New macromolecules for solid polymeric electrolytes

Allcock, Harry R.; Napierala, Mark E.; Olmeijer, David L.; Cameron, Charles G.; Kuharcik, Susan E.; Reed, Carey S.; OʼConnor, Stephen J

doi:10.1016/s0013-4686(97)10012-3

Cited by 42 publications

(31 citation statements)

References 19 publications

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“…Cross-linking indeed surpresses the crystallisation (and offers the additional benefit of an increased mechanical stability), but simultaneously deteriorates the segmental mobility and with this the ionic conductivity. Another route towards a reduction of the crystallinity involves the use of inorganic polymers such as polyphosphazene [17][18][19][20] and polysiloxane based materials [21][22][23], in which polyether or related Li coordinating residues are attached to an inorganic backbone. The rather high flexibility of the inorganic backbone entails both, low T g values and a reduced tendency towards crystallisation and thus offers the promise of high ionic conductivity.…”

Section: Salt-in-polymer-electrolytesmentioning

confidence: 99%

“…Such an interaction has been inferred from a shift in the Raman band for the ClO 4 and CF 3 SO 3 anions in the systems LiClO 4 , LiTf/PEO/TiO 2 [49] and LiClO 4 , LiTf/PMEO/TiO 2 . Donoso and coworkers [50] used 19 F decoupled 7 Li-NMR to find a decrease in the anion-cation interaction in PEO/LiBF 4 /Al 2 O 3 composites which has been interpreted in terms of an interaction between X − and the ceramic surface.…”

Section: Nanocompositesmentioning

confidence: 99%

“…1) [100]. In an attempt to obtain information about the local Li coordination motifs in this polymer electrolyte system we performed an extended solid state NMR study employing 19 F{ 7 Li}-and 13 C{ 7 Li}-REDOR NMR spectroscopy [90,92]. (PEO) 3 : LiTFSI served as a model compound to validate the applicability of the approach.…”

Section: Polyethylene Oxide Based Electrolytesmentioning

confidence: 99%

“…2. In the 19 F MAS NMR spectrum, two different 19 F signals can be identified and assigned to the two crystallographically distinct CF 3 groups of the TFSI anion. In (PEO) 3 : LiTFSI, only one of the CF 3 SO 2 -residues per anion coordinates to the lithium ions, whereas the second residue points away from the PEO helices to the interchain space.…”

Section: Polyethylene Oxide Based Electrolytesmentioning

confidence: 99%

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Local Li Cation Coordination and Dynamics in Novel Solid Electrolytes

Wüllen¹,

Echelmeyer

Voigt

et al. 2010

Zeitschrift Für Physikalische Chemie

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Ionic TransportResearch on solid ionic conductors for use as electrolytes in all solid state batteries still constitutes a rather vivid branch of today's materials science. Despite enormous efforts, neither the development of a solid electrolyte fulfilling the key requirements such as mechanical stability and high ionic conductivity at ambient temperature has been successful nor has an extended understanding of the local Li coordination motifs in the often amorphous systems been obtained. In this contribution, recent progress both in the development of novel solid state electrolytes with high ionic conductivity and mechanical stability and in the characterization of the local Li coordination motifs in these electrolytes from our laboratory is presented. The work was performed as a project within the framework of the Collaborative Research Centre SFB 458 "Ionic Motion in Materials with Disordered Structures -From Elementary Steps to Macroscopic Transport". Results will be given for polymer electrolytes based on polyethylene oxide (PEO), polyphosphazene (PPZ) and polyacrylonitrile (PAN) with various Li salts, nano-composites of these polymer electrolytes and Al 2 O 3 as a ceramic filler, novel inorganic/organic hybrid electrolytes, in which a mixture of an ionic liquid and Li salt is confined within the pore system of a SiO 2 glass, and a crystalline electrolyte, Li 5 La 3 Nb 2 O 12 . Employing a range of advanced solid state NMR methodologies including dipolar based NMR techniques and pulsed field gradient (PFG) NMR and impedance spectroscopy we were able to obtain a detailed knowledge about the local Li cation coordination motifs and the mechanism of Li transport in these electrolytes. Especially the hybrid electrolytes and the salt rich PAN based polymer electrolytes were identified as rather promising materials which combine a high ionic conductivity and mechanical stability.

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Section: Salt-in-polymer-electrolytesmentioning

confidence: 99%

Section: Nanocompositesmentioning

confidence: 99%

Section: Polyethylene Oxide Based Electrolytesmentioning

confidence: 99%

Section: Polyethylene Oxide Based Electrolytesmentioning

confidence: 99%

See 2 more Smart Citations

Local Li Cation Coordination and Dynamics in Novel Solid Electrolytes

Wüllen¹,

Echelmeyer

Voigt

et al. 2010

Zeitschrift Für Physikalische Chemie

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“…The disadvantage of such compounds relates to the instability of sizes. However the electrolytes, which are formed from the polyethylene oxide, exhibit mechanical stability at high ionic conductivity and temperature, which is far below melting point [29,30].…”

Section: Introductionmentioning

confidence: 99%

Spectroscopic Investigation of Composite Polymeric and Monocrystalline Systems with Ionic Conductivity

Radziuk¹,

Möhwald²

2011

Polymers

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Abstract:The conductivity mechanism is studied in the LiCF 3 SO 3 -doped polyethylene oxide by monitoring the vibrations of sulfate groups and mobility of Li + ion along the polymeric chain at different EO/Li molar ratios in the temperature range from 16 to 90 °С. At the high EO/Li ratio (i.e., 30), the intensity of bands increases and a triplet appears at 1,045 cm −1 , indicating the presence of free anions, ionic pairs and aggregates. The existence of free ions in the polymeric electrolyte is also proven by the red shift of bands in Raman spectra and a band shift to the low frequency Infra-red region at 65 < T < 355 °С. Based on quantum mechanical modeling, (method MNDO/d), the energies (minimum and maximum) correspond to the most probable and stable positions of Li + along the polymeric chain. At room temperature, Li + ion overcomes the intermediate state (minimum energy) through non-operating transitions (maximum energy) due to permanent intrapolymeric rotations (rotation of C, H and O atoms around each other). In solid electrolyte (Li 2 SO 4 ) the mobility of Li + ions increases in the temperature range from 20 to 227 °С, yielding higher conductivity. The results of the present work can be practically applied to a wide range of compact electronic devices, which are based on polymeric or solid electrolytes.

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Polyphosphazenes

Allcock¹

2005

Encyclopedia of Inorganic Chemistry

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Polyphosphazenes comprise the largest class of inorganic polymers. During the past 10 years, new synthetic developments have arisen that allow carefully tailored macromolecules to be assembled with precise chain lengths and with access to star geometries and a range of hybrid phosphazene‐organic polymer systems. This has stimulated research in the use of polyphosphazenes in biomedicine, optoelectronics (photonics), lithium battery technology, and fuel cell membranes, as well as in new elastomers and hydrogels.

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New macromolecules for solid polymeric electrolytes

Cited by 42 publications

References 19 publications

Local Li Cation Coordination and Dynamics in Novel Solid Electrolytes

Local Li Cation Coordination and Dynamics in Novel Solid Electrolytes

Spectroscopic Investigation of Composite Polymeric and Monocrystalline Systems with Ionic Conductivity

Polyphosphazenes

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