Ion Transport in Cryptand and Crown Ether Lithium Salt Complexes

Dillon, Rensl E. A.; Shriver, Duward F.

doi:10.1021/cm990376f

Cited by 48 publications

(42 citation statements)

References 41 publications

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“…3 shows the temperature dependence of ionic conductivity of the (12-Crown-4)-LiTFSI complexes at (1/1, 1/0.95 and 1/0.67 molar ratios). At temperatures below the second plastic transition, ∼89 • C, the 1/1 complex showed the highest conductivity throughout the plastic range reaching 4.6 × 10 −6 Scm −1 at 50 • C, a value close to the one reported by others [13]. The 1/0.95 complex showed lower conductivity than that of the 1/1 contradicting what we predicted that the availability of ion-free crown rings in the solid would provide a lower energy barrier for the Li ions to move from a complexed ring to an ion-free one.…”

Section: (18-crown-6)-litfsi Complexessupporting

confidence: 87%

Plastic crystalline phases of crown ether:salt complexes and their utilization in lithium-metal batteries

Abouimrane

Alarco

Abu-Lebdeh

et al. 2007

Journal of Power Sources

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/npsi/ctrl?action=rtdoc&an=9064982&lang=en http://nparc.cisti-icist.nrc-cnrc.gc.ca/npsi/ctrl?action=rtdoc&an=9064982&lang=frAccess and use of this website and the material on it are subject to the Terms and Conditions set forth at http://nparc.cisti-icist.nrc-cnrc.gc.ca/npsi/jsp/nparc_cp.jsp?lang=en NRC Publications Archive Archives des publications du CNRCThis publication could be one of several versions: author's original, accepted manuscript or the publisher's version. / La version de cette publication peut être l'une des suivantes : la version prépublication de l'auteur, la version acceptée du manuscrit ou la version de l'éditeur. For the publisher's version, please access the DOI link below./ Pour consulter la version de l'éditeur, utilisez le lien DOI ci-dessous.http://dx.doi.org/10.1016/j.jpowsour.2007.06. 044 Journal of Power Sources, 174, 2, pp. 1193Sources, 174, 2, pp. -1196Sources, 174, 2, pp. , 2007 Plastic crystalline phases of crown ether:salt complexes and their utilization in lithium-metal batteries Abouimrane, Ali; Alarco, Pierre-Jean; Abu-Lebdeh, Yaser; Davidson, Isobel; Armand, Michel AbstractWe have shown that crown ether complexes with the lithium salt, lithium bis-(trifluoromethanesulphonyl) imide (LiTFSI), are plastic crystals as evidenced by DSC and their mechanical properties. The conductivity of the complexes was measured and found to vary as a function of crown ether:salt molar ratio. Our study of the (18-Crown-6)-LiTFSI (1/1) solid complex showed that it has a high conductivity reaching ∼10 −4 Scm −1at 50• C and an electrochemical stability of over 4 V enabling its use in a lithium-metal battery. A lithium battery with 1:1 (18-Crown-6)-LiTFSI as electrolyte was assembled, tested, and found to exhibit reversible Li + transport. Crown

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Section: (18-crown-6)-litfsi Complexessupporting

confidence: 87%

Plastic crystalline phases of crown ether:salt complexes and their utilization in lithium-metal batteries

Abouimrane

Alarco

Abu-Lebdeh

et al. 2007

Journal of Power Sources

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“…In all the DSC curves, no peak due to the melting of pure glymes is observed (see Supporting Information (SI) Table S1), 10 suggesting that no free glyme molecules exist in the equimolar mixtures. It has been reported that the equimolar complexes of crown ethers (12-crown-4 (12C4) and 15-crown-5 (15C5)) and LiTFSA are solids at room temperature, 11 although 12C4 and 15C5 have the same number of oxygen atoms as G3 and G4, respectively. The glymes have higher conformational flexibility than the crown ethers, and the flexible structure of glymes may also give rise to conformational freedom in the molten complexes.…”

Section: ¹1mentioning

confidence: 99%

Physicochemical Properties of Glyme–Li Salt Complexes as a New Family of Room-temperature Ionic Liquids

