High-conductivity electrolytes composed of polystyrene carrying pendant oligo(oxyethylene)cyclotriphosphazenes and lithium perchlorate

Inoue, Kenzo; Nishikawa, Yasumitsu; Tanigaki, Teiichi

doi:10.1021/ja00020a024

Cited by 47 publications

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“…Similar behavior has been observed in (EO) n -containing comblike polystyrene. 30 Molecular dynamics simulations 31 and neutron diffraction data 32 indicate that the Li + ions are coordinated with PEO through five ether oxygens of a polymer chain. 33 p(Nte) 20 has longer side chains that appear to be more effective in coordinating Li + .…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Structure–Conductivity Relationship for Peptoid-Based PEO–Mimetic Polymer Electrolytes

et al. 2012

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Polymer electrolytes offer great potential for application in lithium batteries. In order to systematically optimize the performance of these materials, atomic level synthetic control over the polymer chemical structure is desired. In this study, we designed a series of chemically defined, monodisperse peptoid polymers to explore the impact of side-chain structure on the thermal and electrical properties. A series of comblike peptoid homopolymers with ethylene oxide (EO) n side chains of varying length were synthesized by a rapid solid phase synthetic method. The electrical properties of these materials with dissolved lithium salt were characterized by ac impedance. The temperature dependence of the ionic conductivity of the polypeptoid electrolytes is consistent with the Vogel−Tamman−Fulcher equation. The optimum ionic conductivity of 2.6 × 10 −4 S/cm achieved for oligo-N-2-(2-(2-methoxyethoxy)ethoxy)ethylglycine−Li salt complex at 100°C, is approximately 10-fold lower than the analogous PEO−salt complex. It is, however, nearly 2 orders of magnitude higher than previously reported comblike PEO−mimetic polypeptides. The ionic conductivities of these side chain analogs vary by 3 orders of magnitude, but this variation is entirely governed by the proximity of the system to the glass transition temperature. This investigation shows that polypeptoids provide a unique platform for examining the structure−property relationships of solid polymer electrolytes.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Structure–Conductivity Relationship for Peptoid-Based PEO–Mimetic Polymer Electrolytes

et al. 2012

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“…However, linear PEG shows comparatively low ion conductivity at low temperature, due to the existence of crystalline domains, which interfere with the ionic transport. 18 In this context, we have expected that if the OEGs are densely grafted along the backbone, carrier ions could move in the continuous conducting phase to achieve a high conductivity, even though the backbone is expected to be rigid due to the densely-grafted side chains. Actually, higher conductivities compared to PEO/Li salt systems have been achieved with some comb-like polymers in which OEG side chains are attached to a flexible polymer backbone with a low glass transition temperature, such as polysiloxanes 16 and polyphosphazenes.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of polymers with densely-grafted oligo(ethylene glycol)s by Pd-initiated polymerization of oxyethylene-containing diazoacetates

et al. 2015

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Synthesis and characterization of polymers with densely-grafted oligo(ethylene glycol)s (OEGs) are described. Polymerization of OEG-containing diazoacetates with (η 3 -C 3 H 5 )PdCl-based initiating systems afforded C-C main chain polymers bearing OEGs on each main chain carbon atom. The polymers with a short OEG side chain showed a lower critical solution temperature-type phase separation in an aqueous medium; the transition temperatures were higher than those of the corresponding vinyl polymers with the same oxyethylene chain length. In addition, the Li-ion conductivity was examined to reveal that the polymers with densely-grafted OEGs showed higher values than the corresponding vinyl polymers, despite the fact that no significant difference in the glass transition temperature was observed between the two types of polymers. † Electronic supplementary information (ESI) available: 1 H NMR spectra, turbidity measurements, and DSC thermograms of OEG-containing polymers. See

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“…Inoue et al have described the synthesis and characterization of a related polymer. These “polycascade polymers” contain an oligoethylenoxy-bearing cyclotriphosphazene linked to polystyrene and poly(vinylbiphenyl). , These polymers were found to have low T g values and to give conductivities in the range of 10 -5 S cm -1 at 30 °C. These relatively high conductivities were thought to be due to the formation of a conducting phase associated with the ethyleneoxy units on the cyclotriphosphazene units attached to a nonconducting phase, namely, the polystyrene backbone.…”

Section: Resultsmentioning

confidence: 99%

Polyphosphazenes with Novel Architectures: Influence on Physical Properties and Behavior as Solid Polymer Electrolytes

et al. 1998

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Three types of polyphosphazenes with different architectures have been synthesized and characterized. The influence of the polymer architecture on solid ionic conductivity was of particular interest. The first type includes linear oligo- and polyphosphazenes with the general formula [NP(OCH2CH2OCH2CH2OCH3)2] n (MEEP) with different chain lengths. The second type consists of a series of triarmed star-branched polyphosphazenes with the general formula N{CH2CH2NH(CF3CH2O)2P[NP(OCH2CH2OCH2CH2OCH3)2] n }3 with different arm lengths. These were synthesized via the reaction of the tridentate initiator [N{CH2CH2NH(CF3CH2O)2PN−PCl3 +}3][PCl6 -]3 with the phosphoranimine Cl3PNSiMe3 in CH2Cl2 followed by halogen replacement with sodium (methoxyethoxy)ethoxide. The molecular weights in this system were carefully controlled by variation of the monomer-to-initiator ratios, and the effect of polymer molecular weight on solid ionic conductivity was examined. The third polymer system was designed to examine the effect of complex branching on ionic conductivity. Thus, a highly branched polymer containing five branches from a cyclotriphosphazene pendent side group (with 26 ethyleneoxy units per repeat unit) was synthesized. The conductivity of this polymer in the presence of three different salts has been measured and compared to the behavior of MEEP with a corresponding molecular weight. The mechanism of ion transport in these systems is discussed.

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High-conductivity electrolytes composed of polystyrene carrying pendant oligo(oxyethylene)cyclotriphosphazenes and lithium perchlorate

Cited by 47 publications

References 0 publications

Structure–Conductivity Relationship for Peptoid-Based PEO–Mimetic Polymer Electrolytes

Structure–Conductivity Relationship for Peptoid-Based PEO–Mimetic Polymer Electrolytes

Synthesis of polymers with densely-grafted oligo(ethylene glycol)s by Pd-initiated polymerization of oxyethylene-containing diazoacetates

Polyphosphazenes with Novel Architectures: Influence on Physical Properties and Behavior as Solid Polymer Electrolytes

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