“…These bands are very consistent throughout the range of anions used (unlike their 18-C-6 analogues). Our group has previously reported similar results for [Na⊂2.2.2] complexes. , …”
Complexes of lithium salts LiCF3SO3, LiI, LiCH3CO2, LiBF4, LiSCN, and Li[R−NSO2CF3] with the macrocyclic ligands 18-C-6 and 2.2.2-cryptand were examined by differential
scanning calorimetry, infrared and Raman spectroscopy, and complex impedance. The
formation of an amorphous phase appears to be facilitated by the presence of an unsymmetrical anion containing an ether oxygen of the type [R−NSO2CF3]-. An X-ray crystal
structure was determined for Li[CF3SO2N(CH2)2OCH3]; these data and that for the previously
reported Li[CF3SO2N(CH2)3OCH3] structure was correlated with the physical properties of
their 18-C-6 and 2.2.2-cryptand complexes.
“…These bands are very consistent throughout the range of anions used (unlike their 18-C-6 analogues). Our group has previously reported similar results for [Na⊂2.2.2] complexes. , …”
Complexes of lithium salts LiCF3SO3, LiI, LiCH3CO2, LiBF4, LiSCN, and Li[R−NSO2CF3] with the macrocyclic ligands 18-C-6 and 2.2.2-cryptand were examined by differential
scanning calorimetry, infrared and Raman spectroscopy, and complex impedance. The
formation of an amorphous phase appears to be facilitated by the presence of an unsymmetrical anion containing an ether oxygen of the type [R−NSO2CF3]-. An X-ray crystal
structure was determined for Li[CF3SO2N(CH2)2OCH3]; these data and that for the previously
reported Li[CF3SO2N(CH2)3OCH3] structure was correlated with the physical properties of
their 18-C-6 and 2.2.2-cryptand complexes.
Amorphous solid electrolytes were formed by the interaction of cryptands or crown ethers
with a lithium salt, Li[CF3SO2N(CH2)3OCH3], when the cavity size of the macrocycle does
not match the diameter of the lithium cation. With the exception of [Li⊂18-C-6][(CF3SO2)2N]
(the mathematical symbol of inclusion, ⊂, is used to indicate Li+ included in 18-C-6), the
complexes of Li[(CF3SO2)2N] with cryptand and crown ethers do not form amorphous
electrolytes. Complexes of Li[CF3SO2N(CH2)3OCH3] and Li[(CF3SO2)2N] were examined by
thermal, spectroscopic, and conductivity methods to determine the role of the anion on ionic
glass formation.
“…According to the fitted data in Table 1, the A term increases as the AlCl 3 content increases, up to a mole fraction of 0.67, and then decreases. Compared with those in the polymer electrolyte NaCF 3 SO 3 /aPEO systems, 22 the B terms for the AlCl 3 /NaN(CN) 2 systems are generally smaller than that of the PEO system, indicating lower pseudoactivation energies for the ionic inorganic system. Both the relatively low value of the conductivity and the bent curves in Figure 4 suggest the coupling of diffusion with the medium, which is in contrast to that in superionic glasses (such as AgCl/AgI/CsCl).…”
Section: Resultsmentioning
confidence: 89%
“…According to the fitted data in Table , the A term increases as the AlCl 3 content increases, up to a mole fraction of 0.67, and then decreases. Compared with those in the polymer electrolyte NaCF 3 SO 3 /aPEO systems, the B terms for the AlCl 3 /NaN(CN) 2 systems are generally smaller than that of the PEO system, indicating lower pseudoactivation energies for the ionic inorganic system. 4 Ionic conductivity of AlCl 3 /NaN(CN) 2 mixtures. 5 Ionic conductivity versus 100/( T − T 0 ) for AlCl 3 /NaN(CN) 2 mixtures ( T 0 ≈ T g − 50).…”
Ambient temperature alkali glassy salt mixtures, x[AlCl3]/(1 − x)[NaN(CN)2] (x = 0.4−0.75), were prepared. A large increase in the C⋮N stretching frequencies for these materials
indicate complex formation between the anion [N(CN)2]- and AlCl3 molecule. Ab initio
calculations confirm the assignments of the vibrational frequencies. The 1:1 adduct has a
glass transition at 27 °C, and the glassy state persists for 4 weeks at room temperature.
The room temperature ionic conductivity of this glass is 6.6 × 10-6 S/cm, and it increases as
the AlCl3 content increases. The temperature dependence of the conductivity follows the
Vogel−Tamman−Fulcher equation, suggesting that ion transport is coupled to local motion
in the glassy salt mixture system.
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