A sobering examination of the feasibility of aqueous aluminum batteries

Pastel, Glenn R.; Chen, Ying; Pollard, Travis P.; Schroeder, Marshall A.; Bowden, Mark E.; Zheng, Allen; Hahn, Nathan T.; Ma, Lin; Murugesan, Vijayakumar; Ho, Janet; Garaga, Mounesha; Borodin, Oleg; Mueller, Karl; Greenbaum, Steven; Xu, Kang

doi:10.1039/d2ee00134a

A sobering examination of the feasibility of aqueous aluminum batteries

Journal Article · Sat Apr 23 00:00:00 EDT 2022 · Energy & Environmental Science

DOI:https://doi.org/10.1039/d2ee00134a· OSTI ID:1882605

Pastel, Glenn R. ^[1]; Chen, Ying ^[2]; Pollard, Travis P. ^[1]; ^[1]; ^[2]; ^[3]; ^[4]; ^[1]; ^[2]; Ho, Janet ^[1]; Garaga, Mounesha ^[3]; ^[1]; Mueller, Karl ^[2]; ^[3]; Xu, Kang ^[1]

Army Research Lab., Adelphi, MD (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Joint Center for Energy Storage Research (JCESR)
City Univ. of New York (CUNY), NY (United States)
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Joint Center for Energy Storage Research (JCESR)

Aqueous aluminum (Al) batteries are posited to be a cheap and energy dense alternative to conventional Li-ion chemistries, but an aqueous electrolyte mediating trivalent aluminum cations (Al3+) warrants greater scrutiny. This study provides a rigorous examination of aqueous Al electrolytes, with the first compelling evidence for a dynamic octahedral solvation structure around the Al³⁺, without Al–OTf contact ion pairs, even at high concentrations. This solvation behavior and the concomitant, transient electrostatic hydrolysis of Al–OH₂ ligands contrasts strongly with previously reported water-in-salt electrolytes, and occurs due to the high charge density of the Lewis acidic Al³⁺. Nuclear magnetic resonance spectroscopy and other physicochemical measurements quantitatively reveal how species activity evolves with concentration and temperature. Additionally, this new understanding exposes practical concerns related to the corrosiveness of the acidic aqueous solutions, the degree of hydration of aluminum trifluoromethanesulfonate (Al(OTf)₃) salt, and the grossly insufficient reductive stability of the proposed electrolytes (>1 V between HER onset and Al³⁺/Al). Collectively, these factors constitute multiple fundamental barriers to the feasibility of rechargeable aqueous Al batteries.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: NA0003525

OSTI ID:: 1882605

Alternate ID(s):: OSTI ID: 1866133

Report Number(s):: SAND2022-10012J; 708545

Journal Information:: Energy & Environmental Science, Journal Name: Energy & Environmental Science Journal Issue: 6 Vol. 15; ISSN 1754-5692

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (33)

