Diffusion, conductivity and DSC studies of a polymer gel electrolyte composed of cross-linked PEO, Î³-butyrolactone and LiBF4

Hayamizu, Kikuko; Aihara, Yûichi; Arai, Shigemasa; Price, William S.

doi:10.1016/s0167-2738(97)00527-4

Cited by 73 publications

(47 citation statements)

References 18 publications

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“…We may thus assume that anions are prime ionic carriers in PPO/LiClO 4 complexes. The larger diffusion coefficient of anions as compared with cations has been confirmed with the pulsed field gradient NMR method 17. In Figure 8 we found a close correlation between f ′ seg and Λ m at 20 °C.…”

Section: Discussionsupporting

confidence: 66%

Microphase separation and ion‐conduction mechanisms in polypropylene oxide/lithium perchlorate (LiClO₄) complexes

Furukawa

Mukasa

Suzuki

et al. 2002

J Polym Sci B Polym Phys

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Broadband dielectric spectroscopy was used to examine ion-conduction mechanisms in polypropylene oxide (PPO) with a molecular weight of 4000 complexed with LiClO 4 . Two distinct conduction mechanisms were proposed with respect to high and low salt concentration regions. In a concentrated regime (Li/O Ͼ10%), the segmental motion of PPO molecules is significantly slowed down by enhanced cation coordination that results in a marked decrease in molar conductivity. We found a linear relationship between the ionic diffusion coefficient and the relaxation frequency of slowed segmental motion over broad temperature and salt-concentration ranges. The use of a random walk scheme revealed that ions hop around at the same rate as slowed segmental motion for a monomer length. In a dilute regime (Li/O Ͻ0.1%), ions are temporarily localized in a limited domain. The direct current conductivity is achieved by structural renewal that releases ions from such localization and provides a diffusional character. At intermediate salt concentrations, microphase separation into iondepleted and ion-rich regions was evidenced by the coexistence of fast and slow segmental processes. The molar conductivity revealed a maximum at Li/O ϭ 3%. Its decrease at higher salt concentrations was attributed to the slowing down of segmental motion, and that at lower salt concentrations was attributed to localization of ionic motion.

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Section: Discussionsupporting

confidence: 66%

Microphase separation and ion‐conduction mechanisms in polypropylene oxide/lithium perchlorate (LiClO₄) complexes

Furukawa

Mukasa

Suzuki

et al. 2002

J Polym Sci B Polym Phys

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“…The pseudo activation energy E a and the pre‐exponent factor A are estimated and listed in Table 3. The values of E a are in the range of 5.1–5.9 KJ/mol, which are small and much smaller than that of the PEO‐LiClO 4 ‐Al 2 O 3 system24 but comparable or higher than that of the PEG400/LiCl system reported by Munchow et al26 The values of A are within 0.84–1.15 S cm −1 K 1/2 , which rank in the middle among values in many reports,27, 28 but one order of magnitude higher than PEG400/LiCl 26. The appreciable ionic conductivity of the CPE films is attributed to the small E a and intermediately high A .…”

Section: Resultsmentioning

confidence: 99%

Li_1.3Al_0.3Ti_1.7(PO₄)₃ filler effect on (PEO)LiClO₄ solid polymer electrolyte

Wang¹,

Pan²

2005

J Polym Sci B Polym Phys

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Composite polymer electrolyte (CPE) films consisting of PEO, LiClO 4 , and Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 with fixed EO/Li ϭ 8 but different relative compositions of the two lithium salts were prepared by the solution casting method. The CPE films were characterized using SEM, DSC, electrical impedance spectroscopy (EIS), and ion transference number measurement. It was found that the incorporation of LiClO 4 and Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 into PEO by keeping EO/Li ϭ 8 reduced the crystallinity of PEO from 50.34% to the range of 3.57-15.63% depending upon the relative composition of the two salts. The room temperature impedance spectra of the CPE films all exhibited a shape of depressed semicircle in the high frequency range and inclined line in the low frequency range, but the high temperature ones were mainly inclined lines. The Li ϩ ionic conductivity of the CPE films mildly increased and then decreased with increasing Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 content, and the maximum conductivities were obtained at Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 content of 15 wt % for all measuring temperatures, for example, 1.378 ϫ 10 Ϫ3 S/cm at 100°C and 1.387 ϫ 10 Ϫ5 S/cm at 25°C. The temperature dependence of the ionic conductivity of the CPE films follows the Vogel-Tamman-Fulcher (VTF) equationThe pseudo activation energies (E a ) were rather low, 0.053-0.062 eV, indicating an easy migration of Li ϩ in the amorphous phase dominant PEO. The pre-exponent constant A and ion transference number t Liϩ were found to have a similar variation tendency with increasing Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 content and reached their maximums also at Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 content of 15 wt %.

