Ion conductive electrolyte membranes based on co-continuous polymer blends

Elmér, Anette Munch; Wesslén, Bengt; Sommer‐Larsen, Peter; West, Keld; Hassander, Helén; Jannasch, Patric

doi:10.1039/b304462a

Cited by 31 publications

(10 citation statements)

References 33 publications

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“…The shoulder indicated a broadened phase distribution of the blend components. A similar broadening of the tan δ curves has previously been observed for solid electrolyte membranes based on PVDF‐HFP and PEG methacrylate macromonomers 17. It was then concluded that the broadening was indicative of an interphase between the components.…”

Section: Resultssupporting

confidence: 77%

“…The concept of blending a soft conductive polymer component with a mechanically stable polymer to enhance the dimensional stability is an attractive approach to polymeric electrolytes where a high conductivity is combined with mechanical stability 16. In a previous study, we have prepared co‐continuous polymer blend electrolytes using poly(ethylene glycol) (PEG) methacrylate macromonomers and PVDF‐HFP 17. The components were found to phase separate during the casting process and the macromonomer was subsequently polymerized by UV‐initiation.…”

Section: Introductionmentioning

confidence: 99%

“…The components were found to phase separate during the casting process and the macromonomer was subsequently polymerized by UV‐initiation. The resulting morphology was a three‐dimensional matrix of PVDF‐HFP holding a continuous phase of ionically conductive PEG‐grafted polymethacrylate networks 17. In the present article, we report on the properties of solid polymer blend electrolytes containing polymethacrylates grafted with poly(ethylene carbonate‐ co ‐ethylene oxide) side chains and PVDF‐HFP, and compare them with the corresponding electrolytes without the PVDF‐HFP component.…”

Section: Introductionmentioning

confidence: 99%

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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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Section: Resultssupporting

confidence: 77%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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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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“…This shift indicates the decrease in bond energy between C and O, 31 and generally happens when O acts as electron donor. As reported by Wieczorek et al 24 the shift of the C-O-C peak in PEO-based composites is caused by the coordination of Li + and C-O-C. That is, the ether group (C-O-C) can act as electron donors, and Li + ion tends to coordinated with O atoms.…”

Section: Resultsmentioning

confidence: 72%

In Situ Polymerization of Methoxy Polyethylene Glycol (350) Monoacrylate and Polyethyleneglycol (200) Dimethacrylate Based Solid-State Polymer Electrolyte for Li-Ion Batteries

Wang

et al. 2012

J. Electrochem. Soc.

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In-situ polymerization of PEG350mA and PEG200diA is attempted to prepare solid-state polymer electrolytes (SPEs) for Li-ion Batteries. Effects of composition and LiClO 4 content on properties and performances of the SPEs are investigated by TG, EIS. The role of cross-linking and lithium salt in the IPN type SPEs is investigated by DSC and FT-IR analysis. The IPNs-LiClO 4 SPEs show ionic conductivity of 1.5 × 10 −5 S cm −1 at ambient temperature and applicable thermal stability under 270 • C. A Li/SPEs/LiCoO 2 coin cell shows acceptable charge/discharge performance. This paves an effective way to develop SPEs for lithium ion batteries.Many attempts have been made recently to develop solid polymer electrolytes (SPEs) for Li-ion batteries because the SPEs have advantages such as non-volatile, non-explosive, flexible and electrochemically stable, 1-15 since Wright 16 and Armand 17 put forward the concept of SPEs for lithium batteries in 1970s. However, the poor ionic conductivity of SPEs limits their applications. Since Li + migration in SPEs occurs primarily in the amorphous regions and is associated with the coordination sites (ionic hopping) and the polymeric chain segmental motions (micro-Brownian motions). 18 The crystallinity of the polymer matrix and lithium salt concentration is the two main aspects to particularly govern the magnitude of ionic conductivity in SPEs. The dynamic bond percolation theory developed by Ratner et al. explains the charge migration in such systems in terms of renewal of hopping probabilities. 19,20 Of all the polymers, polymers with (CH 2 -CH 2 -O) n segment, such as PEO, behave high compatibility with general lithium salt as well as high ionic conductivity due to the coordination between O and Li + , while their thermal and mechanical stabilities need to be improved.On the other hand, interpenetrating polymer networks (IPN) are attractive in terms of thermal and mechanical stability, homogeneity and low degree of crystallinity, due to their unique three-dimensional network structure. From this perspective, to graft (CH 2 -CH 2 -O) n segments into IPNs matrix is a feasible strategy to obtain promising SPEs. Hudson et al. 21 reported SPEs prepared with epoxy resin interpenetrating polymer and polyethylene glycol (PEG). And the results showed that IPNs structure enhanced the ionic conductivity. Kaskhedikar et al. 22 prepared another IPN type SPEs by in-situ polymerization of MEEP (poly[bis(methoxyethoxy)phosphazene]) and CVEEP which was prepared by substituting all the chlorine atoms in hexachlorocyclotriphosphazene with vinyloxyethoxyethoxy groups. And the asprepared SPEs showed good mechanical properties and an attractive ambient ionic conductivity of 1.3 × 10 −5 S cm −1 . Anette et al. 23,24 designed IPN type SPEs by commixing PVDF-HFP and comb structured PEG. Generally, the reported ambient ionic conductivities of IPN type SPEs are about 10 −6 -10 −5 S cm −1 , and the cross-linking degree of the IPN matrix shows weak effect on the conductivity.The similar structure of methoxy polye...

