Synthesis and characterization of dextrin-based polymer electrolytes for potential applications in energy storage devices

An attempt has been made to synthesise a new proton conducting polymer electrolyte using the biopolymer dextrin doped with ammonium thiocyanate salts using solution casting technique. The complexation has been studied using X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR). The differential scanning calorimetry (DSC) thermograms of dextrin with NH₄SCN showed that T_g value increases with respect to the increase of NH₄SCN concentration. The electrical conductivity was measured using AC impedance analyser which showed that ionic conductivity increases with increase in salt concentration up to 40%. Transference number measurement was carried out to investigate the nature of the charge transport species in the polymer electrolyte. Surface morphology of the electrolytes was determined using scanning electron microscope (SEM) studies, and the chemical composition of the elements present was determined using EDAX. The proton battery was constructed with the highest conducting polymer electrolyte Dex-40%NH₄SCN and its open circuit voltage with load were carried out.     

Performance of lithium-ion cells using 1 M LiPF<Subscript>6</Subscript> in EC/DEC (<Emphasis Type="Italic">v</Emphasis>/<Emphasis Type="Italic">v</Emphasis> = 1/2) electrolyte with ethyl propionate additive

In this work, 1 M LiPF₆:EC:DEC (v/v = 1/2) was used as a baseline electrolyte where EC is ethylene carbonate and DEC is diethyl carbonate. Ethyl propionate (EP) was used as an additive. The conductivity of the liquid electrolyte was obtained at ambient and elevated temperatures. The highest room temperature conductivity was observed at (8.05 ± 0.16) mS cm⁻¹ for the electrolyte containing 28.6 vol.% EP. Viscosity of the baseline and EP added baseline electrolytes have been measured at room and elevated temperatures. The electrolyte was also characterized by linear sweep voltammetry. The highest conducting electrolyte with 28.6 vol.% EP and the baseline electrolyte were used to fabricate several batteries. The batteries were charged and discharged at room temperature and at −20°C.     

NH<Subscript>4</Subscript>NO<Subscript>3</Subscript> as charge carrier contributor in glycerolized potato starch-methyl cellulose blend-based polymer electrolyte and the application in electrochemical double-layer capacitor

Potato starch (PS)-methyl cellulose (MC) blend solid biopolymer electrolytes infused with ammonium nitrate (NH₄NO₃) and glycerol as plasticizer are made via the solution cast technique. Fourier transform infrared (FTIR) spectroscopy indicates that NH₄NO₃ has interacted with the polymer blend host. The addition of 40 wt% glycerol in the highest conducting plasticizer free electrolyte has improved the conductivity to the order of ～10^?3 S cm^?1. The thermal stability of the electrolytes is identified by thermogravimetric analysis (TGA). Result from X-ray diffraction (XRD) analysis shows that the electrolyte with maximum conductivity value has the lowest degree of crystallinity. Differential scanning calorimetry (DSC) analysis reveals that the highest conducting plasticized electrolyte possesses the lowest glass transition temperature (T _g) of ?27.5 °C. Conductivity trend is further verified by dielectric analysis. Transference numbers of ion (t _ion) and electron (t _e) for the highest conducting electrolyte are identified to be 0.98 and 0.02, respectively, confirming that ions are the dominant charge carriers. Linear sweep voltammetry (LSV) evaluates that the potential window for the electrolyte is 1.88 V. The internal resistance of the electrochemical double-layer capacitor (EDLC) is between 29 and 64 Ω. From the charged-discharged measurement, the value of C _s is 31 F g^?1. The EDLC is stable over 1000 cycles.     

Structural,thermal and electrical properties of polyvinyl alcohol/poly(vinyl pyrrolidone)–sodium nitrate solid polymer blend electrolyte

Sodium ion conducting solid polymer blend electrolyte thin films have been prepared by using polyvinyl alcohol (PVA)/poly(vinyl pyrrolidone) (PVP) with NaNO₃ by solution cast technique. The prepared films were characterized by various methods. The complexation of the salt with the polymer blend was identified by X-ray diffraction (XRD) and Fourier transforms infrared spectroscopy (FTIR), Differential scanning calorimetry was used to analyze the thermal behavior of the samples, and the glass transition temperature is low for the highest conducting polymer material. The scanning electron microscopy gives the surface morphology of the polymer electrolytes. The frequency and temperature dependent of electrical conductivities of the films were studied using impedance analyzer in the frequency range of 1 Hz to 1 MHz. The highest electrical conductivity of 50PVA/50PVP/2 wt% NaNO₃ concentration has been found to be 1.25 × 10^?5 S cm^?1 at room temperature. The electrical permittivity of the polymer films have been studied for various temperatures. The transference number measurements showed that the charge transport is mainly due to ions than electrons. Using this highest conducting polymer electrolyte, an electrochemical cell is fabricated and the parameters of the cells are tabulated.     

