Fast-charging aluminium–chalcogen batteries resistant to dendritic shorting

Pang, Quan; Meng, Jiashen; Gupta, Saransh; Hong, Xufeng; Kwok, Chun Yuen; Ji, Zhao; Jin, Yingxia; Xu, Lidong; Karahan, Özlem; Wang, Ziqi; Toll, Spencer; Mai, Liqiang; Nazar, Linda F.; Balasubramanian, Mahalingam; Narayanan, Badri; Sadoway, Donald R.

doi:10.1038/s41586-022-04983-9

Cited by 120 publications

(85 citation statements)

References 73 publications

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“…This is a common problem in Al-ion batteries and is often ascribed to the large desolvation energy of Al 3+ which can be mitigated with elevated temperatures. 45 Anchoring Mechanism. The charged MCl x species are all, to varying degrees, Lewis acids or bases.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Nonmetal Chloride Cathodes for Al-Ion Batteries

2022

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Aluminum-ion batteries inherently operate at a lower voltage than their lithium counterparts due to the more positive reduction potential of Al 2 Cl 7 − /Al (−0.7 V vs SHE) compared to Li + /Li (−3.04 V vs SHE). In order to compete, these batteries must utilize inexpensive, high capacity materials to make up for this lower voltage. Herein, we showcase the possibility of using nonmetal inorganic chloride cathodes, with the tantalizing possibility of utilizing boron, which has 7438 mAh/g of theoretical capacity; the highest of any conversion material. An experimental capacity of 4500 mAh/g was achieved using B−P@hBN, and capacity retention is enhanced using hBN to help adsorb the charged species. Although capacity retention still leaves something to be desired, this showcases the possibility of ultra-high-capacity cathode materials exceeding even sulfur in halogen based ionic liquid electrolytes with more development.

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Section: ■ Results and Discussionmentioning

confidence: 99%

“…All polarizations of the batteries are large, resulting in a large voltage drop between charging and discharging. This is a common problem in Al-ion batteries and is often ascribed to the large desolvation energy of Al 3+ which can be mitigated with elevated temperatures …”

Section: Resultsmentioning

confidence: 99%

Nonmetal Chloride Cathodes for Al-Ion Batteries

2022

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“…We next interrogated the solvation species in the ammonium-based and imidazolium-based IL electrolytes using 27 Al NMR from chemical shifts; 103.8 ± 2.0 ppm for AlCl4 - (6,(17)(18)(19), and 97.5±1.0 ppm for Al2Cl7 -(18) (figs S4-6). There was no detectable concentration of Al3Cl10species, 81 ppm (20) throughout the entire AlCl3 concentration range evaluated in this work.…”

Section: Resultsmentioning

confidence: 99%

Understanding the Reversible Electrodeposition of Al in Low-Cost Room Temperature Molten Salts

Garcia‐Mendez¹,

Zheng²,

Archer³

2022

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Al-based batteries are considered an attractive alternative to Li metal batteries due to the use of Al metal as an anode with lower cost, lower reactivity and larger abundance compared to Li. Despite the aforementioned attributes, few electrolytes permit reversible electrodeposition of Al metal at room temperature. Thus, for the last 30 years, expensive imidazolium-based ionic liquids have dominated the field. Even though extensive research has been conducted on imidazolium-based ionic liquids, a systematic study that sheds light on the structural requirements, physicochemical and transport properties required to enable high reversibility has not been conducted. Here, we investigated two ammonium-based systems that show comparable reversibility to imidazolium-based ionic liquids with Coulombic efficiencies up to 99.1% for over 1000 cycles (1 mAh/cm2, 4 mA/cm2). We reveal that high reversibility in ammonium- and imidazolium- based electrolytes is achieved when a critical ratio of the solvation species (AlCl4 - and Al2Cl7 -) is obtained, where Lewis’s acidity and beneficial interfacial reactions continuously etch the Al2O3 resistive interfacial layer and uniform current distribution is attained on the anode. Insights were obtained via construction of phase diagrams, 27Al quantitative NMR, structural considerations, chemical analyses, transport properties and electrochemical measurements. The findings yield quantitative molecular-level understanding of Al electrodeposition in room-temperature ammonium-based molten salts that are up to five times cheaper than the commonly used imidazolium-based electrolytes. The fundamental understanding gained on the structural, physicochemical and transport properties that enable high reversibility of Al electrodeposition in electrolytes can guide engineering approaches for other electrolyte systems for Al-based batteries. Furthermore, the development of low-cost, high-rate capability and long-term stability electrolytes can accelerate the development of high-capacity cathodes leading to higher energy densities relevant for electric vehicles.

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“…A tight Li supply-demand balance is expected in the near future unless new supply lines come online, which may have undesirable socio-environmental impacts once full-fledged lithium mining is underway [2]. Hence, the uncertainty in the lithium supply is pushing the battery research and development toward non-lithium chemistries, which utilize earth-abundant metals, including Na, K, Mg, Ca, Zn and Al [3][4][5][6][7][8][9][10]. Among all, Al-metal chemistry is the most promising because of: (1) highest abundance (among metals) in the earth's crust, (2) highest volumetric capacity (~ 8000 mAh cm −3 ) and (3) economically sustainable raw material supply because of an already matured Al industry [11].…”

Section: Introductionmentioning

confidence: 99%

Additive-Driven Interfacial Engineering of Aluminum Metal Anode for Ultralong Cycling Life

et al. 2022

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Rechargeable Al batteries (RAB) are promising candidates for safe and environmentally sustainable battery systems with low-cost investments. However, the currently used aluminum chloride-based electrolytes present a significant challenge to commercialization due to their corrosive nature. Here, we report for the first time, a novel electrolyte combination for RAB based on aluminum trifluoromethanesulfonate (Al(OTf)3) with tetrabutylammonium chloride (TBAC) additive in diglyme. The presence of a mere 0.1 M of TBAC in the Al(OTf)3 electrolyte generates the charge carrying electrochemical species, which forms the basis of reaction at the electrodes. TBAC reduces the charge transfer resistance and the surface activation energy at the anode surface and also augments the dissociation of Al(OTf)3 to generate the solid electrolyte interphase components. Our electrolyte's superiority directly translates into reduced anodic overpotential for cells that ran for 1300 cycles in Al plating/stripping tests, the longest cycling life reported to date. This unique combination of salt and additive is non-corrosive, exhibits a high flash point and is cheaper than traditionally reported RAB electrolyte combinations, which makes it commercially promising. Through this report, we address a major roadblock in the commercialization of RAB and inspire equivalent electrolyte fabrication approaches for other metal anode batteries.

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Fast-charging aluminium–chalcogen batteries resistant to dendritic shorting

Cited by 120 publications

References 73 publications

Nonmetal Chloride Cathodes for Al-Ion Batteries

Nonmetal Chloride Cathodes for Al-Ion Batteries

Understanding the Reversible Electrodeposition of Al in Low-Cost Room Temperature Molten Salts

Additive-Driven Interfacial Engineering of Aluminum Metal Anode for Ultralong Cycling Life

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