Water‐in‐Salt Electrolyte (WiSE) for Aqueous Batteries: A Long Way to Practicality Droguet, Léa; Grimaud, Alexis; Fontaine, Olivier Advanced Energy Materials, Vol. 10, Issue 43 https://doi.org/10.1002/aenm.202002440	journal	October 2020
Solid Electrolyte Interphase Engineering for Aqueous Aluminum Metal Batteries: A Critical Evaluation Dong, Tony; Ng, Kok Long; Wang, Yijia Advanced Energy Materials, Vol. 11, Issue 20 https://doi.org/10.1002/aenm.202100077	journal	April 2021
The Grotthuss mechanism Agmon, Noam Chemical Physics Letters, Vol. 244, Issue 5-6 https://doi.org/10.1016/0009-2614(95)00905-J	journal	October 1995
Et tu, Grotthuss! and other unfinished stories Cukierman, Samuel Biochimica et Biophysica Acta (BBA) - Bioenergetics, Vol. 1757, Issue 8 https://doi.org/10.1016/j.bbabio.2005.12.001	journal	August 2006
Uncharted Waters: Super-Concentrated Electrolytes Borodin, Oleg; Self, Julian; Persson, Kristin A. Joule, Vol. 4, Issue 1 https://doi.org/10.1016/j.joule.2019.12.007	journal	January 2020
FTIR analysis of water structure and its influence on the flotation of arcanite (K2SO4) and epsomite (MgSO4·7H2O) Cheng, Fangqin; Cao, Qinbo; Guan, Yunshan International Journal of Mineral Processing, Vol. 122 https://doi.org/10.1016/j.minpro.2013.04.007	journal	July 2013
Nonaqueous Rechargeable Aluminum Batteries: Progresses, Challenges, and Perspectives Tu, Jiguo; Song, Wei-Li; Lei, Haiping Chemical Reviews, Vol. 121, Issue 8 https://doi.org/10.1021/acs.chemrev.0c01257	journal	March 2021
Origin of Unusual Acidity and Li ⁺ Diffusivity in a Series of Water-in-Salt Electrolytes Han, Kee Sung; Yu, Zhou; Wang, Hui The Journal of Physical Chemistry B, Vol. 124, Issue 25 https://doi.org/10.1021/acs.jpcb.0c02483	journal	June 2020
Operando MAS NMR Reaction Studies at High Temperatures and Pressures Walter, Eric D.; Qi, Long; Chamas, Ali The Journal of Physical Chemistry C, Vol. 122, Issue 15 https://doi.org/10.1021/acs.jpcc.7b11442	journal	January 2018
Role of Solvent Rearrangement on Mg ²⁺ Solvation Structures in Dimethoxyethane Solutions using Multimodal NMR Analysis Chen, Ying; Jaegers, Nicholas R.; Wang, Hui The Journal of Physical Chemistry Letters, Vol. 11, Issue 15 https://doi.org/10.1021/acs.jpclett.0c01447	journal	July 2020
Aqueous Aluminum Cells: Mechanisms of Aluminum Anode Reactions and Role of the Artificial Solid Electrolyte Interphase Zhang, Yonglei; Bian, Yinghui; Lv, Zichuan ACS Applied Materials & Interfaces, Vol. 13, Issue 31 https://doi.org/10.1021/acsami.1c08782	journal	August 2021
A 63 m Superconcentrated Aqueous Electrolyte for High-Energy Li-Ion Batteries Chen, Long; Zhang, Jiaxun; Li, Qin ACS Energy Letters, Vol. 5, Issue 3 https://doi.org/10.1021/acsenergylett.0c00348	journal	February 2020
Multivalent-Ion versus Proton Insertion into Battery Electrodes Park, Min Je; Yaghoobnejad Asl, Hooman; Manthiram, Arumugam ACS Energy Letters, Vol. 5, Issue 7 https://doi.org/10.1021/acsenergylett.0c01021	journal	June 2020
Rare-Earth Metal Triflates in Organic Synthesis Kobayashi, Shū; Sugiura, Masaharu; Kitagawa, Hidetoshi Chemical Reviews, Vol. 102, Issue 6 https://doi.org/10.1021/cr010289i	journal	June 2002
An ¹⁷ O-NMR Study of the Exchange of Water on AlOH(H ₂ O) ₅ ²⁺ (aq) Nordin, Jan P.; Sullivan, David J.; Phillips, Brian L. Inorganic Chemistry, Vol. 37, Issue 19 https://doi.org/10.1021/ic980333l	journal	September 1998
Kinetic study of proton exchange between the Al(OH2)63+ ion and water in dilute acid. Participation of water molecules in proton transfer Fong, Dodd-Wing; Grunwald, Ernest Journal of the American Chemical Society, Vol. 91, Issue 10 https://doi.org/10.1021/ja01038a001	journal	May 1969
Architecting a Stable High-Energy Aqueous Al-Ion Battery Yan, Chunshuang; Lv, Chade; Wang, Liguang Journal of the American Chemical Society, Vol. 142, Issue 36 https://doi.org/10.1021/jacs.0c05054	journal	August 2020