Influence of pyrazole on the photovoltaic performance of dye-sensitized solar cell with polyvinylidene fluoride polymer electrolytes

We investigate the influence of the pyrazole content on the polyvinylidene fluoride (PVDF)/KI/I₂ electrolytes for dye-sensitized solar cells (DSSCs). The solid polymer electrolyte films consisting of different weight percentage ratios (0 20, 30, 40, and 50 %) of pyrazole doped with PVDF/KI/I₂ have been prepared by solution casting technique using N,N-dimethyl formamide (DMF) as a solvent. The as-prepared polymer electrolyte films were characterized by various techniques such as Fourier transform infrared spectroscopy (FT-IR spectroscopy), differential scanning calorimetry (DSC), X-ray diffractometer (XRD), alternate current (AC)-impedance analysis, and scanning electron microscopy (SEM). The 40 wt% pyrazole-PVDF/KI/I₂ electrolyte exhibited the highest ionic conductivity value of 9.52?×?10^?5 Scm^?1 at room temperature. This may be due to the lower crystallinity of PVDF and higher ionic mobility of iodide ions in the electrolyte. The DSSC fabricated using this highest ion conducting electrolyte showed an enhanced power conversion efficiency of 3.30 % under an illumination of 60 mW/cm² than that of pure PVDF/KI/I₂ electrolyte (1.42 %).     

Incorporation of NH4Br in PVA-chitosan blend-based polymer electrolyte and its effect on the conductivity and other electrical properties

Polymer electrolyte system based on poly(vinyl alcohol) (PVA)-chitosan blend doped with ammonium bromide (NH₄Br) has been prepared by solution cast method. Fourier transform infrared (FTIR) spectroscopy analysis confirms the complexation between salt and polymer host. The highest ionic conductivity obtained at room temperature is (7.68?±?1.24)?×?10^?4 S cm^?1 for the sample comprising of 30 wt% NH₄Br. X-ray diffraction (XRD) patterns reveal that PVA-chitosan with 30 wt% NH₄Br exhibits the most amorphous structure. Thermogravimetric analysis (TGA) reveals that the electrolytes are stable until ～260 °C. The conductivity variation can also be explained by field emission scanning electron microscopy (FESEM) study. Dielectric properties of the electrolytes follow non-Debye behavior. The conduction mechanism of the highest conducting electrolyte can be represented by the correlated barrier hopping (CBH) model. From linear sweep voltammetry (LSV) result, the highest conducting electrolyte is electrochemically stable at 1.57 V.     

Structural,electrical conductivity,and transport analysis of PAN–NH<Subscript>4</Subscript>Cl polymer electrolyte system

Poly (acrylonitrile) (PAN) and ammonium chloride (NH₄Cl)-based proton conducting polymer electrolytes with different compositions have been prepared by solution casting technique. The amorphous nature of the polymer electrolytes has been confirmed by XRD analysis. The FTIR analysis confirms the complex formation of the host polymer (PAN) with the salt (NH₄Cl). DSC measurements show a decrease in T_g with the increase in salt concentration. The conductivity analysis shows that the 25 mol% ammonium chloride doped polymer electrolyte has a maximum ionic conductivity, and it has been found to be 6.4 × 10^?3 Scm^?1, at room temperature. The temperature dependence of conductivity of the polymer electrolyte complexes appears to obey the Arrhenius nature. The activation energy (E_a = 0.23 eV) has been found to be low for 25 mol% salt doped polymer electrolyte. The dielectric behavior has been analyzed using dielectric permittivity (ε*), and the relaxation frequency (τ) has been calculated from the loss tangent spectra (tan δ). Using this maximum ionic conducting polymer electrolyte, the primary proton conducting battery with configuration Zn + ZnSO₄·7H₂O/75 PAN:25 NH₄Cl/PbO₂ + V₂O₅ has been fabricated and their discharge characteristics have been studied.     

