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Chem Soc Rev Review Article Although the sodium perchlorates have some concern of safety and are notoriously difficult to dry, in terms of only academic interest, the commonly used salt is NaClO4 due to a combination of historical and cost reasons.28,570,573 Delmas et al. demon- strated the electrochemical properties of a P2-type NaxCoO2 electrode in NaClO4 in a propylene carbonate solvent.573 In 2000s, D. A. Stevens and J. R. Dahn et al. investigated the reversible insertion of sodium into hard-carbon host structures at room temperature in 1 M NaClO4 in EC : DEC (30 : 70, v/v) as an electrolyte.247 Alcantara et al. reported the dependency of sodium salts on the electrochemical properties of carbonaceous materials using NaPF6 and NaClO4 salts in EC : DMC 1 : 1 mixture solvents.575 They suggested that using a sodium NaClO4 based electrolyte for a carbonaceous electrode demonstrated a higher capacity with high Coulombic efficiency. They also reported the dependency of electrolyte solvents on the electrochemical properties of carbonaceous materials using an EC : DMC, DME, and EC : THF solvent containing 1 M NaClO4 salt (Fig. 42a). The THF-solvent and EC : THF mixture have shown to improve the electrochemical performance as compared to only carbonate- based solvents. Komaba et al. investigated electrochemical performance of hard carbon anodes in Na cells with various electrolyte solvents of EC, PC, BC, EC : DMC (50 : 50, v/v), EC : EMC (50:50, v/v), EC:DEC (50:50, v/v), and PC:VC (98:2, v/v) containing 1 M NaClO4 salt in beaker-type cells.27 The results show that 1 M NaClO4 in PC, EC and EC:DEC solution demon- strated better electrochemical performances than the other stable, (4) ionically conductive and electronically insulating and (5) low toxicity with low production cost.570,571 These features intrinsically depend on the nature of the salts and the solvents as well as the possible use of additives. For suitable electrolytes, we should consider the major parameter of solvents and salts, which can mainly affect the cell perfor- mances. The salt should exhibit: (1) solubility in the solvent, (2) stability vs. reduction as well as oxidation, and (3) chemical stability with the cell component.568 The solvent should: (1) be polar with a high dielectric constant, (2) exhibit low viscosity in order to improve the ionic mobility, (3) remain inert to the charged surfaces of the cathode and the anode during cell operation, and (4) have a wide liquid range (i.e. a low melting point and a high boiling point).568 Over the past few decades, based on such basic properties, the scientific community has made tremendous efforts in finding the best combination of suitable electrolytes; however, not yet currently available for the direct use for practical SIBs. While being of only academic interest, carbonate ester-based electrolyte solution containing sodium salts is considered to be one of the most appropriate electrolyte media for SIB applications. In early reports, in the 1980s, the properties of sodium ion cells are tested using NaI, NaPF6, and NaClO4 salts in organic solvents as the electrolyte.572,573 Then, either NaClO4 or NaPF6 is used as the electrolyte salts in carbonate-ester binary or ternary mixtures, which have become the main stream electrolyte composition used for Na+ chemistry.571 View Article Online Fig. 42 (a) Voltage/capacity plots corresponding to the first discharge/charge cycles of carbon aerogel microspheres in sodium cells, 1 M NaClO4 dissolved in EC:DMC, DME, THF, and EC:THF as electrolytes. (Reproduced with permission from ref. 575 Copyright 2005 The Electrochemical Society.) (b) Linear sweep voltammetry of a sodium cell using two electrolytes, namely, 1 M NaClO4 in PC + 2 vol% FEC and 1 M NaClO4 in EMS + 2 vol% FEC. (Reproduced with permission from ref. 51, Copyright 2014 American Chemical Society.) (c) DSC heating curves of fully sodiated hard carbon in various electrolyte formulations. (Reproduced with permission from ref. 28, Copyright 2012 The Royal Society of Chemistry.) (d) Comparison of capacity retention of hard carbon electrodes between reagent grade and battery grade NaPF6 PC solution. Photographs of the electrolyte solution use are inserted. (Reproduced with permission from ref. 18, Copyright 2015 The Electrochemical Society.) (e) Initial reduction/oxidation curves for hard-carbon electrodes in 1 M NaClO4 PC solution without and with FEC. Inset shows variation in reversible oxidative capacities for the hard-carbon during successive cycle test. (Reproduced with permission from ref. 577, Copyright 2011 American Chemical Society.) (f) Cycle performance of Sn4P3 and Sn electrodes obtained with or without an FEC additive. (Reproduced from ref. 460 with permission, Copyright 2014 Wiley-VCH Verlag GmbH & Co. KGaA.) (g) Structure of polymer binder: PVDF, PVA, CMC-NA, PAA. (Reproduced with permission from ref. 610, Copyright 2011 American Chemical Society.) (a) Cyclic performance of Na0.11Li3.89Ti5O12 electrodes with different binders. (Reproduced with permission from ref. 616, Copyright 2016 The Electrochemical Society.) Thisjournalis©TheRoyalSocietyofChemistry2017 Chem.Soc.Rev.,2017,46,3529--3614 | 3591 Open Access Article. Published on 28 March 2017. Downloaded on 7/1/2019 3:41:21 AM. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.PDF Image | Sodium-ion batteries present and future
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