An AlCl3 based ionic liquid with a neutral substituted pyridine ligand for electrochemical deposition of aluminum

Fang, Youxing; Yoshii, Kazuki; Jiang, Xueguang; Sun, Xiao‐Guang; Tsuda, Tetsuya; Mehio, Nada; Dai, Sheng

doi:10.1016/j.electacta.2015.02.020

Cited by 114 publications

(113 citation statements)

References 33 publications

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“…Next, we investigated the speciation in several AlCl 3 /urea electrolytes. In the AlCl 3 /urea = 1.0 ILA electrolyte, it was suggested (3) that aluminum deposition must have occurred from a cationic species of the form [AlCl 2 ·(ligand) n ] + , because Al 2 Cl 7 − was not present and AlCl 4 − cannot be reduced in the relevant voltage window. We performed Raman spectroscopy studies of five electrolytes with AlCl 3 /urea in the range of 1.0-1.5 (Fig.…”

Section: Resultsmentioning

confidence: 99%

“…For this reason, ionic liquids (ILs) have been investigated for energy storage due to their low vapor pressure and wide electrochemical windows, unfortunately with the caveat of high cost in most cases. A new class of ionic liquids, referred to as ionic liquid analogs (ILAs) or so-called deep eutectic solvents, generally formed through a mixture of a strongly Lewis acidic metal halide and Lewis basic ligand, have gained significant attention due to their comparable electrochemical and physical properties with reduced cost and minimal environmental footprint (2 (4)(5)(6).…”

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confidence: 99%

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High Coulombic efficiency aluminum-ion battery using an AlCl ₃ -urea ionic liquid analog electrolyte

Angell

Pan

Rong

et al. 2017

Proc. Natl. Acad. Sci. U.S.A.

344

285

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In recent years, impressive advances in harvesting renewable energy have led to a pressing demand for the complimentary energy storage technology. Here, a high Coulombic efficiency (∼99.7%) Al battery is developed using earth-abundant aluminum as the anode, graphite as the cathode, and a cheap ionic liquid analog electrolyte made from a mixture of AlCl 3 and urea in a 1.3:1 molar ratio. The battery displays discharge voltage plateaus around 1.9 and 1.5 V (average discharge = 1.73 V) and yielded a specific cathode capacity of ∼73 mAh g −1 at a current density of 100 mA g −1 (∼1.4 C). High Coulombic efficiency over a range of charge-discharge rates and stability over ∼150-200 cycles was easily demonstrated. In situ Raman spectroscopy clearly showed chloroaluminate anion intercalation/deintercalation of graphite (positive electrode) during charge-discharge and suggested the formation of a stage 2 graphite intercalation compound when fully charged. + cations. This battery is a promising prospect for a future high-performance, low-cost energy storage device.aluminum-ion battery | urea electrolyte | ionicity | ionic liquid | energy storage C heap, high-rate (fast charge/discharge) rechargeable batteries with long cycle lives are urgently needed for grid-scale storage of renewable energy, as it is becoming increasingly important to replace fossil fuels (1). Lithium-ion batteries (LIBs) are expensive and have limited cycle life, which makes them nonideal for grid-scale energy storage. Furthermore, high-rate capability is necessary for use in the grid, under which conditions LIBs become increasingly unsafe due to the flammability of the electrolytes used. Batteries based on aluminum offer a viable alternative due to aluminum's three-electron redox properties (offers potential for high-capacity batteries), stability in the metallic state, and very high natural abundance. Furthermore, the development of these batteries based on nonflammable electrolytes of low toxicity is critical for minimizing safety hazard and environmental impact. Recently, our group developed a secondary Al battery system based on the reversible deposition/stripping of aluminum at the Al negative electrode and reversible intercalation/deintercalation of chloroaluminate anions at the graphite positive electrode in a nonflammable 1-ethyl-3-methylimidazolium chloroaluminate (EMIC-AlCl 3 ) IL electrolyte (7,8). A ratio of AlCl 3 /EMIC = 1.3 by mole was used such that Al 2 Cl 7 − was present in the (acidic) electrolyte to facilitate aluminum deposition (9). During charging, Al 2 Cl 7 − is reduced to deposit aluminum metal, and AlCl 4 − ions intercalate (to maintain neutrality) in graphite as carbon is oxidized. During discharge, this battery exhibited a cathode specific capacity of ∼70 mAh g −1 with a Coulombic efficiency (CE) of 97-98%, and ultrahigh charge/discharge rate (up to 5,000 mA g −1 ) for over 7,000 cycles. However, room for improvement exists as the parameter space for the Al battery remains largely unexplored. The three-electron redox properti...

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Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 99%

High Coulombic efficiency aluminum-ion battery using an AlCl ₃ -urea ionic liquid analog electrolyte

Angell

Pan

Rong

et al. 2017

Proc. Natl. Acad. Sci. U.S.A.

