Salt-in-Polymer Electrolytes for Lithium Ion Batteries Based on Organo-Functionalized Polyphosphazenes and Polysiloxanes

Burjanadze, M.; Karatas, Yunus; Kaskhedikar, N.; Kogel, Lutz; Kloss, S.; Gentschev, Ann-Christin; Hiller, Martin M.; Müller, Romek; Stolina, R.; Vettikuzha, Preeya; Wiemhöfer, Hans‐Dieter

doi:10.1524/zpch.2010.0046

Cited by 20 publications

(8 citation statements)

References 83 publications

(102 reference statements)

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“…Several processes were adopted to optimize the lithiation process and determine their effect on the ionic conductivity of the nanoscale polymer films. It is widely reported that the size of the counterion (anion) in the lithium salt used in the lithiation process can influence the ionic conductivity . As shown in Figure , as anion size increases from LiCl to LiClO 4 , it promotes the improved dissociation of the salt into Li + and counterion, thereby resulting in reduced ion pairing and improved solvation of Li + by the O atoms present in the siloxane film.…”

Section: Resultsmentioning

confidence: 99%

A Group of Cyclic Siloxane and Silazane Polymer Films as Nanoscale Electrolytes for Microbattery Architectures

Reeja‐Jayan¹,

Chen²,

Lau

et al. 2015

Macromolecules

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Nanoscale (10−50 nm) thin films of cyclic siloxane and silazane polymers were synthesized by initiated chemical vapor deposition (iCVD). We have previously demonstrated that the non-line-of-sight iCVD synthesis process can create uniform conformal coverage of these films over complex nonplanar surfaces. This work will introduce the protocols used to convert these dielectric polymer films into ionic conductors at room temperature. The excellent thickness and morphological stability of these films will be demonstrated along with experiments that determine the ion content in the films. Finally, computational calculations will be used to elucidate the chemical nature of the ion doping and transport processes. These nanoscale, conformal, ionically conducting polymer thin films are attractive as a novel class of nanoscale electrolytes for emerging miniaturized or microbattery architectures such as three-dimensional (3D) batteries which combine high energy (due to high surface area) and power density (due to short ionic transport lengths) within small areal footprints. ■ INTRODUCTIONMicroelectromechanical systems (MEMS) have established high-volume markets for multiple commercial products over the past 20 years and possess further potential for widespread application in sensors, microfluidics, wireless communications, and optics. 1−4 However, MEMS devices require miniaturized or microbatteries with higher areal energy densities (>100 J/cm 2 ) than current planar lithium-ion (Li + ) batteries can provide (<5 J/cm 2 ). 5,6 Three-dimensional or 3D battery architectures comprising of high surface area, nonplanar electrode structures (e.g., interdigitated rods, cylinder, plates, and microporous networks) instead of the traditional planar electrodes can address this challenge by increasing areal energy density, while also maintaining the short ion-transport distances necessary for high power densities. 5−7 A key obstacle to the development of such 3D battery architectures is the synthesis of a suitable electrolyte, which must be conformal, pinhole-free, electronically insulating, and ionically conducting. 5 Unlike liquid electrolytes, conformal, solid-state electrolytes that uniformly "shrink-wrap" nonplanar electrode structures can minimize the volume devoted to the electrochemically inactive electrolyte and thus increase energy density to levels suitable for powering autonomous MEMS devices. 6 Liquid electrolytes further suffer from surface tension and dewetting effects, which lead to "soft" shorts that can create undesirable current shunting pathways in a battery. 8 Finally, solid-state electrolytes with thicknesses on the nanoscale can provide significantly shorter ionic transport times compared to their micron scale or liquid state counterparts. 6,9 The need for nanoscale thickness uniformity and conformality over the complex geometries of 3D battery electrodes has presented one of the most significant design challenges for the realization of 3D batteries.We recently demonstrated that initiated chemical vapor depositio...

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Section: Resultsmentioning

confidence: 99%

A Group of Cyclic Siloxane and Silazane Polymer Films as Nanoscale Electrolytes for Microbattery Architectures

Reeja‐Jayan¹,

Chen²,

Lau

et al. 2015

Macromolecules

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“…14,15 Conjugating siloxane segments to PEO is reported to increase ionic conductivity and impart improved mechanical and electrochemical stability. [16][17][18][19][20][21][22][23][24] The -Si-O-Sibonds in the siloxane moieties are more ionic than -C-O-Cbonds leading to a more negative charge on the oxygen atom that can chelate Li + . The exible nature and associated free volume of the siloxane linkages further facilitate ionic transport.…”

Section: Introductionmentioning

confidence: 99%

Nanoscale, conformal polysiloxane thin film electrolytes for three-dimensional battery architectures

et al. 2015

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“…For instance, comb-branched block copolymers [254] and cross-linked polymer networks [248] have been found to offer favorable mechanical and electrical properties. This includes polymer electrolytes based on polyphosphazenes [255–258] and polysiloxanes [258–261], as investigated especially by the groups of Wiemhöfer (Germany) and West (USA).…”

Section: An Evolving Scheme Of Materials Sciencementioning

confidence: 99%

Solid State Ionics: from Michael Faraday to green energy—the European dimension

Funke¹

2013

Science and Technology of Advanced Materials

141

102

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Solid State Ionics has its roots essentially in Europe. First foundations were laid by Michael Faraday who discovered the solid electrolytes Ag2S and PbF2 and coined terms such as cation and anion, electrode and electrolyte. In the 19th and early 20th centuries, the main lines of development toward Solid State Ionics, pursued in Europe, concerned the linear laws of transport, structural analysis, disorder and entropy and the electrochemical storage and conversion of energy. Fundamental contributions were then made by Walther Nernst, who derived the Nernst equation and detected ionic conduction in heterovalently doped zirconia, which he utilized in his Nernst lamp. Another big step forward was the discovery of the extraordinary properties of alpha silver iodide in 1914. In the late 1920s and early 1930s, the concept of point defects was established by Yakov Il'ich Frenkel, Walter Schottky and Carl Wagner, including the development of point-defect thermodynamics by Schottky and Wagner. In terms of point defects, ionic (and electronic) transport in ionic crystals became easy to visualize. In an ‘evolving scheme of materials science’, point disorder precedes structural disorder, as displayed by the AgI-type solid electrolytes (and other ionic crystals), by ion-conducting glasses, polymer electrolytes and nano-composites. During the last few decades, much progress has been made in finding and investigating novel solid electrolytes and in using them for the preservation of our environment, in particular in advanced solid state battery systems, fuel cells and sensors. Since 1972, international conferences have been held in the field of Solid State Ionics, and the International Society for Solid State Ionics was founded at one of them, held at Garmisch-Partenkirchen, Germany, in 1987.

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Salt-in-Polymer Electrolytes for Lithium Ion Batteries Based on Organo-Functionalized Polyphosphazenes and Polysiloxanes

Cited by 20 publications

References 83 publications

A Group of Cyclic Siloxane and Silazane Polymer Films as Nanoscale Electrolytes for Microbattery Architectures

A Group of Cyclic Siloxane and Silazane Polymer Films as Nanoscale Electrolytes for Microbattery Architectures

Nanoscale, conformal polysiloxane thin film electrolytes for three-dimensional battery architectures

Solid State Ionics: from Michael Faraday to green energy—the European dimension

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