2.

3 Liquid Electrolytes and Solid Electrolyte Interphase (SEI)

 Most of the reported investigations of liquid electrolytes

for NIBs have been focused on the use of sodium salts
containing perchlorate (ClO-4 ), hexafluorophosphate
(PF-6 ), trifluoromethanesulfonate (CF3SO-3 , Otf-),
bis(fluorosulfonyl)imide ([N(SO2F)2]-, FSI-), and
bis(trifluoromethanesulfonyl)imide ([N(CF3SO2)2]-, TFSI-)
anions, combined with organic solvent mixtures of linear
or cyclic carbonates and ethers.

 While NaClO4 was commonly used as a salt at the early

stages of research for Na-based systems, the use of this
salt is currently not recommended due to its potentially
explosive character. Thus, NaPF6 is the most widely
employed salt in carbonate based electrolytes. It is
important to point out that the purity of NaPF 6 strongly
affects the electrochemical performance of the
investigated systems. Indeed, battery grade NaPF 6, when
dissolved in carbonates, generally leads to colourless and
transparent electrolyte solutions, with improved
electrochemical response compared to chemistry grade,
especially in terms of capacity retention and Coulombic
efficiency.
 Interestingly, ether-based electrolytes have shown excellent performances. They not only have been
successfully employed to enable co-intercalation of solvated Na+ ions into graphite, but they also
present an ability to form a very stable SEI and enhance the Na stripping/plating efficiency. While for
LIBs glyme-based electrolytes have been outperformed by ester-based ones, whether glymes will be a
valid alternative electrolyte system for NIBs is still an open question.

 Cui et al. demonstrated that a highly reversible plating/stripping process (dendritic-free) was achieved
at room temperature by using NaPF6-glyme systems. Such effect is most likely attributable to a
uniform inorganic-rich SEI layer formation, impermeable to electrolyte solvent. The improved sodium
storage behaviour with ether-based electrolytes has been reported for several materials including CuS
nanosheets, bismuth, Sn, high specific surface area carbon and TiO2. In all cases and independently of
the electrode chemistry, the enhanced performance was attributed to the formation of a thin,
compact and uniform SEI enabling fast Na+ ion transport. However, issues related to the use of
glymes were also reported for HC and Sb.

 Besides optimal ionic conductivity, viscosity and satisfactory electrochemical performance, ester- and
ether-based electrolytes suffer from high flammability and low anodic stability respectively. In search
of safer high voltage electrolytes, ionic liquids (IL)-based electrolytes have been widely investigated as a
promising alternative. The research on ILs finds its primary motivation within the green chemistry
approach. Indeed, the general use of non-volatile solvents such as ILs is a well-perceived strategy
toward the reduction of waste, toxicity, and hazards at the industrial scale. ILs generally present
lower conductivity