Development of poly(glycerol suberate) polyester (PGS)–PVA blend polymer electrolytes with NH<Subscript>4</Subscript>SCN and its application

Besides commercially available synthetic polymers, the present work has been undertaken to explore the significance of poly(glycerol suberate) (PGS) polyester synthesised under lab scale in energy storage device. In this regard, a blend polymer electrolyte comprising of polyvinyl alcohol (PVA), poly(glycerol suberate) (PGS) polyester along with the various proportions of ammonium thiocyanate (NH₄SCN) was prepared adopting solution casting technique. The synthesised polyester PGS was characterised by Fourier transform infrared (FT-IR) spectroscopy, ¹H and ¹³C nuclear magnetic resonance (NMR) spectroscopy. The prepared electrolyte film was subjected to FT-IR analysis to study the complexation that has occurred within the blend. Its amorphous nature was revealed from X-ray diffraction (XRD) studies. Influence of NH₄SCN on the glass transition temperature (T_g) was drawn from differential scanning calorimetry (DSC) technique. The dispersion of dopant within the polymer matrix was supported by scanning electron microscopy (SEM) followed by its elemental composition from energy dispersive spectroscopy (EDS). From the AC impedance technique, maximum conductivity of 3.01?×?10^?4 S cm^?1 was elicited for the optimised electrolyte (1 g PVA?+?0.75 g PGS?+?0.6 g NH₄SCN). Frequency-dependent dielectric and modulus spectra were analysed to study the mechanism of transportation. Transport parameters evaluated by Wagner’s polarisation method proved that the conductivity was predominantly due to cations. Proton conducting battery was configured with the highest conducting electrolytic film and its cell parameters are presented.     

Biopolymeric electrolyte based on glycerolized methyl cellulose with NH<Subscript>4</Subscript>Br as proton source and potential application in EDLC

In the present work, biopolymer electrolyte films based on MC doped with NH₄Br salt and plasticized with glycerol were prepared by solution casting method. Fourier transform infrared (FTIR) spectroscopy analysis confirms the interaction between MC, NH₄Br, and glycerol. X-ray diffraction (XRD) explains that the enhancement of conductivity is affected by the degree of crystallinity. This result is verified by field emission scanning electron microscopy (FESEM). For unplasticized system, sample containing 25 wt% of NH₄Br possesses the highest ionic conductivity of (1.89 ± 0.05) × 10^?4 S cm^?1. The addition of 30 wt% glycerol increases the conductivity value up to (1.67 ± 0.04) × 10^?3 S cm^?1. The conduction mechanism was best presented by the correlated barrier hopping (CBH) model. The linear sweep voltammetry (LSV) and cyclic voltammetry (CV) result confirms the suitability of the highest conducting electrolyte to be employed in the fabrication of electrochemical double layer capacitor (EDLC).     

Vibrational,electrical, and ion transport properties of PVA-LiClO<Subscript>4</Subscript>-sulfolane electrolyte with high cationic conductivity

Novel solid polymer electrolytes, poly(vinylalcohol)-lithium perchlorate (PVA-LiClO₄) and PVA-LiClO₄-sulfolane are prepared by solvent casting method. The experimental results show that sulfolane addition enhances the ionic conductivity of PVA-LiClO₄ complex by three orders. The maximum ionic conductivity of 1.14 ± 0.20 × 10^?2 S cm^?1 is achieved for 10 mol% sulfolane-added electrolyte at ambient temperature. Polymer-salt-plasticizer interactions are analyzed through attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. Lithium ion transference number is found by AC impedance spectroscopy combined with DC potentiostatic measurements. The results confirm that sulfolane improves the Li⁺ transference number of PVA-LiClO₄ complex to 0.77 from 0.40. The electrochemical stability window of electrolytes is determined by cyclic voltammetry (CV). The broad electrochemical stability window of 5.45 V vs. lithium is obtained for maximum conducting electrolyte. All-solid-state cell is fabricated using maximum conducting electrolyte, and electrochemical impedance study is carried out. It reveals that electrolyte interfacial resistance with Li electrode is very low. The use of PVA-LiClO₄-sulfolane as a viable electrolyte material for high-voltage lithium ion batteries is ensured.     

