Preparation and properties of solid electrolytes on the basis of alkali metal salts and poly(2,2-dimethyltrimethylene carbonate)-block-poly(ethylene oxide)-block-poly(2,2-dimethyltrimethylene carbonate)

Melchiors, Martin; Keul, Helmut; Höcker, Hartwig

doi:10.1016/0032-3861(96)83699-8

Cited by 15 publications

(8 citation statements)

References 21 publications

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“…Recently, there have been a large number of basic studies of ionic complexes made up of a polar polymer matrix and low lattice energy metal salts. Most investigations have been carried out on Li-based polyether complexes, because of their possible applications in a broad range of electrochemical devices. − In studies of polymer electrolytes, the variation of the glass transition temperature ( T g ) with metal salt concentration is of special interest. − The dissolution of metal salts into the polymer matrixes not only generates charge carrier ions but also increases the rigidity of the polymer chains up to a moderately high salt concentration, resulting in a higher T g . Because these two competing factors each have an opposite bearing on ion transport, the number of research efforts attempting to understand this glass transition behavior has been on the increase.…”

Section: Introductionmentioning

confidence: 99%

Analysis of the Glass Transition Behavior of Polymer−Salt Complexes: An Extended Configurational Entropy Model

et al. 2003

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A new molecular thermodynamic model is developed of the glass transition temperatures (T g) of binary polymer−salt complexes by combining configurational entropy theory with Guggenheim's form of the Debye−Hückel theory. The interactions between the polymer chains and the salt as well as those between cations and anions are accounted for by this model. The predictions of this extended configurational entropy theory are compared with the T g values of poly(2-ethyl-2-oxazoline) (POZ) complexed with AgBF4, AgClO4, AgCF3SO3, and AgNO3 at various compositions, as obtained by differential scanning calorimetry (DSC). The model accurately predicts the experimental T g values even at high concentrations of silver salt (i.e., up to a mole ratio of [Ag]/[CO] = 1/1), where the deviation of the simple configurational entropy theory from experimental data is large. Moreover, the maximum in the glass transition temperature, i.e., the increase in T g with salt concentration at low salt concentrations but its decrease at high salt concentrations, is explicable with this model.

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Section: Introductionmentioning

confidence: 99%

Analysis of the Glass Transition Behavior of Polymer−Salt Complexes: An Extended Configurational Entropy Model

et al. 2003

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“…Additional plasticizers, solvents, and ceramic additives have been mixed with PEO; PEO can be cross-linked, and the matrices can be swollen with solvents to improve conduction and flexibility . Random copolymers , or block copolymers − can be used. “Internal” plasticization can be accomplished by branches or combs within PEO, where the enhanced side-chain relaxations improve the mobility of ions. ,,− Finally, oligomeric ethylene oxide side chains can be covalently connected to several types of polymer backbones to form other types of comb copolymers. ,− Low-dimensional conductors due to self-organized or smectic lamellar structures have been constructed to suppress aggregation due to the charges − which can lead to anisotropic conductivity.…”

Section: Introductionmentioning

confidence: 99%

“…Additional plasticizers, solvents, and ceramic additives have been mixed with PEO; PEO can be crosslinked, and the matrices can be swollen with solvents to improve conduction and flexibility. 12 Random copolymers 16,17 or block copolymers [18][19][20][21][22] can be used. "Internal" plasticization can be accomplished by branches or combs within PEO, where the enhanced side-chain relaxations improve the mobility of ions.…”

Section: Introductionmentioning

confidence: 99%

Mesomorphic Structure of Poly(styrene)-block-poly(4-vinylpyridine) with Oligo(ethylene oxide)sulfonic Acid Side Chains as a Model for Molecularly Reinforced Polymer Electrolyte

