Understanding the reversible electrodeposition of aluminum in low-cost room-temperature molten salts

Garcia-Mendez, Regina; Zheng, Jingxu; Bock, David C.; Jaye, Cherno; Fischer, Daniel A.; Marschilok, Amy C.; Takeuchi, Kenneth J.; Takeuchi, Esther S.; Archer, Lynden A.

doi:10.1016/j.xcrp.2023.101452

Understanding the reversible electrodeposition of aluminum in low-cost room-temperature molten salts

Journal Article · Tue Jun 06 00:00:00 EDT 2023 · Cell Reports Physical Science

DOI:https://doi.org/10.1016/j.xcrp.2023.101452· OSTI ID:2440524

Garcia-Mendez, Regina ^[1]; Zheng, Jingxu ^[2]; Bock, David C. ^[3]; Jaye, Cherno ^[4]; Fischer, Daniel A. ^[4]; Marschilok, Amy C. ^[3]; Takeuchi, Kenneth J. ^[3]; Takeuchi, Esther S. ^[3]; ^[1]

Cornell Univ., Ithaca, NY (United States)
Cornell Univ., Ithaca, NY (United States); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)

Aluminum is the most earth-abundant metal, trivalent, and inert in ambient air; it also has a density approximately five times that of lithium at room temperature, making it attractive for cost-effective, long-duration storage in batteries. Here, we investigate structural requirements and physicochemical and transport properties of ionic liquid (IL) electrolytes thought to enable high reversibility of Al battery anodes. We find that intentionally designed, low-cost IL analogs, including ammonium-based molten salts, offer comparable Al anode reversibility to state-of-the-art imidazolium-based IL melts. A critical ratio of solvated Al-ion species is required to balance the effects of Lewis acidity needed to continuously etch native Al₂O₃ and form a stable solid electrolyte interphase on Al. Our findings open new opportunities for developing simple, cost-effective, room-temperature Al batteries that enable long-duration electrical energy storage.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2m#S)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012673; SC0012704

OSTI ID:: 2440524

Report Number(s):: BNL--226049-2024-JAAM

Journal Information:: Cell Reports Physical Science, Journal Name: Cell Reports Physical Science Journal Issue: 6 Vol. 4; ISSN 2666-3864

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (56)

