Polymer electrolytes—the early days

Wright, Peter V.

doi:10.1016/s0013-4686(97)10011-1

Cited by 214 publications

(129 citation statements)

References 41 publications

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“…Increase of ionic conductivity following the addition of ferroelectric BaTiO 3 to different polymer matrices is ascribed to the high polarity of the filler. Money et al 63 showed that the ionic conductivity of the LiClO 4 :P(EO) 4 polymer electrolyte containing 4wt% δ-Al 2 O 3 is coupled to the structural (α) relaxation time. The strength of the β-relaxation of polymer chains increases in the presence of salt and filler particles, while the γ-relaxation remains unaffected.…”

Section: Amorphous Polymer Electrolytesmentioning

confidence: 99%

Review—On Order and Disorder in Polymer Electrolytes

Golodnitsky

Strauss

Greenbaum

2015

J. Electrochem. Soc.

203

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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Section: Amorphous Polymer Electrolytesmentioning

confidence: 99%

Review—On Order and Disorder in Polymer Electrolytes

Golodnitsky

Strauss

Greenbaum

2015

J. Electrochem. Soc.

203

135

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“…PEO based electrolytes represent the archetype of this material class ever since the pioneering work of Wright et al [8,9] and Armand et al [10,11] who observed that Li salts can be dissolved in polyethylene oxide and exhibit ionic conductivity. A rather important characteristic of the PEO based polymer electrolytes is their strong tendency towards crystallisation and the concomitant formation of a mixture of different phases.…”

Section: Salt-in-polymer-electrolytesmentioning

confidence: 99%

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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“…One essential component in Li-ion batteries is the polymer electrolyte (PE) consisting of a macromolecular system (polymer with salts in its constitution [6]) with high ionic conductivity (>10 -7 at 10 -1 S/cm) [7,8]. Further, polymer electrolytes can be used in multiple applications, including electrochromic devices [9][10][11], fuel cells [12,13] and sensors/actuators [14], supercapacitors/ultracapacitors [15], together with Li-ion batteries [4,16].…”

Section: Introductionmentioning

confidence: 99%