Kosonen¹,

Valkama²,

Hartikainen³

et al. 2002

Macromolecules

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Mesomorphic structure of poly(styrene)-block-poly(4-vinylpyridine) with oligo(ethylene oxide)sulfonic acid side chains as a model for molecularly reinforced polymer electrolyte Citation for published version (APA): Kosonen, H., Valkama, S., Hartikainen, J., Eerikainen, H., Torkkeli, M., Jokela, K., ... Eerikäinen, H. (2002). Mesomorphic structure of poly(styrene)-block-poly(4-vinylpyridine) with oligo(ethylene oxide)sulfonic acid side chains as a model for molecularly reinforced polymer electrolyte. Macromolecules, 35(27), ABSTRACT: We report self-organized polymer electrolytes based on poly(styrene)-block-poly(4-vinylpyridine) (PS-block-P4VP). Liquidlike ethylene oxide (EO) oligomers with sulfonic acid end groups are bonded to the P4VP block, leading to comb-shaped supramolecules with the PS-block-P4VP backbone. Lithium perchlorate (LiClO 4) has been added to the EO-rich domains. Small-and wide-angle X-ray scattering in combination with Fourier transformation infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), ac impedance, and dynamic mechanical spectroscopy (DMA) suggests alternating lamellae of reinforcing glassy PS domains and ionically conducting "nanochannels" consisting of poly(4-vinylpyridinium), oligomeric ethylene oxide sulfonates, and LiClO 4. The long period of the self-organization is ca. 300 Å. So far, the ionic conductivity levels remained relatively low, i.e., 10 -7 -10 -6 S/cm at room temperature and 10 -5 -10 -4 S/cm at 80°C. However, as self-organization of polymeric supramolecules allows combining glassy reinforcing domains and well-plasticized domains consisting of oligomers with high segmental motions, there may exist possibilities to tune feasible combination of electrical and mechanical properties.

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“…For example, ethylene carbonate has a high dielectric constant, ε = 95, and is broadly used as a solvent component in polymer gel electrolytes because it efficiently dissociates lithium salts 6. Similarly, polymers containing carbonate groups, such as poly(ethylene carbonate‐ co ‐ethylene oxide), have gained an interest as constituents for polymer electrolytes 7–13…”

Section: Introductionmentioning

confidence: 99%

Polymer electrolyte membranes by in situ polymerization of poly(ethylene carbonate‐co‐ethylene oxide) macromonomers in blends with poly(vinylidene fluoride‐co‐hexafluoropropylene)

Elmér

Jannasch

2006

J Polym Sci B Polym Phys

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Salt-containing membranes based on polymethacrylates having poly(ethylene carbonate-co-ethylene oxide) side chains, as well as their blends with poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), have been studied. Self-supportive ion conductive membranes were prepared by casting films of methacrylate functional poly(ethylene carbonate-co-ethylene oxide) macromonomers containing lithium bis(trifluorosulfonyl)imide (LiTFSI) salt, followed by irradiation with UV-light to polymerize the methacrylate units in situ. Homogenous electrolyte membranes based on the polymerized macromonomers showed a conductivity of 6.3 Â 10 À6 S cm À1 at 20 8C. The preparation of polymer blends, by the addition of PVDF-HFP to the electrolytes, was found to greatly improve the mechanical properties. However, the addition led to an increase of the glass transition temperature (T g ) of the ion conductive phase by $5 8C. The conductivity of the blend membranes was thus lower in relation to the corresponding homogeneous polymer electrolytes, and 2.5 Â 10 À6 S cm À1 was recorded for a membrane containing 10 wt % PVDF-HFP at 20 8C. Increasing the salt concentration in the blend membranes was found to increase the T g of the ion conductive component and decrease the propensity for the crystallization of the PVDF-HFP component. V V C 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: [79][80][81][82][83][84][85][86][87][88][89][90] 2007

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Preparation and properties of solid electrolytes on the basis of alkali metal salts and poly(2,2-dimethyltrimethylene carbonate)-block-poly(ethylene oxide)-block-poly(2,2-dimethyltrimethylene carbonate)

Cited by 15 publications

References 21 publications

Analysis of the Glass Transition Behavior of Polymer−Salt Complexes: An Extended Configurational Entropy Model

Analysis of the Glass Transition Behavior of Polymer−Salt Complexes: An Extended Configurational Entropy Model

Mesomorphic Structure of Poly(styrene)-block-poly(4-vinylpyridine) with Oligo(ethylene oxide)sulfonic Acid Side Chains as a Model for Molecularly Reinforced Polymer Electrolyte

Polymer electrolyte membranes by in situ polymerization of poly(ethylene carbonate‐co‐ethylene oxide) macromonomers in blends with poly(vinylidene fluoride‐co‐hexafluoropropylene)

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