Ionic Liquid Analogs of AlCl ₃ with Urea Derivatives as Electrolytes for Aluminum Batteries Angell, Michael; Zhu, Guanzhou; Lin, Meng‐Chang Advanced Functional Materials, Vol. 30, Issue 4 https://doi.org/10.1002/adfm.201901928	journal	October 2019
Electroceramics: Characterization by Impedance Spectroscopy Irvine, John T. S.; Sinclair, Derek C.; West, Anthony R. Advanced Materials, Vol. 2, Issue 3 https://doi.org/10.1002/adma.19900020304	journal	March 1990
An Overview and Future Perspectives of Aluminum Batteries Elia, Giuseppe Antonio; Marquardt, Krystan; Hoeppner, Katrin Advanced Materials, Vol. 28, Issue 35 https://doi.org/10.1002/adma.201601357	journal	June 2016
Carnelley's Rule and the Prediction of Melting Point Yalkowsky, Samuel H. Journal of Pharmaceutical Sciences, Vol. 103, Issue 9 https://doi.org/10.1002/jps.24034	journal	September 2014
Determination of peak positions and areas from wide-scan XPS spectra Turner, N. H.; Single, A. M. Surface and Interface Analysis, Vol. 15, Issue 3 https://doi.org/10.1002/sia.740150305	journal	March 1990
The role of noncrystalline films in the oxidation and corrosion of metals Revesz, A. G.; Fehlner, F. P. Oxidation of Metals, Vol. 15, Issue 3-4 https://doi.org/10.1007/BF01058831	journal	April 1981
Electrodeposition of aluminium in aluminium chloride/1-methyl-3-ethylimidazolium chloride Lai, P. K.; Skyllas-Kazacos, M. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 248, Issue 2, p. 431-440 https://doi.org/10.1016/0022-0728(88)85103-9	journal	July 1988
Electrodeposition and dissolution of aluminium in ambient temperature molten salt system aluminium chloride n-butylpyridinium chloride Qin, Qi-Xian; Skyllas-Kazacos, M. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 168, Issue 1-2 https://doi.org/10.1016/0368-1874(84)87098-7	journal	May 1984
Graphite intercalation of bis(trifluoromethanesulfonyl) imide and other anions with perfluoroalkanesulfonyl substituents Zhang, Xuerong; Sukpirom, Nipaka; Lerner, Michael M. Materials Research Bulletin, Vol. 34, Issue 3 https://doi.org/10.1016/S0025-5408(99)00035-5	journal	February 1999
Structure of thin aluminium-oxide films determined from valence band spectra measured using XPS Snijders, P. C.; Jeurgens, L. P. H.; Sloof, W. G. Surface Science, Vol. 496, Issue 1-2 https://doi.org/10.1016/S0039-6028(01)01591-6	journal	January 2002
The probing depth of total electron yield in the sub-keV range: TEY-XAS and X-PEEM Frazer, Bradley H.; Gilbert, Benjamin; Sonderegger, Brandon R. Surface Science, Vol. 537, Issue 1-3 https://doi.org/10.1016/S0039-6028(03)00613-7	journal	July 2003
Technological and scientific issues of room-temperature molten salts Takahashi, S.; Koura, N.; Kohara, S. Plasmas & Ions, Vol. 2, Issue 3-4 https://doi.org/10.1016/S1288-3255(99)00105-7	journal	October 1999
The first graphite intercalation compounds containing tris(pentafluoroethyl)trifluorophosphate Özmen-Monkul, Bahar; Lerner, Michael M. Carbon, Vol. 48, Issue 11 https://doi.org/10.1016/j.carbon.2010.05.005	journal	September 2010
Electrochemical oxidation of urea in aqueous solutions using a boron-doped thin-film diamond electrode Cataldo Hernández, M.; Russo, N.; Panizza, M. Diamond and Related Materials, Vol. 44 https://doi.org/10.1016/j.diamond.2014.02.006	journal	April 2014
Geometry and fast diffusion of AlCl 4 cluster intercalated in graphite Wu, M. S.; Xu, B.; Chen, L. Q. Electrochimica Acta, Vol. 195 https://doi.org/10.1016/j.electacta.2016.02.144	journal	March 2016
Electrochemical investigation of urea oxidation reaction on β Ni(OH)2 and Ni/Ni(OH)2 Singh, Ramesh Kumar; Schechter, Alex Electrochimica Acta, Vol. 278 https://doi.org/10.1016/j.electacta.2018.05.049	journal	July 2018
A group contribution method to predict the melting point of ionic liquids Lazzús, Juan A. Fluid Phase Equilibria, Vol. 313 https://doi.org/10.1016/j.fluid.2011.09.018	journal	January 2012
Efficient Aluminum Chloride–Natural Graphite Battery Kravchyk, Kostiantyn V.; Wang, Shutao; Piveteau, Laura Chemistry of Materials, Vol. 29, Issue 10 https://doi.org/10.1021/acs.chemmater.7b01060	journal	May 2017
Synchrotron X-ray Analytical Techniques for Studying Materials Electrochemistry in Rechargeable Batteries Lin, Feng; Liu, Yijin; Yu, Xiqian Chemical Reviews, Vol. 117, Issue 21 https://doi.org/10.1021/acs.chemrev.7b00007	journal	September 2017
Flexible Few-Layered Graphene for the Ultrafast Rechargeable Aluminum-Ion Battery Jung, Sung Chul; Kang, Yong-Ju; Yoo, Dong-Joo The Journal of Physical Chemistry C, Vol. 120, Issue 25 https://doi.org/10.1021/acs.jpcc.6b03657	journal	June 2016
