Cycling Non-Aqueous Lithium-Air Batteries with Dimethyl Sulfoxide and Sulfolane Co-Solvent Evaluating Influence of Sulfolane on Cell Chemistry
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https://doi.org/10.1595/205651318X15233499272318 Johnson Matthey Technol. Rev., 2018, 62, (3), 332–340 www.technology.matthey.com Cycling Non-Aqueous Lithium-Air Batteries with Dimethyl Sulfoxide and Sulfolane Co-Solvent Evaluating influence of sulfolane on cell chemistry Gunwoo Kim electrolyte leads to formation of a peroxide- Department of Chemistry, University hydroxide mixture as discharge products of Cambridge, Lensfield Road, Cambridge, and the removal of both LiOH and lithium CB2 1EW, UK; Cambridge Graphene Centre, peroxide (Li2O2) on charging from 3.2–3.6 V University of Cambridge, Cambridge, (vs. Li+/Li) is observed. In the presence of CB3 0FA, UK sulfolane as co-solvent, a mixture of Li2O2 and LiOH is formed as major discharge products with Tao Liu, Israel Temprano slightly more LiOH formation than in the absence Department of Chemistry, University of of sulfolane. The presence of sulfolane has also Cambridge, Lensfield Road, Cambridge, CB2 significant effects on the charging behaviour, – 1EW, UK exhibiting a clearer 3 e /O2 oxygen evolution reaction profile during the entire charging process. Enrico A. Petrucco, Nathan Barrow This work provides insights into understanding the Johnson Matthey, Blounts Court Road, Sonning effects of the primary solvent on promoting LiOH Common, Reading, RG4 9NH, UK formation and decomposition in lithium iodide (LiI) mediated non-aqueous Li-O2 batteries. Clare P. Grey* Department of Chemistry, University of 1. Introduction Cambridge, Lensfield Road, Cambridge, CB2 1EW, UK The non-aqueous Li-O2 battery has drawn considerable scientific attention due to its higher *Email: [email protected] theoretical energy density compared to the values achieved by conventional Li-ion batteries (1–3). The successful operation of a Li-O2 battery necessitates Despite considerable research efforts, finding the reversible formation and decomposition of a a chemically stable electrolyte mixture in the discharge product, typically Li2O2 (4–6). However, presence of reduced oxygen species remains a this process is often limited by the considerable great challenge. Previously, dimethyl sulfoxide parasitic reactions caused by highly reactive (DMSO) and sulfolane (tetramethylene sulfone reduced oxygen species, reaction intermediates (TMS))-based electrolytes were reported (such as lithium superoxide (LiO2)) and the final to be stable for lithium air (Li-O2) battery product Li2O2 (7). These undesired reactions are applications. Recently lithium hydroxide (LiOH) accelerated at high charge overpotentials (8, 9) based chemistries have been demonstrated to and addressing such a fundamental issue remains involve supressed side reactions in water-added a major challenge hindering its commercial ether- and DMSO-based electrolytes. Herein, we implementation. One promising strategy to investigate the impact of DMSO-based electrolyte address this issue is the formation of chemically and sulfolane co-solvent on cell chemistry in the more stable discharge products, so that fewer presence of water. We found that DMSO-based side-reactions occur. Recently, LiOH formation and 332 © 2018 Johnson Matthey https://doi.org/10.1595/205651318X15233499272318 Johnson Matthey Technol. Rev., 2018, 62, (3) decomposition has been proposed as an alternative Li-O2 batteries. A range of ex situ and operando mechanism to cycle non-aqueous Li-O2 batteries techniques were used to evaluate the influence using LiI as a redox mediator, in a water-added of sulfolane on cell chemistry, and especially ether-based electrolyte (10), and with ruthenium whether it promotes dominant and reversible LiOH catalysed cells with water-added DMSO-based chemistry. electrolyte (11). The search for chemically stable electrolytes 2. Experimental against reactive reduced oxygen species with the appropriate physicochemical properties is another Electrospun carbonised polyacrylonitrile (C-PAN) crucial research topic in this field. In this regard, electrodes were prepared using a standard recipe for a wide range of solvents such as carbonates, preparation of carbon nanofibers with an electrode ethers and sulfones have been investigated so diameter of 18 mm and the typical carbon loading far (7, 12, 13). In particular, sulfur-containing around 1.2 mg cm–2. Polyacrylonitrile (Sigma- solvents such as DMSO and sulfolane have shown Aldrich, average Mw = 150 k) was dissolved at to be promising candidates for Li-O2 batteries 7.5 wt% in dimethylformamide (DMF) and because they possess high oxidation potentials electrospun using a custom-built device onto (4.8 V and 5.6 V vs. Li+/Li, respectively), and high aluminium foil wrapped on a rotating drum –1 boiling points (189°C and 285°C, respectively) at >1 kV cm field strength. The resulting (14–16). Although initial studies have reported electrospun mat was dried in a vacuum oven at good reversibility of cells with either DMSO 50°C for 12 h, then stabilised by heating in air at –1 or sulfolane-based electrolytes via formation 5 K min up to 300°C and held for 1 h. Sections and removal of Li2O2, various issues related to were cut to size, allowing for shrinkage, and –1 cell performance were reported in later studies carbonised in flowing N2 by heating 10 K min to (13, 17). In the case of DMSO, its electrochemical 1200°C and held for 2 h. The resulting electrodes instability with Li metal anodes has been reported were dried at 110°C under vacuum for 20 h in a as a major issue. It has been suggested that Büchi oven and stored in a dry argon glove box for the addition of N-butyl-N-methylpyrrolidinium further use. bis(trifluoromethanesulfonyl) imide (Pyr14TFSI) Electrodes were assembled into cells for testing ionic liquid can mitigate this issue (18) through the in an argon glove box using EL-CELL differential formation of a stable solid electrolyte interphase electrochemical mass spectrometry (DEMS) (SEI) via TFSI– anion decompositions (19) as well hardware with 1.55 mm EL-CELL glass fibre as lowering the charging overpotential by stabilising separator, lithium metal anode (Alfa Aesar, 99.9% superoxide species (20). Similarly, sulfolane-based metals basis) and 360 µl of electrolyte. The electrolytes have shown to promote the reversible electrolyte used is a mixture of 5000 ppm water, formation and removal of Li2O2 but capacity 0.9 M Pyr14TFSI, 0.7 M LiTFSI and 0.05 M LiI in fading was observed due to the accumulation of DMSO solvent and a 1:1 DMSO:sulfolane mole ratio side-reaction products such as LiOH and lithium for the sulfolane-containing electrolyte. Added carbonate (Li2CO3) (13). water content was carefully chosen on the basis Early chemistries reported for DMSO-based of recent studies (10, 11) and the water content electrolytes were equivocally described as of 5000 ppm is sufficient to promote dominant promoting Li2O2 with significant amounts of side- LiOH formation up to the discharge capacity of reactions (17, 21). In order to increase stability 5.35 mAh. Cell temperature was controlled at the formation of LiOH as discharge product has 25°C and all cell testing was potential limited at been attempted with DMSO-based electrolytes. 2.2–3.7 V. Exhaust gas was continuously analysed Ru-catalysed Li-O2 cells cycled with LiTFSI/DMSO in using Stanford Research Systems UGA/RGA200 the presence of added water exhibited a dominant with a heated capillary and channel electron LiOH chemistry with supressed side-reactions, multiplier (CEM) gain 200. Cell purge gas flow –1 but the charging process undergoes dimethyl rate was 5 ml min at 1.5 bar with cell charge sulfone (DMSO2) accumulation rather than oxygen performed in pure argon and cell discharge in evolution reaction (11). 20% oxygen in argon. Mass signal response was In this report, we investigate the effect of calibrated against standard concentrations to sulfolane as co-solvent in DMSO based electrolytes confirm linearity while background levels and drift containing LiI as redox mediator, LiTFSI salt with were subtracted using a linear fit before and after water and Pyr14TFSI as additives in non-aqueous the target dataset. 333 © 2018 Johnson Matthey https://doi.org/10.1595/205651318X15233499272318 Johnson Matthey Technol. Rev., 2018, 62, (3) X-ray diffraction (XRD) measurements were carried Solid-state NMR data were acquired at 11.7 T on TM out using a Panalytical Empyrean with Cu Kα1 radiation a Bruker Avance III HD spectrometer using a (λ = 1.5406 Å). Scanning electron microscopy 2.5 mm HX probehead. A rotor synchronised Hahn- (SEM) images were recorded with a Hitachi S-5500 echo pulse sequence was used to acquire 1H and 7Li in-lens field emission electron microscope. Post- magic angle spinning (MAS) spectra with a spinning mortem electrode characterisations were performed speed of 30 kHz, with recycle delays of 150 s and with samples to avoid air exposure during transfer 20 s for 1H and 7Li, respectively. Radiofrequency (RF) and data acquisition. In the case of SEM, electrodes field strength was 100 kHz and either 256 transients were exposed to air for a maximum of 20 s prior for 1H or 128 transients for 7Li were acquired. to insertion into the high vacuum chamber. For 1H and 7Li chemical shifts were externally referenced nuclear magnetic resonance (NMR), electrodes to solid adamantane at 1.87 and Li2CO3 at 0 ppm, were scrapped and packed in an argon glovebox. respectively. (a) (b) Capacity, mAh Capacity, mAh 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 0.0 0.1 0.2 0.3 0.4 0.5 3.8 3.8 3.6 3.6 3.4 3.4 V Potential, 3.2 3.2 3.0 3.0 Potential, V Potential, 2.8 2.8 2.6 2.6 2.4 2.4 (c) (d) Discharge Charge LiOH Li2O2 30 35 40 45 50 55 60 65 70 75 80 30 35 40 45 50 55 60 65 70 75 80 2θ, degrees 2θ, degrees Fig.