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Prospects for Anion-Exchange Membranes in Alkali Metal–Air Batteries

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Prospects for Anion-Exchange Membranes in Alkali Metal–Air Batteries energies Review Prospects for Anion-Exchange Membranes in Alkali Metal–Air Batteries Misgina Tilahun Tsehaye , Fannie Alloin * and Cristina Iojoiu * Univ. Grenoble Alpes, Univ. Savoie Mont Blanc, CNRS, Grenoble INP, LEPMI, 38 000 Grenoble, France; [email protected] * Correspondence: [email protected] (F.A.); [email protected] (C.I.) Received: 18 October 2019; Accepted: 6 December 2019; Published: 10 December 2019 Abstract: Rechargeable alkali metal–air batteries have enormous potential in energy storage applications due to their high energy densities, low cost, and environmental friendliness. Membrane separators determine the performance and economic viability of these batteries. Usually, porous membrane separators taken from lithium-based batteries are used. Moreover, composite and cation-exchange membranes have been tested. However, crossover of unwanted species (such as zincate ions in zinc–air flow batteries) and/or low hydroxide ions conductivity are major issues to be overcome. On the other hand, state-of-art anion-exchange membranes (AEMs) have been applied to meet the current challenges with regard to rechargeable zinc–air batteries, which have received the most attention among alkali metal–air batteries. The recent advances and remaining challenges of AEMs for these batteries are critically discussed in this review. Correlation between the properties of the AEMs and performance and cyclability of the batteries is discussed. Finally, strategies for overcoming the remaining challenges and future outlooks on the topic are briefly provided. We believe this paper will play a significant role in promoting R&D on developing suitable AEMs with potential applications in alkali metal–air flow batteries. Keywords: energy storage; alkali metal–air batteries; zinc–air batteries; anion-exchange membranes; recent advances; remaining challenges 1. Introduction to Alkali Metal–Air Batteries The gradual depletion of fossil fuels and environmental concerns associated with their use have been challenging the energy sector. Thus, vast development and deployment of sustainable renewable energy sources, such as solar and wind are required [1]. Wind and solar are known to be the world’s fastest-growing energy sources [2]. Despite their economic feasibility and environmental friendliness, their intermittent nature and geographical limitations are the major challenges for their full employment as next-generation energy sources. To counteract their fluctuating energy outputs and thus improve the stability of the electrical grid, an efficient and stable electrical energy storage system is needed [3–5]. Over the years, various electrical energy storages have been identified and used. Currently, lithium (Li)-ion and lead–acid batteries are the leading energy storage technologies. Lead–acid batteries are well-established electrochemical energy storages for both automotive and industrial applications [6]. However, they have low energy density (30–50 Wh/kg), low cycling life (500–1000 cycles), and are dependent on toxic lead [7,8]. Similarly, Li-ion batteries play an important role in our daily lives, as they are the most commonly used battery in electric vehicles and electronics today. Unfortunately, their high cost per kWh and recent concerns over their safety have restricted their application, thus requiring the development of new storage technologies for the next generation [3,9,10]. The thermal runaway of the cell, which leads to whole battery pack failure, is believed to be caused by mechanical, electrical, or thermal abuses [11]. Moreover, Li-ion batteries’ energy density is only about 100–200 Wh/Kg, which Energies 2019, 12, 4702; doi:10.3390/en12244702 www.mdpi.com/journal/energies Energies 2019, 12, x FOR PEER REVIEW 2 of 27 EnergiesEnergies2019 2019, 12, 12, 4702, x FOR PEER REVIEW 2 of2 of 26 27 only about 100–200 Wh/Kg, which cannot provide the extended use needed for electric vehicles and largeonly stationary about 100 –applications200 Wh/Kg, [12]which. Therefore, cannot provide safe and the high extended-energy use-density needed energy for electr storageic vehicles systems and arecannotlarge extremely stationary provide desired. the applications extended Figure 1 use shows[12] needed. Therefore, the chemistries for electric safe and vehiclesand high principal-energy and largecomponents-density stationary energy of lead applications storage–acid and systems [ 12Li-]. ionTherefore,are batteries. extremely safe anddesired. high-energy-density Figure 1 shows the energy chemistries storage systemsand principal are extremely components desired. of lead Figure–acid1 shows and Li- theion chemistries batteries. and principal components of lead–acid and Li-ion batteries. FigureFigure 1. 1. PPrincipalrincipal components components of of lead lead–acid–acid ( (leftleft)) and and Li Li-ion-ion ( (rightright)) batteries batteries [6] [6].. Figure 1. Principal components of lead–acid (left) and Li-ion (right) batteries [6]. AmongAmong several several potential potential candidates, candidates, metal metal–air–air batteries batteries are a are promising a promising and competitive and competitive high- energyhigh-energyAmong alternative alternativeseveral to Li potential-ion to batteries Li-ion candidates, batteries[13]. Metal metal [–13air].–air batteries Metal–airbatteries are are high batteries a promising energy are density highand competitiveelectroch energy densityemical high - electrochemical cells that use air at the cathode (+ve) and metal as the anode ( ve) with an aqueous cellsenergy that alternativeuse air at the to Licathode-ion batteries (+ve) and [13] metal. Metal as–air the batteries anode (− areve) high with energy an aqueous density− electrolyte electroch emical[14]. Roughlyelectrolytecells that speaking, use [14]. air Roughly at athe metal cathode speaking,–air (+ve)battery a metal–airand consists metal batteryas of the four anode consists components: (−ve) of fourwith components:metalan aqueous anode, electrolyte metal electrolyte, anode, [14] . electrolyte, membrane separator, and an air cathode. The metal anode can be an alkali metal (e.g., membraneRoughly separatorspeaking,, anda metal an air–air cathode. battery The consists metal ano of defour can components: be an alkali metal metal (e.g., anode, Li, Na, electrolyte, and K), alkalineLi,membrane Na, andearth K),separator metal alkaline (e.g.,, and earthMg), an airor metal firstcathode.- (e.g.,row Thetransition Mg), metal or first-row metalanode (e.g., can transition be Fe an and alkali metalZn) metal[15] (e.g.,. 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The main processes occurring in metal–air batteries during charge (left) and discharge (right) cycles. (rightFigure) cycles. 2. The main processes occurring in metal–air batteries during charge (left) and discharge Alkaline(right) cycles. metal–air batteries (Zn–air, Al–air and Fe–air) are known to be inexpensive and non-toxicAlkaline [17 ].metal These–air batteries,batteries (Zn due–air to, their Al–air lower and Fe reactivity,–air) are easierknown handling, to be inexpensive and safety, and can non be- toxicchosen [17]Alkaline over. 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