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      Chloroaluminate Gel Electrolytes Prepared with Copolymers Based on Imidazolium Ionic Liquids and Deep Eutectic Solvent AlCl 3:Urea

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          Abstract

          Polymer gel electrolytes (PGEs) have been prepared with copolymers based on imidazolium ionic liquids and the deep eutectic mixture of AlCl 3:urea (uralumina) as liquid electrolyte. The copolymers were synthesized by photopolymerization of vinylpirrolidone or methylmethacrylate with imidazolium bis (trifluoromethane sulfonyl) imide (TFSI) ionic liquid monomer and mixed in an increasing range of wt.% with uralumina. The rheology and electrochemical activity of PGEs were highly dependent on the molar ratio of charged groups and copolymer content. Structure of the PGEs was studied by FTIR and Raman spectroscopy and a correlation between interactions polymer/uralumina and changes in speciation of uralumina was established. Despite the low molecular weight of the copolymers, the resulting polymer electrolytes develop elastomeric character associated with the binding ionic species. Although there is room to improve the electrochemical activity, in this study these new gels provide sufficient electroactivity to make them feasible alternatives as electrolytes in secondary aluminum batteries.

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          An Overview and Future Perspectives of Aluminum Batteries.

          Giuseppe Antonio Elia, Krystan Marquardt, Katrin Hoeppner … (2016)
          A critical overview of the latest developments in the aluminum battery technologies is reported. The substitution of lithium with alternative metal anodes characterized by lower cost and higher abundance is nowadays one of the most widely explored paths to reduce the cost of electrochemical storage systems and enable long-term sustainability. Aluminum based secondary batteries could be a viable alternative to the present Li-ion technology because of their high volumetric capacity (8040 mAh cm(-3) for Al vs 2046 mAh cm(-3) for Li). Additionally, the low cost aluminum makes these batteries appealing for large-scale electrical energy storage. Here, we describe the evolution of the various aluminum systems, starting from those based on aqueous electrolytes to, in more details, those based on non-aqueous electrolytes. Particular attention has been dedicated to the latest development of electrolytic media characterized by low reactivity towards other cell components. The attention is then focused on electrode materials enabling the reversible aluminum intercalation-deintercalation process. Finally, we touch on the topic of high-capacity aluminum-sulfur batteries, attempting to forecast their chances to reach the status of practical energy storage systems.
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            High Coulombic efficiency aluminum-ion battery using an AlCl3-urea ionic liquid analog electrolyte

            Michael Angell, Chun-Jern Pan, Youmin Rong … (2017)
            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 AlCl3 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. Raman spectroscopy and NMR suggested the existence of AlCl4-, Al2Cl7- anions and [AlCl2·(urea)n]+ cations in the AlCl3/urea electrolyte when an excess of AlCl3 was present. Aluminum deposition therefore proceeded through two pathways, one involving Al2Cl7- anions and the other involving [AlCl2·(urea)n]+ cations. This battery is a promising prospect for a future high-performance, low-cost energy storage device.
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              Aluminium-ion batteries: developments and challenges

              Shyamal K. Das, Homen Lahan, Sadhan Mahapatra (2017)
              The resurgence of aluminium-ion batteries re-establishes and reinforces the goal of developing affordable electrical energy storage and generation devices. The concept of exploring the superior benefits of electropositive metals as anodes in rechargeable metal-batteries has resurfaced in recent times in anticipation of the future societal need for high energy density and affordable batteries. A rechargeable battery based on aluminium chemistry is envisioned to be a low cost energy storage platform, considering that aluminium is the most abundant metal in the Earth's crust. The high volumetric capacity of aluminium, which is four and seven times larger than that of lithium and sodium respectively, unarguably has the potential to boost the energy density of aluminium-batteries on a per unit volume basis. Efforts to develop rechargeable aluminium-batteries can be traced to as early as the 1970s, however this area of research has seen a surge in activity since 2010, when the possibility of achieving an ambient temperature aluminium system was convincingly demonstrated. In recent times, rechargeable aluminium-batteries have been rechristened as aluminium-ion batteries. This review aims to comprehensively illustrate the developments regarding rechargeable non-aqueous aluminium-batteries or aluminium-ion batteries. Additionally, the challenges that impede progress in achieving a practical aluminium-ion battery are also discussed.
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                Author and article information

                Contributors
                Stefano Vecchio Ciprioti: Role: Academic Editor
                Journal
                Journal ID (nlm-ta): Polymers (Basel)
                Journal ID (iso-abbrev): Polymers (Basel)
                Journal ID (publisher-id): polymers
                Title: Polymers
                Publisher: MDPI
                ISSN (Electronic): 2073-4360
                Publication date (Electronic): 27 March 2021
                Publication date Collection: April 2021
                Volume: 13
                Issue: 7
                Electronic Location Identifier: 1050
                Affiliations
                Instituto de Ciencia y Tecnología de Polímeros (ICTP-CSIC), Juan de la Cierva 3, 28006 Madrid, Spain; ptiemblo@ 123456ictp.csic.es (P.T.); gary@ 123456ictp.csic.es (G.E.)
                Author notes
                Author information
                https://orcid.org/0000-0001-8504-8836
                https://orcid.org/0000-0002-3917-0504
                https://orcid.org/0000-0003-4851-6092
                https://orcid.org/0000-0002-0171-2283
                Article
                Publisher ID: polymers-13-01050
                DOI: 10.3390/polym13071050
                PMC ID: 8037023
                PubMed ID: 33801632
                SO-VID: 7f093b3e-cd1f-4e25-b317-44b112025f0f
                Copyright © © 2021 by the authors.
                License:

                Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license ( http://creativecommons.org/licenses/by/4.0/).

                History
                Date received : 23 February 2021
                Date accepted : 25 March 2021
                Categories
                Subject: Article

                Keywords: polymer gel electrolyte,chloroaluminate ionogel,imidazolium ionic liquid,aluminium secondary battery
                Data availability:
                Keywords: polymer gel electrolyte, chloroaluminate ionogel, imidazolium ionic liquid, aluminium secondary battery

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