344

285

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“…• C, and also in this case, one could notice that d 11 and d 14 do not change significantly from room temperature to 100…”

Section: H5264mentioning

confidence: 97%

“…Electrodeposition of aluminum and its alloys has been intensively studied both in molten salts, 4,6 as well as in ionic liquid [7][8][9][10][11][12] electrolytes. Electroless deposition of Al films in room temperature ionic liquids has also been recently reported.…”

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confidence: 99%

An Electrochemical Quartz Crystal Microbalance Study on Electrodeposition of Aluminum and Aluminum-Manganese Alloys

Ispas

Wolff

Bund

2017

J. Electrochem. Soc.

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The electrodeposition process of aluminum and aluminum-manganese alloys was studied in situ, by using an electrochemical quartz crystal microbalance, EQCM, with damping monitoring, in AlCl 3 based ionic liquids. Cyclic voltammetry, potentiostatic and galvanostatic deposition were performed at different temperatures, from 25 • C up to 100 • C. The morphology of the deposits was investigated by SEM and AFM, and their composition by EDX. The stoichiometry of the alloys was calculated from the EQCM data, based on Sauerbrey's equation. We could show that for thin films electrodeposited on gold electrodes, one can tune their morphology, and in the case of the alloys, also their composition, by modifying the deposition current or potential, as well as by modifying the temperature of the electrolyte. The morphology of the deposits changed gradually with increasing the amount of Mn in the electrolyte from a polyhedral like structure for Al films to round granules for the AlMn alloys. The mechanism for electrodeposition and dissolution of Al and AlMn alloys were analyzed and discussed based on the EQCM data. Some of the chemicals used nowadays in industrial applications are toxic and/or environmentally benign. Alternatives are searched for those chemicals both by industry, as well as in academia. One of the metals of concern is Cd. Its corrosion and wear behavior are excellent. However, it is one of the metals of high concern for our health. According to some recent reports published by the Rowan Technology Group, 1 one promising alternative to replace Cd layers which could offer similar properties to these coatings are Al and Al alloys, in particular Al-Mn.2 It was previously shown that alloying of Al with Mn produces layers that have better corrosion resistance 3,4 and improved mechanical properties 5 compared to pure Al films. This was the reason for choosing in this paper Al and AlMn alloys for a detailed study. The aim was to understand better the effect of the deposition parameters on the properties of the deposited films.Electrodeposition of aluminum and its alloys has been intensively studied both in molten salts, 4,6 as well as in ionic liquid 7-12 electrolytes. Electroless deposition of Al films in room temperature ionic liquids has also been recently reported. 13 The reason for the interest in obtaining dense and uniform aluminum films is due to the special properties of this metal and its alloys, such as good corrosion resistance and wear resistance, light weight, and other more.14 Thus, Al is well known to self-passivate in air, which means it forms an oxide layer that protects it from further corrosion. Aluminum and its alloys can be used in both decorative and functional coatings.Different types of electrolytes were used for electrodeposition of Al and its alloys, such as organic electrolytes (toluene in the SIGAL process), 14 molten salts (such as Li + /K + /AlCl 3 eutectic system) 14 and ionic liquids (with ammonium, pyrrolidinium and imidazolium based cations).14 The source for deposition of aluminum is...

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“…Since the first pioneeristic studies in the 90 th [2], a large number of investigations successfully reported, at lab scale, the electrodeposition of aluminium at room or nearly room temperature. Different type of ionic liquids [3][4][5][6][7], ionic liquid mixtures and additives [8,9] were proposed to achieve the electrodeposition of bulk or nanostructured, dull or matt Al-coatings. However, with the aim of the process industrialization for the deposition of thick al coatings, chloroaluminate ionic liquids, without additives, seems to constitute the better compromise between the quality of the deposit and the stability of the electroplating bath.…”

Section: Introductionmentioning

confidence: 99%

Aluminium electrodeposition fron ionic liquid: effect of deposition temperature and sonication

Caporali

Berretti

Giaccherini

et al. 2016

Proceedings of 2nd International Electronic Conference on Materials

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Abstract:Since their discovery, ionic liquids (IL) have attracted a wide interest for their potential use as medium for many chemical processes, which vary from extraction, to catalysis, to organic synthesis to energy storage. Th eir use as electrochemical media allowed the electrodeposition of metals that are impossible to reduce in aqueous media. In particular, the first generation ILs, namely chloroaluminated ILs, have made possible the deposition of aluminium from his chloride salt. Despite the discovery of this process in the nineties, nowadays aluminium electrodeposition from chloroaluminate ILs still maintains a number of open issues regarding both fundamental and technological aspects. The present communication aims to shed some light about this process as concerns the effect of deposition parameters on the quality of the deposits. Thick (20 μm) Al-coatings were electrodeposited on brass substrates at different temperature and mixing conditions. The so obtained coatings were investigated by means of scanning electron microscope, rugosimetry and X-ray diffraction to asses their morphology and phase composition. Finally, with the intent to correlate the coating structures with their corrosion properties, electrochemical corrosion tests were performed.

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An AlCl3 based ionic liquid with a neutral substituted pyridine ligand for electrochemical deposition of aluminum

Cited by 114 publications

References 33 publications

High Coulombic efficiency aluminum-ion battery using an AlCl ₃ -urea ionic liquid analog electrolyte

High Coulombic efficiency aluminum-ion battery using an AlCl ₃ -urea ionic liquid analog electrolyte

An Electrochemical Quartz Crystal Microbalance Study on Electrodeposition of Aluminum and Aluminum-Manganese Alloys

Aluminium electrodeposition fron ionic liquid: effect of deposition temperature and sonication

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An AlCl3 based ionic liquid with a neutral substituted pyridine ligand for electrochemical deposition of aluminum

Cited by 114 publications

References 33 publications

High Coulombic efficiency aluminum-ion battery using an AlCl 3 -urea ionic liquid analog electrolyte

High Coulombic efficiency aluminum-ion battery using an AlCl 3 -urea ionic liquid analog electrolyte

An Electrochemical Quartz Crystal Microbalance Study on Electrodeposition of Aluminum and Aluminum-Manganese Alloys

Aluminium electrodeposition fron ionic liquid: effect of deposition temperature and sonication

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High Coulombic efficiency aluminum-ion battery using an AlCl ₃ -urea ionic liquid analog electrolyte

High Coulombic efficiency aluminum-ion battery using an AlCl ₃ -urea ionic liquid analog electrolyte