Study of the ion conduction of polymer electrolytes confined in micro and nanopores

Vorrey, Seshumani; Teeters, Dale

doi:10.1016/s0013-4686(03)00196-8

Cited by 61 publications

(56 citation statements)

References 33 publications

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“…Nyquist plots of empty alumina membranes and a plain film of the PEO electrolyte were Two semicircles seen for each composite polymer electrolyte membrane indicate that there are two paths for ionic conduction. The first one at higher relative resistance can be assigned to ionic conduction which occurs throughout the bulk of the polymer electrolyte, while the second one at low relative resistances can be assigned to a mechanism of ionic conduction along the interfaces bet- (1) Z' "SsE 9 R p ween the pores and the polymer surfaces [20,22]. While calculating the specific conductivity of "interfacial" conduction may be impossible to achieve because the geometry of any interfacial conduction region would be difficult to determined, there is no doubt that this conduction is much larger than that of the bulk conduction.…”

Section: Resultsmentioning

confidence: 99%

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Impedance spectroscopy of PEO-lithium triflate confined in nanopores of alumina membranes

Castriota

Teeters

2005

Ionics

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Abstract. Polymeric electrolytes are very useful for their technological applications in different electrochemical devices such as batteries, electrochromic devices, smart windows, etc. One of the most studied solid electrolyte system is PEO (poly-ethylene oxide) complexed with various lithium salts. A limitation of this polymer electrolyte is low ionic conductivity. However, nanoscale manipulation of the solid polymer electrolyte has the potential to address this issue. This work discusses how it is possible to increase the PEO conductivity when this polymer is contained in nanostructures, specifically nanopores. The nanostructures used are alumina filtration membranes (thickness = 6 ~tm, diameter = 13 mm) with three different pore sizes 0.02 p~m, 0.1 ~tm and 0.2 p~m. Electrochemical characterization has been performed with an HP4194A Impedance/Gain phase analyser and Solartron 1260 Impedance/Gain phase analyser. The former instrument tests these films at a high frequency (from 100 Hz to 40 MHz) while the later at low frequency (from 1 Hz to 1 MHz). From these experiments, it has been determined that two regions of ion conduction exit. One is conduction through the bulk polymer electrolyte in the pores while the other is an interfacial conduction at the interface between the pore walls and the PEO electrolyte. The conductivity of the PEO is increased when confined in these nanostructures.

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Section: Resultsmentioning

confidence: 99%

“…Some quite promising results have been found when the nanoporous template for polymer electrolyte confinement was made by polycarbonate filtration membranes [20][21].…”

Section: Introductionmentioning

confidence: 99%

Impedance spectroscopy of PEO-lithium triflate confined in nanopores of alumina membranes

Castriota

Teeters

2005

Ionics

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“…The ordering of polymer electrolytes by confinement in a ceramic matrix was proposed by Teeters et al 104 The authors found that the confinement of PEO polymer electrolytes in the nanopores of alumina, increases the ionic conduction as the pore narrows, with the highest conductivity of 0.24 mS/cm observed in 30 nm-diameter pores. This is almost two orders of magnitude higher than that of a polymerelectrolyte film of the same composition but not confined in nanopores.…”