Room-Temperature Electrodeposition of Aluminum via Manipulating Coordination Structure in AlCl₃ Solutions Wen, Xiaoyu; Liu, Yuhang; Xu, Da The Journal of Physical Chemistry Letters, Vol. 11, Issue 4 https://doi.org/10.1021/acs.jpclett.0c00256	journal	February 2020
Engineering Multiscale Coupled Electron/Ion Transport in Battery Electrodes Zheng, Jingxu; Garcia-Mendez, Regina; Archer, Lynden A. ACS Nano, Vol. 15, Issue 12 https://doi.org/10.1021/acsnano.1c08719	journal	December 2021
Melting Point and Molecular Symmetry Brown, R. J. C.; Brown, R. F. C. Journal of Chemical Education, Vol. 77, Issue 6 https://doi.org/10.1021/ed077p724	journal	June 2000
Spectroscopic investigations of complexes between acetonitrile and aluminum trichloride. 2. Study of AlCl3 in acetonitrile mixtures of tetramethylammonium chloride, water, or nitromethane Dalibart, M.; Derouault, J.; Granger, P. Inorganic Chemistry, Vol. 21, Issue 6 https://doi.org/10.1021/ic00136a023	journal	June 1982
Aluminum-27 and carbon-13 NMR studies of aluminum chloride-dialkylimidazolium chloride molten salts Wilkes, John S.; Frye, James S.; Reynolds, G. Fredric Inorganic Chemistry, Vol. 22, Issue 26 https://doi.org/10.1021/ic00168a011	journal	December 1983
Crystal structures of tetratellurium(2+) tetrachloroaluminate and heptachlorodialuminate, Te42+(AlCl4-)2 and Te42+(Al2Cl7-)2 Couch, Thomas W.; Lokken, Donald A.; Corbett, John D. Inorganic Chemistry, Vol. 11, Issue 2 https://doi.org/10.1021/ic50108a031	journal	February 1972
Core electron binding energies in some Group IIIA, VB, and VIB compounds McGuire, G. E.; Schweitzer, G. K.; Carlson, Thomas A. Inorganic Chemistry, Vol. 12, Issue 10 https://doi.org/10.1021/ic50128a045	journal	October 1973
Properties of 1,3-dialkylimidazolium chloride-aluminum chloride ionic liquids. 2. Phase transitions, densities, electrical conductivities, and viscosities Fannin, Armand A.; Floreani, Danilo A.; King, Lowell A. The Journal of Physical Chemistry, Vol. 88, Issue 12 https://doi.org/10.1021/j150656a038	journal	June 1984
Theoretical x-ray absorption fine structure standards Rehr, J. J.; Mustre de Leon, J.; Zabinsky, S. I. Journal of the American Chemical Society, Vol. 113, Issue 14 https://doi.org/10.1021/ja00014a001	journal	July 1991
Reversible Al Metal Anodes Enabled by Amorphization for Aqueous Aluminum Batteries Yan, Chunshuang; Lv, Chade; Jia, Bei-Er Journal of the American Chemical Society, Vol. 144, Issue 25 https://doi.org/10.1021/jacs.2c04820	journal	June 2022
Pulsed-Gradient Spin−Echo ¹ H and ¹⁹ F NMR Ionic Diffusion Coefficient, Viscosity, and Ionic Conductivity of Non-Chloroaluminate Room-Temperature Ionic Liquids Noda, Akihiro; Hayamizu, Kikuko; Watanabe, Masayoshi The Journal of Physical Chemistry B, Vol. 105, Issue 20 https://doi.org/10.1021/jp004132q	journal	May 2001
Combining X-ray Absorption and X-ray Diffraction Techniques for in Situ Studies of Chemical Transformations in Heterogeneous Catalysis: Advantages and Limitations Frenkel, A. I.; Wang, Q.; Marinkovic, N. The Journal of Physical Chemistry C, Vol. 115, Issue 36 https://doi.org/10.1021/jp205204e	journal	August 2011
An ultrafast rechargeable aluminium-ion battery Lin, Meng-Chang; Gong, Ming; Lu, Bingan Nature, Vol. 520, Issue 7547 https://doi.org/10.1038/nature14340	journal	April 2015
Regulating electrodeposition morphology in high-capacity aluminium and zinc battery anodes using interfacial metal–substrate bonding Zheng, Jingxu; Bock, David C.; Tang, Tian Nature Energy, Vol. 6, Issue 4 https://doi.org/10.1038/s41560-021-00797-7	journal	April 2021
Fast-charging aluminium–chalcogen batteries resistant to dendritic shorting Pang, Quanquan; Meng, Jiashen; Gupta, Saransh Nature, Vol. 608, Issue 7924 https://doi.org/10.1038/s41586-022-04983-9	journal	August 2022
Sulfone-based electrolytes for aluminium rechargeable batteries Nakayama, Yuri; Senda, Yui; Kawasaki, Hideki Physical Chemistry Chemical Physics, Vol. 17, Issue 8 https://doi.org/10.1039/C4CP02183E	journal	January 2015
The staging mechanism of AlCl ₄ intercalation in a graphite electrode for an aluminium-ion battery Bhauriyal, Preeti; Mahata, Arup; Pathak, Biswarup Physical Chemistry Chemical Physics, Vol. 19, Issue 11 https://doi.org/10.1039/C7CP00453B	journal	January 2017
The rechargeable aluminum-ion battery Jayaprakash, N.; Das, S. K.; Archer, L. A. Chemical Communications, Vol. 47, Issue 47 https://doi.org/10.1039/c1cc15779e	journal	January 2011
Growth kinetics and mechanisms of aluminum-oxide films formed by thermal oxidation of aluminum Jeurgens, L. P. H.; Sloof, W. G.; Tichelaar, F. D. Journal of Applied Physics, Vol. 92, Issue 3 https://doi.org/10.1063/1.1491591	journal	August 2002