Cooperativity in Al ³⁺ Hydrolysis Reactions from Density Functional Theory Calculations Bogatko, Stuart; Moens, Jan; Geerlings, Paul The Journal of Physical Chemistry A, Vol. 114, Issue 29 https://doi.org/10.1021/jp102787e	journal	July 2010
Group additivity-Pourbaix diagrams advocate thermodynamically stable nanoscale clusters in aqueous environments Wills, Lindsay A.; Qu, Xiaohui; Chang, I-Ya Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms15852	journal	June 2017
Electrochemically activated spinel manganese oxide for rechargeable aqueous aluminum battery Wu, Chuan; Gu, Sichen; Zhang, Qinghua Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-018-07980-7	journal	January 2019
Aluminum-copper alloy anode materials for high-energy aqueous aluminum batteries Ran, Qing; Shi, Hang; Meng, Huan Nature Communications, Vol. 13, Issue 1 https://doi.org/10.1038/s41467-022-28238-3	journal	January 2022
Practical assessment of the performance of aluminium battery technologies Faegh, Ehsan; Ng, Benjamin; Hayman, Dillon Nature Energy, Vol. 6, Issue 1 https://doi.org/10.1038/s41560-020-00728-y	journal	December 2020
Highly reversible zinc metal anode for aqueous batteries Wang, Fei; Borodin, Oleg; Gao, Tao Nature Materials, Vol. 17, Issue 6 https://doi.org/10.1038/s41563-018-0063-z	journal	April 2018
Fluorinated interphase enables reversible aqueous zinc battery chemistries Cao, Longsheng; Li, Dan; Pollard, Travis Nature Nanotechnology, Vol. 16, Issue 8 https://doi.org/10.1038/s41565-021-00905-4	journal	May 2021
Aluminum electrolytes for Al dual-ion batteries Kravchyk, Kostiantyn V.; Kovalenko, Maksym V. Communications Chemistry, Vol. 3, Issue 1 https://doi.org/10.1038/s42004-020-00365-2	journal	August 2020
Towards Al ³⁺ Mobility in Crystalline Solids: Critical Review and Analysis Nestler, Tina; Fedotov, Stanislav; Leisegang, Tilmann Critical Reviews in Solid State and Materials Sciences, Vol. 44, Issue 4 https://doi.org/10.1080/10408436.2018.1490248	journal	April 2019
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
The Origin of Aluminum Flocs in Polluted Streams Furrer, G. Science, Vol. 297, Issue 5590 https://doi.org/10.1126/science.1076505	journal	September 2002
Suppressing corrosion in primary aluminum–air batteries via oil displacement Hopkins, Brandon J.; Shao-Horn, Yang; Hart, Douglas P. Science, Vol. 362, Issue 6415 https://doi.org/10.1126/science.aat9149	journal	November 2018
Perspective—Electrochemical Stability of Water-in-Salt Electrolytes Kühnel, Ruben-Simon; Reber, David; Battaglia, Corsin Journal of The Electrochemical Society, Vol. 167, Issue 7 https://doi.org/10.1149/1945-7111/ab7c6f	journal	January 2020
Electrolyte Solvation and Ionic Association. VII. Correlating Raman Spectroscopic Data with Solvate Species Henderson, Wesley A.; Seo, Daniel M.; Han, Sang-Don Journal of The Electrochemical Society, Vol. 167, Issue 11 https://doi.org/10.1149/1945-7111/aba44a	journal	July 2020
Aluminum Bis(trifluoromethanesulfonyl)imide as a Chloride-Free Electrolyte for Rechargeable Aluminum Batteries Chiku, Masanobu; Matsumura, Shota; Takeda, Hiroki Journal of The Electrochemical Society, Vol. 164, Issue 9 https://doi.org/10.1149/2.0701709jes	journal	January 2017
The Aluminum-Ion Battery: A Sustainable and Seminal Concept? Leisegang, Tilmann; Meutzner, Falk; Zschornak, Matthias Frontiers in Chemistry, Vol. 7 https://doi.org/10.3389/fchem.2019.00268	journal	May 2019

Similar Records

A Sobering Examination of the Feasibility of Aqueous Aluminum Batteries

Journal Article · Wed Jun 01 00:00:00 EDT 2022 · Energy & Environmental Science · OSTI ID:2998789

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 · OSTI ID:2440524

Related Subjects

25 ENERGY STORAGE

A sobering examination of the feasibility of aqueous aluminum batteries

Citation Formats

References (33)

Linked Research (1)

Similar Records

Related Subjects