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“…In the case of a gel-type electrolyte containing lithium salt (between 0.5 M and 1.5 M) lithium self-diffusion coefficients between 3 Â 10 À11 and 6 Â 10 À11 m 2 s À1 at 22 C were found, despite the fact that the electrolytes had signicantly higher amounts of solvent uptake. 65 For a solid SIPE, a self-diffusion coefficient of 1.2 Â 10 À11 m 2 s À1 at 20 C was determined. 32 From comparison of experimental and estimated self-diffusion coefficients, it is evident that D Li + ,calc is lower than D Li + ,meas derived from PFG-NMR.…”

Section: Polymer Membrane Composition and Ionic Transportmentioning

confidence: 99%

“…This is reasonable considering that for ionic conductivity measurements an external electric eld is applied, so that primarily charged species are taken into account, whereas data from PFG-NMR reect diffusion from all lithium species present in the electrolyte, including neutral clusters or aggregates as well as motion of otherwise associated lithium ions. 66 In principle, the degree of ion association a may be determined from the ratio of the two diffusion coefficients, as reported for some liquid or polymer electrolytes suitable for lithium ion batteries, 34,65,[67][68][69][70] as dividing D Li + ,calc by D Li + ,meas yields (1 À a), the degree of Li ion dissociation (cf. Table 1).…”

Section: Polymer Membrane Composition and Ionic Transportmentioning

confidence: 99%

Fluorinated polysulfonamide based single ion conducting room temperature applicable gel-type polymer electrolytes for lithium ion batteries

et al. 2019

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Diffusion, conductivity and DSC studies of a polymer gel electrolyte composed of cross-linked PEO, Î³-butyrolactone and LiBF4

Cited by 73 publications

References 18 publications

Microphase separation and ion‐conduction mechanisms in polypropylene oxide/lithium perchlorate (LiClO₄) complexes

Microphase separation and ion‐conduction mechanisms in polypropylene oxide/lithium perchlorate (LiClO₄) complexes

Li_1.3Al_0.3Ti_1.7(PO₄)₃ filler effect on (PEO)LiClO₄ solid polymer electrolyte

Fluorinated polysulfonamide based single ion conducting room temperature applicable gel-type polymer electrolytes for lithium ion batteries

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Diffusion, conductivity and DSC studies of a polymer gel electrolyte composed of cross-linked PEO, Î³-butyrolactone and LiBF4

Cited by 73 publications

References 18 publications

Microphase separation and ion‐conduction mechanisms in polypropylene oxide/lithium perchlorate (LiClO4) complexes

Microphase separation and ion‐conduction mechanisms in polypropylene oxide/lithium perchlorate (LiClO4) complexes

Li1.3Al0.3Ti1.7(PO4)3 filler effect on (PEO)LiClO4 solid polymer electrolyte

Fluorinated polysulfonamide based single ion conducting room temperature applicable gel-type polymer electrolytes for lithium ion batteries

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Product

Resources

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Microphase separation and ion‐conduction mechanisms in polypropylene oxide/lithium perchlorate (LiClO₄) complexes

Microphase separation and ion‐conduction mechanisms in polypropylene oxide/lithium perchlorate (LiClO₄) complexes

Li_1.3Al_0.3Ti_1.7(PO₄)₃ filler effect on (PEO)LiClO₄ solid polymer electrolyte