Tamura¹,

Yoshida²,

Hachida³

et al. 2010

Chemistry Letters

278

294

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Certain glymeLi salt complexes, which are composed of equimolar mixtures of a glyme and a Li salt, are liquid under ambient conditions with physicochemical properties such as high thermal stability, wide potential window, high ionic conductivity, and high Li + transference number and can be regarded as a new family of room-temperature ionic liquids.Room-temperature ionic liquids (RTILs), which are liquid at room temperature and composed entirely of ions, have attracted much attention because of their unique properties such as nonflammability, low-volatility, high chemical stability, and high ionic conductivity.1 RTILs are expected to be applied to electrochemical devices, including electric double-layer capacitors, 2 fuel cells, 3 dye-sensitized solar cells, 4 and lithium ion batteries (LIBs).5 Most of the RTILs reported to date can be classified as combinations of weakly Lewis-acidic cations and weakly Lewis-basic anions, which leads to ionic dissociation without strong coordination of solvent molecules around each ion. Thus, the most common compositions of RTILs are combinations of onium cations such as imidazolium cations, quaternary ammonium cations, and quaternary phosphonium cations and soft anions such as bis(trifluoromethylsulfonyl)-amide (TFSA ¹ ), tetrafluoroborate (BF 4 ¹ ), and hexafluorophosphate (PF 6 ¹ ). There are few reports of RTILs consisting of strongly Lewis-acidic cations such as Li + and Na + and strongly Lewis-basic anions such as F ¹ and Cl ¹ . Melting points of salts consisting of strongly Lewis-acidic cations and strongly Lewisbasic anions are generally much higher than room temperature, resulting in the formation of ionic crystals at room temperature. So far, we have reported the preparation of lithium ionic liquids consisting of lithium salts of borates having electron-withdrawing groups, to reduce the anionic basicity, and lithium coordinating ether-ligands, to dissociate the lithium cations from the anionic centers.6 However, possibly due to the strong Lewis acidity of Li + , the viscosity and ionicity (dissociativity) of the lithium ionic liquids at room temperature are as high as 500 mPa s and as low as 0.10.2, respectively, resulting in a low ionic conductivity of 10 ¹5 S cm ¹1 at its maximum. Weakly Lewis-basic anions such as BF 4 ¹ and PF 6 ¹ are prepared by the reactions between Lewis acids (BF 3 and PF 5 ) and a Lewis base (F ¹ ) by forming coordination bonds. However, the preparation of weakly Lewis-acidic cations for RTILs by the reaction between a Lewis acid and a Lewis base has not been proposed. It is anticipated that weakly Lewis-acidic cations can be prepared by the combination of alkali metal cations (Lewis acid) and suitable ligands (Lewis base).Ethers are relatively strong Lewis bases, and alkali metal cations are strongly coordinated with ethers. It is well-known that particular molar ratio mixtures of Li salts and oligoethers such as crown ethers, triglyme (G3), and tetraglyme (G4) form complexes. Henderson et al. have conducted a systematic study of glymeLi salt...

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“…Cryptands can also be used as phase-transfer catalysts 8 and solid electrolytes 9 . In addition, they have been recently tested as fluorescent sensors for radioactive perthecnetate anions with very promising results 10 .…”

Section: Introductionmentioning

confidence: 99%

Metal containing cryptands as hosts for anions: evaluation of Cu(i)⋯X and π⋯X interactions in halide–tricopper(i) complexes through relativistic DFT calculations

Ponce-Vargas

Muñoz-Castro

2015

Phys. Chem. Chem. Phys.

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More selective than crown ethers, cryptands arise as suitable hosts for several ions, with the size of the cavity and the behavior of the atoms belonging to the structure being the main factors governing their selectivity. Similar to metallacrowns, inorganic counterparts of crown ethers, the presence of metal centers in cryptands can offer significant advantages in terms of ion recognition as they provide positively charged sites, which allow them to encapsulate anions. Here, through density functional methodologies, we evaluate the preference of a tricopper(I) cryptand host toward a series of halide ions ranging from the hard fluoride to the soft iodide, where the more intense interactions are established with the hardest one, and the electrostatic term is the more relevant contributor to total interaction energy. Upon exploration of this electrostatic contribution in more detail, it is observed that as the guest becomes softer, the increase of higher order Coulombic terms, such as dipole-dipole, dipole-quadrupole, and quadrupole-quadrupole, acquires more relevance on going from 9.22% to 41.25%, denoting the key role and variation of such forces in inclusion systems with metal-containing hosts.

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Ion Transport in Cryptand and Crown Ether Lithium Salt Complexes

Cited by 48 publications

References 41 publications

Plastic crystalline phases of crown ether:salt complexes and their utilization in lithium-metal batteries

Plastic crystalline phases of crown ether:salt complexes and their utilization in lithium-metal batteries

Physicochemical Properties of Glyme–Li Salt Complexes as a New Family of Room-temperature Ionic Liquids

Metal containing cryptands as hosts for anions: evaluation of Cu(i)⋯X and π⋯X interactions in halide–tricopper(i) complexes through relativistic DFT calculations

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