Institute of Physical Chemistry, Justus-Liebig-University Giessen, Heinrich-Buff-Ring 58, 35392 Giessen, Germany.
Phys Chem Chem Phys. 2013 Oct 14;15(38):15876-87. doi: 10.1039/c3cp52125g. Epub 2013 Aug 14.
Research on sodium-ion batteries has recently been rediscovered and is currently mainly focused on finding suitable electrode materials that enable cell reactions of high energy densities combined with low cost. Naturally, an assessment of potential electrode materials requires a rational comparison with the analogue reaction in lithium-ion batteries. In this paper, we systematically discuss the broad range of different conversion reactions for sodium-ion batteries based on their basic thermodynamic properties and compare them with their lithium analogues. Capacities, voltages, energy densities and volume expansions are summarized to sketch out the scope for future studies in this research field. We show that for a given conversion electrode material, replacing lithium by sodium leads to a constant shift in cell potential ΔE°(Li-Na) depending on the material class. For chlorides ΔE°(Li-Na) equals nearly zero. The theoretical energy densities of conversion reactions of sodium with fluorides or chlorides as positive electrode materials typically reach values between 700 W h kg(-1) and 1000 W h kg(-1). Next to the thermodynamic assessment, results on several conversion reactions between copper compounds (CuS, CuO, CuCl, CuCl2) and sodium are being discussed. Reactions with CuS and CuO were chosen because these compounds are frequently studied for conversion reactions with lithium. Chlorides are interesting because of ΔE°(Li-Na)≈ 0 V. As a result of chloride solubility in the electrolyte, the conversion process proceeds at defined potentials under rather small kinetic limitations.
钠离子电池的研究最近重新受到关注,目前主要集中在寻找合适的电极材料,使电池反应具有高能量密度和低成本。当然,对潜在电极材料的评估需要与锂离子电池中类似的反应进行合理比较。在本文中,我们系统地讨论了基于基本热力学性质的钠离子电池的广泛不同的转化反应,并将它们与锂的类似物进行了比较。总结了容量、电压、能量密度和体积膨胀,以勾勒出该研究领域未来研究的范围。我们表明,对于给定的转化电极材料,用钠代替锂会导致电池电势ΔE°(Li-Na)根据材料类别恒定移动。对于氯化物,ΔE°(Li-Na)几乎为零。作为正极材料的氟化物或氯化物与钠的转化反应的理论能量密度通常达到 700 W h kg-1 和 1000 W h kg-1 之间的值。除了热力学评估外,还讨论了几种铜化合物(CuS、CuO、CuCl、CuCl2)与钠之间的转化反应的结果。选择 CuS 和 CuO 进行反应是因为这些化合物经常被研究用于与锂的转化反应。氯化物很有趣,因为ΔE°(Li-Na)≈0 V。由于氯化物在电解质中的溶解度,转化过程在较小的动力学限制下在确定的电势下进行。