Preparation and characterization of blend polymer electrolyte film based on poly(vinyl alcohol)-poly(acrylonitrile)/MgCl<Subscript>2</Subscript> for energy storage devices

The development of magnesium electrolytes for battery applications has been the demand for electrochemical devices. To meet such demand, in this work solid blend polymer electrolytes were prepared using polyvinyl alcohol (PVA) and polyacrylonitrile (PAN) (92.5PVA:7.5PAN) as host polymer, magnesium chloride (MgCl₂) of different molar mass percentage (m.m.%) (0.1, 0.2, 0.3, 0.4, 0.5, and 0.6%) as salt and dimethylformamide (DMF) as solvent. Structural, vibrational, thermal, electrical, and electrochemical properties of the prepared electrolytes were investigated using different techniques such as X-ray diffraction pattern, FTIR spectroscopy analysis, differential scanning calorimetry (DSC), AC impedance measurement, and transference number measurement. X-ray diffraction studies confirm the minimum volume fraction of crystalline phase for the polymer electrolyte with 0.5 m.m.% of MgCl₂. FTIR confirms the complex formation between host polymer and salt. DSC analysis proves the thermal transition of the prepared films are affected by salt concentration. The optimized material with 0.5 m.m.% of MgCl₂ offers a maximum electrical conductivity of 1.01 × 10^?3 S cm^?1 at room temperature. The Mg²⁺ ion conduction in the blend polymer electrolyte is confirmed from transference number measurement. Electrochemical analysis demonstrates the promising characteristic of these polymer films suitable as electrolytes for primary magnesium batteries. Output potential and discharge characteristics have been analyzed for primary magnesium battery which is constructed using optimized conducting electrolyte.     

Effect of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanofiller on the electrical,thermal and structural properties of PEO:PPG based nanocomposite polymer electrolyte

A new series of nanocomposite polymer electrolyte (NCPE) system comprising of polyethylene oxide (PEO) and polypropylene glycol (PPG) as blended polymer host, zinc trifluoromethanesulfonate [Zn(CF₃SO₃)₂] as dopant salt and nanocrystalline alumina [Al₂O₃] as filler was prepared by solution casting technique. The present system consisting of five different compositions of 87.5 wt% (PEO:PPG)–12.5 wt% Zn(CF₃SO₃)₂ + x wt% Al₂O₃ [where x = 1, 3, 5, 7 and 9, respectively] has been thoroughly characterized by various analytical techniques such as electrical impedance spectroscopy, X-ray diffraction (XRD) studies, differential scanning calorimetry (DSC), scanning electron microscopic (SEM) analysis and linear sweep voltammetry (LSV). The maximum room temperature ionic conductivity exhibited by the NCPE was found to be 2.1 × 10^?4 S cm^?1 for 3 wt% loading of Al₂O₃ which is an order higher than that of the optimized filler-free zinc salt doped polymer electrolyte system at 298 K. The evidence of a decrease in the degree of crystallinity responsible for the enhanced conductivity was revealed by the XRD data and further confirmed by DSC and SEM results. Moreover, the electrochemical stability window of the highly conducting electrolyte matrix has been experimentally determined by linear sweep voltammetry and found to be 3.6 V which is fairly adequate for the construction of zinc primary batteries as well as zinc-based rechargeable batteries at ambient conditions.     

Structural and ionic conductivity studies on proton conducting polymer electrolyte based on polyvinyl alcohol

An attempt has been made to prepare a new proton conducting polymer electrolyte based on polyvinyl alcohol (PVA) doped with NH₄NO₃ by solution casting technique. The complex formation between polymer and dissociated salt has been confirmed by X-ray diffraction analysis. The ionic conductivity of the prepared polymer electrolyte has been found by ac impedance spectroscopic analysis. The highest ionic conductivity has been found to be 7.5 × 10⁻³ Scm⁻¹ at ambient temperature for 20 mol% NH₄NO₃-doped PVA with low activation energy (~0.19 eV). The temperature-dependent conductivity of the polymer electrolyte follows an Arrhenius relationship, which shows hopping of ions in the polymer matrix.     

Effect of PVAc dispersal into PVA-NH4SCN polymer electrolyte

The present paper deals with ion transport studies on a new proton conducting composite polymer electrolyte — (PVA_x:NH₄SCN)_y:PVAc system. Complexation and morphology of the composite electrolyte films are discussed on the basis of X-ray diffraction and differential scanning calorimetry data. Coulometry and transient ionic current measurements revealed charge transport through protons. The maximum ion conductivity was found to be 7.4·10⁻⁴ S·cm⁻¹ for the composition: x=0.15, y=0.12. The observed conductivity behaviour is correlated to the morphology of the films. The temperature dependence of the electrical conductivity exhibits Arrhenius characteristics in two different temperature ranges separated by a plateau region related to morphological changes occurring in the electrolyte.     

