Ionic conductivity and interfacial properties of polymer electrolytes based on PEO and boroxine ring polymer

Yang, Yuan; Inoue, Takayoshi; Fujinami, Tatsuo; Mehta, Mary Anne

doi:10.1002/app.10090

Cited by 29 publications

(22 citation statements)

References 18 publications

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“…In 1997, Mehta and Fujinami 476 reported a method for enhancing the Li + transfer number by incorporating boroxine ring groups into the polymer host. And they prepared anion trapping polymer [477][478][479][480][481] The materials exhibited high Li + transfer number. The polymer electrolytes containing boroxine rings showed electrochemical and thermal stability.…”

Section: Boron Corementioning

confidence: 99%

Poly(ethylene oxide)-based electrolytes for lithium-ion batteries

2015

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This article reviews the PEO-based electrolytes for lithium-ion batteries.Poly(ethylene oxide) (PEO) based materials are widely considered as promising candidates of polymer hosts in solid-state electrolytes for high energy density secondary lithium batteries. They have several specific advantages such as high safety, easy fabrication, low cost, high energy density, good electrochemical stability, and excellent compatibility with lithium salt. However, the typical linear PEO does not reach the production requirement because its insufficient ionic conductivity due to the high crystallinity of the ethylene oxide (EO) chains, which can restrain the ionic transition due to the stiff structure especially at low temperature. The scientists have explored different approaches to reduce the crystallinity hence to improve the ionic conductivity of PEO-based electrolytes, including: blending, modifying and making PEO derivatives etc. This review is focused on surveying the recent developments and issues about PEO-based electrolytes for lithium-ion batteries.

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Section: Boron Corementioning

confidence: 99%

Poly(ethylene oxide)-based electrolytes for lithium-ion batteries

2015

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“…It can be found in the literature that many ion-conducting polymer electrolytes were developed on the basis of CS and its blends [ 17 , 18 , 19 , 20 , 21 ]. Various polymers for example poly(vinylidene fluoride) (PVDF)[ 22 ], polyvinyl pyrrolidone (PVP) [ 23 ], boroxine ring polymer (BP) [ 24 ], polymethylhydrogen-siloxane (PMHS) [ 25 ], poly(vinyl alcohol) (PVA) [ 26 ] as well as poly(dithiooxamide) (PDTOA) [ 27 ] were mixed with PEO to fabricate polymer electrolytes. PEO polymer possesses a small melting point [ 28 ] and, therefore, its mixing with large glass transition temperature polymers for example CS is vital for constructing flexible films.…”

Section: Introductionmentioning

confidence: 99%

Drawbacks of Low Lattice Energy Ammonium Salts for Ion-Conducting Polymer Electrolyte Preparation: Structural, Morphological and Electrical Characteristics of CS:PEO:NH4BF4-Based Polymer Blend Electrolytes

et al. 2020

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In the present work it was shown that low lattice energy ammonium salts are not favorable for polymer electrolyte preparation for electrochemical device applications. Polymer blend electrolytes based on chitosan:poly(ethylene oxide) (CS:PEO) incorporated with various amounts of low lattice energy NH4BF4ammonium salt have been prepared using the solution cast technique. Both structural and morphological studies were carried out to understand the phenomenon of ion association. Sharp peaks appeared in X-ray diffraction (XRD) spectra of the samples with high salt concentration. The degree of crystallinity increased from 8.52 to 65.84 as the salt concentration increased up to 40 wt.%. These are correlated to the leakage of the associated anions and cations of the salt to the surface of the polymer. The structural behaviors were further confirmed by morphological study. The morphological results revealed the large-sized protruded salts at high salt concentration. Based on lattice energy of salts, the phenomena of salt leakage were interpreted. Ammonium salts with lattice energy lower than 600 kJ/mol are not preferred for polymer electrolyte preparation due to the significant tendency of ion association among cations and anions. Electrical impedance spectroscopy was used to estimate the conductivity of the samples. It was found that the bulk resistance increased from 1.1 × 104 ohm to 0.7 × 105 ohm when the salt concentration raised from 20 wt.% to 40 wt.%, respectively; due to the association of cations and anions. The low value of direct current (DC) conductivity (7.93 × 10−7 S/cm) addressed the non-suitability of the electrolytes for electrochemical device applications. The calculated values of the capacitance over the interfaces of electrodes-electrolytes (C2) were found to drop from 1.32 × 10−6 F to 3.13 × 10−7 F with increasing salt concentration. The large values of dielectric constant at low frequencies are correlated to the electrode polarization phenomena while their decrements with rising frequency are attributed to the lag of ion polarization in respect of the fast orientation of the applied alternating current (AC) field. The imaginary part of the electric modulus shows obvious peaks known as conduction relaxation peaks.

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“…As only the Li + ‐ions contribute to the ion conductivity, the transference number of the immobilized anion is negligible small. This has several advantages as compared to PEO‐based electrolytes with physically dissolved Li‐salts as loss of performance, undesired side reactions, or voltage loss in electrochemical devices caused by aggregation of the anions is prevented. However, several approaches to achieve SIC functionality in PEO‐based materials have been reported, that is, the insertion of organic or inorganic groups such as carboxylates, sulfonates, sulfonimides, phosphates, or borates .…”

Section: Introductionmentioning

confidence: 99%

Enhanced ion conductivity of poly(ethylene oxide)‐based single ion conductors with lithium 1,2,3‐triazolate end groups

Thümmler

Pulst

Kreßler

2018

J of Applied Polymer Sci

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Poly(ethylene oxide) (PEO)-based single ion conductors (SICs) are of great interest for applications in modern lithium ion batteries. They have several advantages over other common electrolytes such as high cation transference numbers, low toxicity, and nonflammability, but their major disadvantage is the low ion conductivity. Here, linear PEO-based SICs with lithium 1,2,3-triazolate (TrLi) end groups are synthesized and studied in terms of crystallinity by differential scanning calorimetry, and with respect to ion conductivity by impedance spectroscopy. Introduction of TrLi end groups to PEO chains reduces its crystallinity and melting temperature as well as an enhancement of the ion conductivity up to 8.0Á10 −6 S cm −1 at 70 C is observed. The increased ion conductivity is a direct result of the Tr rings, which can actively contribute to the conduction mechanism. In comparison with conductivities of other PEO-based SICs reached so far (σ 0 ≤ 10 −6 S cm −1 ), the results of this study show that the introduction of TrLi end groups is a new approach to enhance the Li + -ion conductivity of PEO-based SICs that have also a good electrochemical stability versus lithium electrodes as revealed by linear sweep voltammetry.

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Ionic conductivity and interfacial properties of polymer electrolytes based on PEO and boroxine ring polymer

Cited by 29 publications

References 18 publications

Poly(ethylene oxide)-based electrolytes for lithium-ion batteries

Poly(ethylene oxide)-based electrolytes for lithium-ion batteries

Drawbacks of Low Lattice Energy Ammonium Salts for Ion-Conducting Polymer Electrolyte Preparation: Structural, Morphological and Electrical Characteristics of CS:PEO:NH4BF4-Based Polymer Blend Electrolytes

Enhanced ion conductivity of poly(ethylene oxide)‐based single ion conductors with lithium 1,2,3‐triazolate end groups

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