Section: 91mentioning

confidence: 93%

Review—On Order and Disorder in Polymer Electrolytes

Golodnitsky

Strauss

Greenbaum

2015

J. Electrochem. Soc.

202

135

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This contribution presents an overview of more than three-decades-long studies of the structure and mechanism of ion conduction in polyethylene-oxide-based solid polymer electrolytes. Conductivity in polymer electrolytes has long been viewed as confined to the amorphous phase above the glass-transition temperature (Tg). Above Tg, polymer chain motion creates a dynamic, disordered environment that was thought to play a critical role in facilitating ion transport. Difficulty of finding the amorphous polymer with sufficient ionic conductivity has raised the fundamental question of whether polymer electrolytes are intrinsically inferior to other electrolytes in terms of their charge-transport capability. Recently, enhanced ionic conductivity has been detected in ordered (longitudinally stretched and cast under gradient magnetic field) polymer electrolytes, in crystalline ion-polyether 1:6 complexes and polymer-in-salt electrolytes. These results have opened a new trend in the search for ion transport in solid polymer electrolytes. The very latest publications present new hybrid-and block-co-polymers, a new class of functional materials (polymerized ionic liquids), and new promising approaches aimed at the development of polymer-based superionic conductors with rigid nanochannel architectures that enable rapid ion transport decoupled from segmental relaxation. Solid Polymer Electrolytes-Structure and Mechanism of Ion TransportMuch research deals with high-ionic-conductive polymer electrolytes because of their current and potential applications as electrochromic and temperature-sensitive printed electronics devices, biomedical sensors, supercapacitors, solar cells and batteries. Polymer electrolytes offer pronounced advantages over conventional liquid electrolytes. These include: a versatile shape, mechanical strength and stable contact between the electrode and electrolyte interfaces. In addition, solid electrolytes are safer than liquid electrolytes as they do not have a leakage problem and because of their nontoxic, low-vaporpressure, and non-flammable properties. [1][2][3][4][5][6][7] Ion-polyether complexes (or polymer electrolytes) were first discovered by Fenton, Parker and Wright in 1973. 8 Since then, such complexes have been prepared with many different monatomic ions and indeed many different polymeric ligands. Armand in 1979 recognized that Li + -polyether complexes could be used as solid electrolytes in electrochemical devices. 9The classic polymer electrolyte comprises organic macromolecules (usually polyether polymer) that are complexed with inorganic salts. The polymer matrix must contain a Lewis base (e.g. ethylene-oxide unit, -OCH 2 CH 2 -) to solvate the lithium salt. The salt-solvent mixing entropy consists mainly of two components: translational and configurational. Contrary to the case of water, the mixing entropy for the formation of polymer electrolytes is small or even positive. The incorporation of salts into the polymer inevitably reduces the freedom of polymer-chain motion, thus causing ...

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“…pore-filling of PCTE (pore diameters, 30-400 nm) with polyethylene oxide (Vorrey and Teeters 2003) and of AAO (pore diameters, 20-200 nm) with poly(phenylene sulfonic acid) (White et al 2008). Direct attachment of sulfonic groups to PCTE pore walls (pore diameter, 10-2000 nm) by graft polymerization was also reported (Chen et al 2006).…”

Section: Anisotropic Pore-filling Membranesmentioning

confidence: 99%

Understanding methods of preparation and characterization of pore-filling polymer composites for proton exchange membranes: a beginner’s guide

Gloukhovski

Freger

Tsur

2017

Reviews in Chemical Engineering

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Abstract Composite membranes based on porous support membranes filled with a proton-conducting polymer appear to be a promising approach to develop novel proton exchange membranes (PEMs). It allows optimization of the properties of the filler and the matrix separately, e.g. for maximal conductivity of the former and maximal physical strength of the latter. In addition, the confinement itself can alter the properties of the filling ionomer, e.g. toward higher conductivity and selectivity due to alignment and restricted swelling. This article reviews the literature on PEMs prepared by filling of submicron and nanometric size pores with Nafion and other proton-conductive polymers. PEMs based on alternating perfluorinated and non-perfluorinated polymer systems and incorporation of fillers are briefly discussed too, as they share some structure/transport relationships with the pore-filling PEMs. We also review here the background knowledge on structural and transport properties of Nafion and proton-conducting polymers in general, as well as experimental methods concerned with preparation and characterization of pore-filling membranes. Such information will be useful for preparing next-generation composite membranes, which will allow maximal utilization of beneficial characteristics of polymeric proton conductors and understanding the complicated structure/transport relationships in the pore-filling composite PEMs.

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Study of the ion conduction of polymer electrolytes confined in micro and nanopores

Cited by 61 publications

References 33 publications

Impedance spectroscopy of PEO-lithium triflate confined in nanopores of alumina membranes

Impedance spectroscopy of PEO-lithium triflate confined in nanopores of alumina membranes

Review—On Order and Disorder in Polymer Electrolytes

Understanding methods of preparation and characterization of pore-filling polymer composites for proton exchange membranes: a beginner’s guide

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