Direct Observation of the Oxidation of Aluminum Single‐Crystal Surfaces Doherty, P. E.; Davis, R. S. Journal of Applied Physics, Vol. 34, Issue 3 https://doi.org/10.1063/1.1729318	journal	March 1963
Commentary: The Materials Project: A materials genome approach to accelerating materials innovation Jain, Anubhav; Ong, Shyue Ping; Hautier, Geoffroy APL Materials, Vol. 1, Issue 1 https://doi.org/10.1063/1.4812323	journal	July 2013
High Coulombic efficiency aluminum-ion battery using an AlCl ₃ -urea ionic liquid analog electrolyte Angell, Michael; Pan, Chun-Jern; Rong, Youmin Proceedings of the National Academy of Sciences, Vol. 114, Issue 5 https://doi.org/10.1073/pnas.1619795114	journal	January 2017
An operando X-ray diffraction study of chloroaluminate anion-graphite intercalation in aluminum batteries Pan, Chun-Jern; Yuan, Chunze; Zhu, Guanzhou Proceedings of the National Academy of Sciences, Vol. 115, Issue 22 https://doi.org/10.1073/pnas.1803576115	journal	May 2018
The oxidation of metals Lawless, K. R. Reports on Progress in Physics, Vol. 37, Issue 2 https://doi.org/10.1088/0034-4885/37/2/002	journal	February 1974
Total-electron-yield current measurements for near-surface extended x-ray-absorption fine structure Erbil, A.; Cargill III, G. S.; Frahm, R. Physical Review B, Vol. 37, Issue 5 https://doi.org/10.1103/PhysRevB.37.2450	journal	February 1988
X-ray-absorption spectroscopy study of the partial devitrification of amorphousNi80B20and the formation of amorphous nickel Gutiérrez, A.; López, M. F.; Hernando, A. Physical Review B, Vol. 56, Issue 9 https://doi.org/10.1103/PhysRevB.56.5039	journal	September 1997
Thermodynamic stability of amorphous oxide films on metals: Application to aluminum oxide films on aluminum substrates Jeurgens, L.; Sloof, W.; Tichelaar, F. Physical Review B, Vol. 62, Issue 7 https://doi.org/10.1103/PhysRevB.62.4707	journal	August 2000
Precise lattice constants of germanium, aluminum, gallium arsenide, uranium, sulphur, quartz and sapphire Cooper, A. S. Acta Crystallographica, Vol. 15, Issue 6 https://doi.org/10.1107/S0365110X62001474	journal	June 1962
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT Ravel, B.; Newville, M. Journal of Synchrotron Radiation, Vol. 12, Issue 4 https://doi.org/10.1107/S0909049505012719	journal	June 2005
Estimation of measurement uncertainties in XAFS data Newville, M.; Boyanov, B. I.; Sayers, D. E. Journal of Synchrotron Radiation, Vol. 6, Issue 3 https://doi.org/10.1107/S0909049598018147	journal	May 1999
An XPS study of the oxidation of AlAs thin films grown by MBE Taylor, J. Ashley Journal of Vacuum Science and Technology, Vol. 20, Issue 3 https://doi.org/10.1116/1.571450	journal	March 1982
Room temperature exchange reaction at the Al–InP(110) interface: Soft x-ray photoemission studies Kendelewicz, T.; Petro, W. G.; Babalola, I. A. Journal of Vacuum Science & Technology B: Microelectronics Processing and Phenomena, Vol. 1, Issue 3 https://doi.org/10.1116/1.582611	journal	July 1983
Solid electrolyte interphases for high-energy aqueous aluminum electrochemical cells Zhao, Qing; Zachman, Michael J.; Al Sadat, Wajdi I. Science Advances, Vol. 4, Issue 11 https://doi.org/10.1126/sciadv.aau8131	journal	November 2018
Confining Sn nanoparticles in interconnected N-doped hollow carbon spheres as hierarchical zincophilic fibers for dendrite-free Zn metal anodes Yu, Huan; Zeng, Yinxiang; Li, Nian Wu Science Advances, Vol. 8, Issue 10 https://doi.org/10.1126/sciadv.abm5766	journal	March 2022
Electrochemical Properties of Imidazolium Salt Electrolytes for Electrochemical Capacitor Applications McEwen, Alan B. Journal of The Electrochemical Society, Vol. 146, Issue 5 https://doi.org/10.1149/1.1391827	journal	January 1999
X-ray Absorption Near-Edge Structure (XANES) Spectroscopy Henderson, G. S.; de Groot, F. M. F.; Moulton, B. J. A. Reviews in Mineralogy and Geochemistry, Vol. 78, Issue 1 https://doi.org/10.2138/rmg.2014.78.3	journal	January 2014

Similar Records

Solid electrolyte interphases for high-energy aqueous aluminum electrochemical cells

Journal Article · Wed Oct 31 20:00:00 EDT 2018 · Science Advances · OSTI ID:1626004

Electrodeposition and stripping of lithium and sodium on inert electrodes in room temperature chloroaluminate molten salts

Journal Article · Thu Feb 29 23:00:00 EST 1996 · Journal of the Electrochemical Society · OSTI ID:220872

Related Subjects

25 ENERGY STORAGE
molten salts
rechargeable aluminum batteries
solid electrolyte interphase

Understanding the reversible electrodeposition of aluminum in low-cost room-temperature molten salts

Citation Formats

References (56)

Similar Records

Related Subjects