Phase Equilibria in Lithium-Chalcogen Systems

Cunningham, P.T.; Johnson, S. A.; Cairns, Elton J.

doi:10.1149/1.2407871

Cited by 39 publications

(52 citation statements)

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“…The PS and PSe distances of ≈204 and ≈220 pm for HT‐Li 7 PS 6 and HT‐Li 7 PSe 6 , respectively, agree perfectly with the average values observed in the compounds Li 3 PS 4 (PS=205 pm14) and K 3 PSe 4 15 (PSe=220 pm), respectively. The average distances LiS (252 pm) and LiSe (264 pm) based on the split position 48 h for Li seem to be slightly increased in comparison to values found for Li 3 PS 4 (LiS=244–251 pm) and Li 2 Se16 (LiSe=260 pm), respectively, with ordered Li atoms.…”

Section: Resultsmentioning

confidence: 57%

Relationship between Channel and Sorption Properties in Coordination Polymers with Interdigitated Structures

Hijikata

Horike

Sugimoto

et al. 2011

Chemistry A European J

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Porous coordination polymers constructed from Zn(2+) and isophthalate with linear bipyridyl-type ligands were synthesized. [Zn(ip)(bpb)](n) (CID-21; ip=isophthalate, bpb=1,4-bis(4-pyridyl)benzene), [Zn(ip)(bpt)](n) (CID-22; bpt=3,6-bis(4-pyridyl)-1,2,4,5-tetrazine), and [Zn(ip)(bpa)](n) (CID-23; bpa=1,4-bis(4-pyridyl)acetylene) all have interdigitated structures of layers and similar void volumes (≈27%). In these compounds, 1D bottleneck-type channels run along the perpendicular direction of the layer stacking and their properties are strongly dominated by the dipyridyl linker ligands. Because of the difference in packing of 2D layers, CID-21 and CID-22 have relatively rigid porous structures, whereas CID-23 has greater flexibility, as indicated by the results of powder X-ray diffraction studies. The micropores of CID-22 surrounded by tetrazine moieties adsorb polar molecules, such as methanol and water. The higher affinity of CID-22 for water than CID-21 is supported by a theoretical study. The 1D channel of CID-23 is wider than that of the other two compounds, which enables the incorporation of aromatic molecules. This is because the shape of the bpa linker ligand generates a wider pore diameter (8.6 Å). Only CID-23 can adsorb a benzene molecule and the isotherm of benzene has a gate-opening-type profile. This offers proof of the guest accommodation process through large structural transformation from a nonporous to a porous structure. The flexibility and restricted pore space of CID-23, at 298 K, allows only benzene, but not cyclohexane, to enter the channels. The porous structure exhibits clear selectivity for these similar guests. The incorporation of an elongated dipyridyl linker ligand in the 2D coordination layers provides a strategy for the design of microporous compounds with different flexibilities, microporous environments, and separation abilities.

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Section: Resultsmentioning

confidence: 57%

Relationship between Channel and Sorption Properties in Coordination Polymers with Interdigitated Structures

Hijikata

Horike

Sugimoto

et al. 2011

Chemistry A European J

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“…The apparatus and the procedures used for calibration and data collection have been previously described (1).…”

Section: Methodsmentioning

confidence: 99%

Phase Equilibria in Lithium-Chalcogen Systems

Cunningham

Johnson

Cairns

1973

J. Electrochem. Soc.

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“…The non-stoichiometry degree of the composition must also be taken into account, since it is known that the ionic conductivity of Cu 2−σ Se decreases with non-stoichiometry degree σ increasing [17], followed by decreasing the concentration of mobile copper ions. Lithium ions in Li x Cu 1.75 Se , in our opinion, are also mobile, since Li 2 Se has a similar with Cu 2 Se the FCC structure of the Fm3m type with close unit cell parameters and exhibits superionic conductivity at elevated temperatures [42]. When the lithium content in Li x Cu 1.75 Se increases, the concentration of mobile ions increases too, which should increase the ionic conductivity, but the mobility of lithium ions is apparently lower than the mobility of copper ions; therefore, the ionic conductivity of the Li x Cu 1.75 Se compounds should be lower than those of binary copper selenides Cu 2−σ Se with the same cation deficiency in the lattice ( σ = 0.25-x), and, in any case, lower than those in Cu 2 Se .…”

Section: Resultsmentioning

confidence: 77%

Effect of lithium doping on electrophysical and diffusion proper-ties of nonstoichiometric superionic copper selenide Cu1.75Se

Balapanov¹,

Kuterbekov²,

Kubenova³

et al. 2017

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The results of studies of the ionic conductivity and the conjugated chemical diffusion coefficients (CCDC) in the nonstoichiometric Li x Cu 1.75 Se (0 ≤ x ≤ 0.25) ternary alloys are presented. It has been observed that the values of the ionic conductivity of Cu 1.75 Se copper selenide decreases with lithium doping in general owing to increasing the the activation energy. The increasing of the conjugate chemical diffusion coefficients of the cations and electron holes was observed with increasing of lithium content, despite the decreasing of self-diffusion coefficients of the cations and decreasing of electron mobilities. The behavior of the conjugate chemical diffusion coefficients explained by a decrease in the degree of non-stoichiometry of the composition, leading to an increase of the internal electric field accelerating the motion of slower particles.

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Phase Equilibria in Lithium-Chalcogen Systems

Cited by 39 publications

References 1 publication

Relationship between Channel and Sorption Properties in Coordination Polymers with Interdigitated Structures

Relationship between Channel and Sorption Properties in Coordination Polymers with Interdigitated Structures

Phase Equilibria in Lithium-Chalcogen Systems

Effect of lithium doping on electrophysical and diffusion proper-ties of nonstoichiometric superionic copper selenide Cu1.75Se

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