Structures of the Polymer Electrolyte Complexes PEO<sub>6</sub>:LiXF<sub>6</sub> (X = P, Sb), Determined from Neutron Powder Diffraction Data

Gadjourova, Zlatka; Marero, D. Martín y; Andersen, K.H.; Andreev, Yuri G.; Bruce, Peter G.

doi:10.1021/cm000949k

Cited by 120 publications

(161 citation statements)

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“…[28][29][30] This is more or less in agreement with our DSC results which give 48% for amorphous polymer. Since the presence of salt may influence the crystal formation of PEO as has been observed by other groups in the past 35,36 we believe that discrepancies between the 45% calculated from literature and the 48% from our DSC data may result from the presence of salt. At the same time, examining the DSC traces shown in Fig.…”

Section: Resultssupporting

confidence: 59%

Supramolecular structures in nanocomposite multilayered films

Stefanescu

Dundigalla

Ferreiro

et al. 2006

Phys. Chem. Chem. Phys.

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We investigate the multilayered structures of poly(ethylene)oxide/montmorillonite nanocomposite films made from solution. The shear orientation of a polymer-clay network in solution combined with simultaneous solvent evaporation leads to supramolecular multilayer formation in the film. The resulting films have highly ordered structures with sheet-like multilayers on the micrometer length scale. The polymer covered clay platelets were found to orient in interconnected blob-like chains and layers on the nanometer length scale. Inside the blobs, scattering experiments indicate the polymer covered and stacked clay platelets oriented in the plane of the film. The polymer is found to be partially crystalline although this is not visible by optical microscopy. Atomic force microscopy suggests that the excess polymer, which is not directly adsorbed to the clay, is wrapped around the stacked platelets building blobs and the polymer also interconnects the polymer-clay layers. Overall our results suggest the re-intercalation of clay platelets in films made from exfoliated polymer-clay solutions as well as the supramolecular order and hierarchical structuring on the nanometer, via micrometer to the centimeter length scale.

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Section: Resultssupporting

confidence: 59%

Supramolecular structures in nanocomposite multilayered films

Stefanescu

Dundigalla

Ferreiro

et al. 2006

Phys. Chem. Chem. Phys.

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“…These models are constructed from the structures in (PEO) 6 :LiAsF 6 , (PEO) 6 :LiPF 6 and (PEO) 6 :LiSbF 6 polymer-salt complexes, i.e. electrolytes, which have been solved ab-initio from X-ray diffraction data recently 28,29 . The reason why we have chosen these structures among variety of PEO-salt complexes is that the conformation of PEO chains within the crystal unit cell for these three models belongs to P2 1 /a space group, quite similar to the distorted D 7 space group between the resonant and non-resonant emission spectra for oxygen atoms.…”

Section: Resultsmentioning

confidence: 99%

Structural Conformation in a Poly(ethylene oxide) Film Determined by X-ray Emission Spectroscopy

et al. 2007

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Abstract:The electronic structure of poly(ethylene oxide) (PEO) in a thin (< 1 μ) film sample was experimentally probed by X-ray emission spectroscopy. The emission spectra from this film were much sharper with more resolved fine structure than the spectra from the bulk polymer from which it was cast. Both non-resonant and resonant X-ray emission spectra were simulated using density functional theory (DFT) applied to four different models representing different conformations in the polymer. Calculated spectra were 2 compared with experimental results for the PEO film. It was found that the best fit was obtained with the polymer conformation in PEO electrolytes from which the salt (LiMF 6 , M=P, As, or Sb) had been removed. This conformation is different from that in the crystalline bulk polymer and implies that film casting, commonly used to form electrolytes for Li polymer batteries, induces the same conformation in the polymer with or without the salt present.