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“…Understanding polymer blend thermodynamics and the roles of molecular architecture and specific interactions is required for the predictive design and fabrication of homogeneous and multiphase polymeric materials, − with applications ranging from tissue engineering and organic photovoltaics to membrane technologies. − Partially miscible lower critical solution temperature (LCST)-type blends are of particular interest, as demixing can be induced upon heating the blend into an unstable region, and the resulting structure can be arrested by rapid cooling below the glass transition temperature ( T g ). Partially miscible blends can be classified as ‘highly interacting’ when the interaction parameter χ changes steeply with the temperature near the stability boundaries, meaning that small demixed phases can be accessed with modest thermal quenches, which is attractive for material design.…”

Section: Introductionmentioning

confidence: 99%

Thermodynamics of Highly Interacting Blend PCHMA/dPS by TOF-SANS

et al. 2023

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We investigate the thermodynamics of a highly interacting blend of poly(cyclohexyl methacrylate)/deuterated poly(styrene) (PCHMA/dPS) with small-angle neutron scattering (SANS). This system is experimentally challenging due to the proximity of the blend phase boundary (>200 °C) and degradation temperatures. To achieve the large wavenumber q-range and flux required for kinetic experiments, we employ a SANS diffractometer in time-of-flight (TOF) mode at a reactor source and ancillary microscopy, calorimetry, and thermal gravimetric analysis. Isothermal SANS data are well described by random-phase approximation (RPA), yielding the second derivative of the free energy of mixing (G″), the effective interaction (χ ̅ ) parameter, and extrapolated spinodal temperatures. Instead of the Cahn−Hilliard−Cook (CHC) framework, temperature (T)-jump experiments within the one-phase region are found to be well described by the RPA at all temperatures away from the glass transition temperature, providing effectively near-equilibrium results. We employ CHC theory to estimate the blend mobility and G″(T) conditions where such an approximation holds. TOF-SANS is then used to precisely resolve G″(T) and χ ̅ (T) during T-jumps in intervals of a few seconds and overall timescales of a few minutes. PCHMA/dPS emerges as a highly interacting partially miscible blend, with a steep dependence of G″(T) [mol/cm 3 ] = −0.00228 + 1.1821/T [K], which we benchmark against previously reported highly interacting lower critical solution temperature (LCST) polymer blends.

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Ion conductive electrolyte membranes based on co-continuous polymer blends

Cited by 31 publications

References 33 publications

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

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

In Situ Polymerization of Methoxy Polyethylene Glycol (350) Monoacrylate and Polyethyleneglycol (200) Dimethacrylate Based Solid-State Polymer Electrolyte for Li-Ion Batteries

Thermodynamics of Highly Interacting Blend PCHMA/dPS by TOF-SANS

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