mater. 2025;e21637.

[39] Fedorov MV, Kornyshev AA. Ionic liquids at electrified interfaces. Chem Rev. 2014; 114(5): 2978-3036.

[40] Kirchner K, Kirchner T, Ivanistsev V, Fedorov MV. Electrical double layer in ionic liquids: structural transitions from multilayer to monolayer structure at the interface. Electrochim Acta. 2013; 110: 762-771.

[41] Takahashi S, Suzuya K, Kohara S, Koura N, Curtiss LA, Saboungi M-L. Structure of l-Ethyl-3-Methylimidazolium Chloroaluminates: neutron diffraction measurements and ab inìtìo calculations. Z Phys Chem. 1999; 209(2): 209-221.

[42] Kirchner B, Seitsonen AP, Hutter J. Ionic liquids from Car-Parrinello simulations, part I: liquid AlCl₃. J Phys Chem B. 2006; 110(23): 11475-11480.

[43] Guo K, Wang W, Jiao H, Song W-L, Jiao S. Chain-transported hypercoordinated chloroaluminate electrolyte for solid-state aluminum-ion batteries. ACS Nano. 2025; 19(36): 32595-32605.

[44] Kumar S, Raghupathy R, Vezzù K, et al. Sodium ion-conducting electrolytes based on chloroaluminate ionic liquids and δ-NaCl. ChemSusChem. 2024; 17(20):e202400863.

[45] Xie Y, Meng Y, Liu M, et al. Optimized electrode/electrolyte interface engineering for dendrite-free Al anode and self-activated graphite cathode. Adv Funct Mater. 2024; 34(48):2411395.

[46] Almodovar P, Giraldo DA, Chancon J, Alvarez-Serrano I, Lopez ML. δ-MnO₂ nanofibers: a promising cathode material for new aluminum-ion batteries. ChemElectroChem. 2020; 7(9): 2102-2106.

[47] Yun YS, Bak H, Jin H-J. Porous carbon nanotube electrodes supported by natural polymeric membrances for PEMFC. Synth Met. 2010; 160(7-8): 561-565.

[48] Hugo V-VV, Alejandro H-SM, Matia V-SA, et al. Molecular modeling and synthesis of ethyl benzeyl carbamates as possible ixodicide activity. Comput Chem. 2019; 7(1): 1-26.

RIGHTS & PERMISSIONS

2026 The Author(s). InfoMat published by UESTC and John Wiley & Sons Australia, Ltd.