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“…[19] In such coordinate structures, the PEO chains have never been found to adopt the all-trans conformation sequence. The computer simulation showed that as table coordinate structure can not be achieved between the Li + ions and the EO segmentsint he alltrans conformation.…”

Section: Fnmr Reveals That the Motions Of LImentioning

confidence: 99%

“…If considering the significant change in the mobility of the Li + in the same temperature range (see Figure 3b and the relatedd iscussion), the 19 …”

mentioning

confidence: 96%

“…À .F igure S2 shows the temperature dependent static 19 FNMR of a-CD-PEO 40 /Li + .I nt he spectra, the 19 F signals show the almostc onstant line shape and wide width over the temperatures range from 273 Kt o3 13 K, indicating the low mobility of the anions. If considering the significant change in the mobility of the Li + in the same temperature range (see Figure 3b and the relatedd iscussion), the 19 …”

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confidence: 97%

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Fast Lithium‐Ion Transportation in Crystalline Polymer Electrolytes

Yang

et al. 2017

ChemPhysChem

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Fast lithium-ion transportation is found in the crystalline polymer electrolytes, a-CD-PEO n /Li + (n = 12, 40), prepared by selfassembly of a-cyclodextrin (CD), polyethylene oxide (PEO) and Li + salts. Ad etailed solid-state NMR study combinedw ith the X-ray diffraction technique reveals the uniques tructural features of the samples, that is, a) the tunnels tructure formedb y the assembled CDs, providing the ordered long-range pathway for Li + ion transportation;b )the all-trans conformational sequenceo ft he PEO chains in the tunnels, attenuating significantly the coordination between Li + and the EO segments. The origin of the fast lithium-ion transportation has been attributed to these unique structural features. This work demonstrates the first example in solid polymer electrolytes (SPEs) for "creating" fast iont ransportation through material design and will find potentiala pplicationsi nt he design of new ionconducting SPE materials.Fast lithium-ion transportation is widely presenti nt he ceramic lithium superionic conductors, [1] and its molecular origin is attributed to the unique structural features, which "create" the highly mobile lithium ions and providet he special ion pathway to facilitate the long distance transportation of lithium ions.[2]The reported lithium superionic conductors often exhibit a very high ionic conductivity at the ordinary temperature. [3] However,t he similar fast lithium-ion transportation has never been found in solid polymer electrolytes (SPEs). Ther eported best-in-class solid polymer electrolytes now can have the conductivity of 10 À4 Scm, [4a] which is still 2-3 order lower than the inorganic superionic conductors. The reasons are at least twofold:1 .T he strong coordinationb etween Li + ions and the polymer segments that often significantly lowerst he mobility of Li + ions;2.The lack of long-rangeordered pathway that suppresses the efficient long-range Li + ion transportation. Many efforts to enhancet he ionic conductivity of SPE have been made in am anner to solvet he above two issues.F or example,t he isovalent doping, which can lower the coordination between Li + ions and the polymer segments and thus increase the Li + mobility,h as been regarded as an effective strategy to facilitatet he Li + transportation.[4] Exploiting the high segmental mobility of oligomeric polyethylene oxide (PEO) to attenuate the coordination between Li + ions and the polymer segmentsa nd in turn increaset he conductivity also falls into this category.[5] Along the line of constructing the ordered structures for the long-range ion transportation, some pioneer works have studied the conductive polyethylene oxide (PEO):Li + complex crystals where PEO chainsa dopt the helical structures to form visual tunnels to facilitate the long-range transportation of the Li + ions.[6] Later,aseries of interesting works on theo riented PEO:Li + complex crystals concretely evidence the influences of long-range ordered structure on the ionic conductivity of material. [7] Recently,w er eported ac rystall...

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Structures of the Polymer Electrolyte Complexes PEO₆:LiXF₆ (X = P, Sb), Determined from Neutron Powder Diffraction Data

Cited by 120 publications

References 12 publications

Supramolecular structures in nanocomposite multilayered films

Supramolecular structures in nanocomposite multilayered films

Structural Conformation in a Poly(ethylene oxide) Film Determined by X-ray Emission Spectroscopy

Fast Lithium‐Ion Transportation in Crystalline Polymer Electrolytes

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Structures of the Polymer Electrolyte Complexes PEO6:LiXF6 (X = P, Sb), Determined from Neutron Powder Diffraction Data

Cited by 120 publications

References 12 publications

Supramolecular structures in nanocomposite multilayered films

Supramolecular structures in nanocomposite multilayered films

Structural Conformation in a Poly(ethylene oxide) Film Determined by X-ray Emission Spectroscopy

Fast Lithium‐Ion Transportation in Crystalline Polymer Electrolytes

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Product

Resources

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Structures of the Polymer Electrolyte Complexes PEO₆:LiXF₆ (X = P, Sb), Determined from Neutron Powder Diffraction Data