Proton Conducting Biopolymer Electrolytes Based on Starch Incorporated with Ammonium Thiocyanate

Zulkefli, F; Navaratnam, Shanti K; Ahmad, Ausaf

doi:10.4028/www.scientific.net/amr.1112.275

Cited by 10 publications

(3 citation statements)

References 16 publications

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“…NH 4 SCN has been recently reported to be used as a dopant salt in polymer electrolytes based electrochemical devices, and the ion complexation dynamics have been linked with the overall conductivity . Interestingly, NH 4 SCN has a strong effect on polymer electrolytes dielectric constant and has been hypothesized to be dependent on association and dissociation dynamics . Thus, quantifying the complexation dynamics provides a molecular picture for more complex electrolyte systems.…”

Section: Resultsmentioning

confidence: 80%

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Association–Dissociation Dynamics of Ionic Electrolytes in Low Dielectric Medium

et al. 2021

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Ionic electrolytes are known to form various complexes which exist in dynamic equilibrium in a low dielectric medium. However, structural characterization of these complexes has always posed a great challenge to the scientific community. An additional challenge is the estimation of the dynamic association− dissociation time scales (lifetime of the complexes), which are key to the fundamental understanding of ion transport. In this work, we have used a combination of infrared absorption spectroscopy, twodimensional infrared spectroscopy, molecular dynamics simulations, and density functional theory calculations to characterize the various ion complexes formed by the thiocyanate-based ionic electrolytes as a function of different cations in a low dielectric medium. Our results demonstrate that thiocyanate is an excellent vibrational reporter of the heterogeneous ion complexes undergoing association−dissociation dynamics. We find that the ionic electrolytes exist as contact ion pairs, dimers, and clusters in a low dielectric medium. The relative ratios of the various ion complexes are sensitive to the cations. In addition to the interactions between the thiocyanate anion and the countercation, the solute−solvent interactions drive the dynamic equilibrium. We have estimated the association− dissociation dynamics time scales from two-dimensional infrared spectroscopy. The exchange time scale involving the cluster is faster than that between a dimer and an ion pair. Moreover, we find that the dynamic equilibrium between the cluster and another ion complex is correlated to the solvent fluctuations.

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Section: Resultsmentioning

confidence: 80%

“…70 Interestingly, NH 4 SCN has a strong effect on polymer electrolytes dielectric constant and has been hypothesized to be dependent on association and dissociation dynamics. 71 Thus, quantifying the complexation dynamics provides a molecular picture for more complex electrolyte systems.…”

Section: Resultsmentioning

confidence: 95%

Association–Dissociation Dynamics of Ionic Electrolytes in Low Dielectric Medium

et al. 2021

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“…The highest ionic conductivity that can be obtained is 6.83 x 10 -4 S cm -1 . The studies by Zulkefli et al (2015) on polymer electrolyte based starch as host polymer and NH4SCN salt as the ionic dopant shown that the highest ionic conductivity is 5.54 × 10 −3 S cm −1 . As a consequence, the aim of this research is to discover the influence of ring type that built a polysaccharide can affect the ionic conductivity of polymer electrolyte system.…”

Section: Introductionmentioning

confidence: 99%

Effect of Monosaccharides and Disaccharides Type on Ionic Conductivity of Liquid Electrolyte Based Lithium Iodide

Ra'il

Mobarak

2021

JIF

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Liquid electrolyte was prepared by dissolving glucose, fructose, sucrose and lactose separately with different percentage of lithium iodide (10 – 35%) in aqueous solution of 1% acetic acid. Liquid electrolyte is characterized using conductivity meter to determine ionic conductivity. Computer simulations of Density Functional Theory (DFT) was used to identify the dominant functional groups on monomers such as glucose, sucrose, fructose and lactose when interact with the lithium salt by using B3LYP/6-31G ++ (d, p) basis set. The highest ionic conductivity for monosaccharide is glucose at 28.20 mS/cm while for disaccharide is lactose at 28.00 mS/cm with percentage of salt at 35 wt.%. Ionic conductivity increases when concentration of salt increase because there is an interaction between salt with functional groups of compounds. Based on computer simulations of DFT, interaction between lithium with compounds can be occurred due to negative electrostatic potential on the molecule. Electronegativity value of oxygen atom in glucose (-0.562e) and lactose (-0.567e) higher than fructose (-0.559e) and sucrose (-0.515e). Functional groups that are dominant to interact when interact with lithium salt are O-15 for glucose and O-17 for lactose due to the shorter bond length, the stronger energy attraction between functional groups with lithium.

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Design of proton conducting solid biopolymer blend electrolytes based on chitosan‐potato starch biopolymers: Deep approaches to structural and ion relaxation dynamics of H⁺ ion

Abdulwahid

Aziz

Kadir

2022

J of Applied Polymer Sci

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The need for flexible energy storage devices for advanced technologies has encouraged researchers to focus on environmental-friendly biopolymers. In this work, chitosan (CS) and potato starch (PS) biopolymers are blended to prepare proton conducting solid electrolytes. Based on the X-ray diffraction (XRD) inspection, the most amorphous blended film with the lowest crystallinity degree was selected to prepare polymer electrolytes. The variation in Fourier-transform infrared spectroscopy (FTIR) bands were used to investigate the occurrence of interactions among the ammonium thiocyanate (NH 4 SCN) salt and CS:PS polymer blends. The experimental results of electrochemical impedance spectroscopy (EIS) were simulated with electrical equivalent circuit (EEC) modeling to determine the circuit elements. The highest value of 1:07 Â 10 À5 S cm À1 was recorded for the sample included 40 wt.% of dopant salt. The dielectric analyses were helpful in separating the regions ascribed to electrode and molecular polarizations. The combination of circuit elements achieved from the EEC modeling and Koops phenomenological interpretation is used to understand the behavior of the loss tangent (tanδ) pattern. The AC conductivity pattern followed Jonscher's power law. The relaxation dynamics interrelated with ions is explained using electric modulus approaches. The peaks hidden in the dielectric loss (ε 00 ) spectra, were manifested in the imaginary part of electric modulus (M 00 ) pattern. The M 0 -M 00 patterns were used to shed light on the coupling between ionic motion and polymer chain dynamics.

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Proton Conducting Biopolymer Electrolytes Based on Starch Incorporated with Ammonium Thiocyanate

Cited by 10 publications

References 16 publications

Association–Dissociation Dynamics of Ionic Electrolytes in Low Dielectric Medium

Association–Dissociation Dynamics of Ionic Electrolytes in Low Dielectric Medium

Effect of Monosaccharides and Disaccharides Type on Ionic Conductivity of Liquid Electrolyte Based Lithium Iodide

Design of proton conducting solid biopolymer blend electrolytes based on chitosan‐potato starch biopolymers: Deep approaches to structural and ion relaxation dynamics of H⁺ ion

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Proton Conducting Biopolymer Electrolytes Based on Starch Incorporated with Ammonium Thiocyanate

Cited by 10 publications

References 16 publications

Association–Dissociation Dynamics of Ionic Electrolytes in Low Dielectric Medium

Association–Dissociation Dynamics of Ionic Electrolytes in Low Dielectric Medium

Effect of Monosaccharides and Disaccharides Type on Ionic Conductivity of Liquid Electrolyte Based Lithium Iodide

Design of proton conducting solid biopolymer blend electrolytes based on chitosan‐potato starch biopolymers: Deep approaches to structural and ion relaxation dynamics of H+ ion

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Design of proton conducting solid biopolymer blend electrolytes based on chitosan‐potato starch biopolymers: Deep approaches to structural and ion relaxation dynamics of H⁺ ion