The cycling performances of lithium–sulfur batteries in TEGDME/DOL containing LiNO3 additive

The cycling performance of lithium–sulfur batteries in binary electrolytes based on tetra(ethylene glycol)dimethyl ether (TEGDME) and 1,3-dioxolane(DOL) with lithium nitrate (LiNO₃) additive were investigated. The highest ionic conductivity was obtained for 1 M LiN(CF₃SO₂)₂ (LiTFSI) in TEGDME/DOL?=?33:67(volume ratio)-based electrolyte. The cyclic efficiency of lithium–sulfur batteries was dramatically increased with LiNO₃ additive as a shuttle inhibitor in electrolytes. The lithium–sulfur cell assembled with 1 M LiTFSI in TEGDME/DOL containing 0.2 M LiNO₃ additive for electrolyte, the elemental sulfur for cathode, and the lithium metal for anode demonstrated the initial discharge capacity of about 900 mAh g^?1 and an enhanced cycling performance.     

Conductivity studies of plasticized proton conducting PVA–PVIM blend doped with NH4BF4

The proton conducting solid-state polymer electrolyte comprising blend of poly(vinyl alcohol) (PVA) and poly(N-vinylimidazole) (PVIM), ammonium tetrafluoroborate (NH₄BF₄) as salt, and polyethylene glycol (PEG) (molecular weight 300 and 600) as plasticizer is prepared at various compositions by solution cast technique. The prepared films are characterized by Fourier transform infrared spectroscopy, differential scanning calorimetry, X-ray diffraction, and scanning electron microscopy analysis. The conductivity–temperature plots are found to follow an Arrhenius nature. The conductivity of solid polymer electrolytes is found to depend on salt and plasticizer content and also on the dielectric constant value and molecular weight of the plasticizer. Maximum ionic conductivity values of 2.20?×?10^?4 and 1.28?×?10^?4?S?cm^?1 at 30 °C are obtained for the system (PVA–PVIM)?+?20 wt.% NH₄BF₄?+?150 wt.% PEG300 and (PVA–PVIM)?+?20 wt.% NH₄BF₄?+?150 wt.% PEG300, respectively. The blended polymer, complexed with salt and plasticizer, is shown to be a predominantly ionic conductor. The proton transport in the system may be expected to follow Grotthuss-type mechanism.     

Influence of nano-sized fumed silica on physicochemical and electrochemical properties of cellulose derivatives-ionic liquid biopolymer electrolytes

Nanocomposite biopolymer electrolyte was prepared by solution-casting technique. Carboxymethyl cellulose from kenaf bast fibre, ammonium acetate, (1-butyl)trimethyl ammonium bis(trifluoromethylsulfonyl)imide ionic liquid and silica nanofiller was used to prepare the biopolymer electrolyte samples. The films were characterized by Fourier transform infrared spectroscopy, electrochemical impedance spectroscopy, scanning electron microscopy, transference number measurement and linear sweep voltammetry. The interactions of doping salt, ionic liquid and inorganic nanofiller with the host biopolymer were confirmed by FTIR study. The highest conductivity achieved was 8.63 × 10^?3 S cm^?1 by the incorporation of 1 wt% of SiO₂ at ambient temperature. The electrochemical stability of the highest conducting sample was stable up to 3.4 V, and the ion transference number in the film was 0.99.     

Thermally activated ionic conduction and local structure in solid LiPON thin films

Compact lithium phosphorous oxynitride (LiPON) thin films, as a solid-state electrolyte for all solid-state Li batteries and electrochromic (EC) devices, with the high ratio of the triply coordinated –N< (N_t) over the doubly coordinated –N= (N_d) structural units was deposited by a conventional reactive RF magnetron sputtering of a Li₃PO₄ target at a low pure N₂ pressure. The effect of heat treatment from 200 to 500 °C on the ionic conductivity and local structure of LiPON thin films were investigated by scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS) core level analysis. A dramatical improvement of ionic conductivity from 1.1 to 3.28 μS/cm and microstructure changes were happened on the LiPON thin films while annealed for 1 h at 300 °C, which was linked to structural differences with a highest ratio of –N< over –N= structural units. The work proves that a proper heat treatment on LiPON thin film can effectively improve its ionic conductivity and change its microstructure.     

Preparation and characterization of cellulose acetate and lithium nitrate for advanced electrochemical devices

Environmental research has the objective of finding solutions to environmental degradation. To this aim, an optimized solid bio-polymer electrolyte (BPE) based on cellulose acetate (CA) with lithium nitrate (LiNO₃) has been developed to achieve the possible energy storage Li-ion batteries. CA is one of the natural polymers with very good film forming capacity. The widespread use of CA is attributed to the availability of renewable resources, non-toxic nature, low cost, and bio-compatible material. Here, we demonstrate an extremely simplest process of solution-casting technique for the development of BPE by incorporating various LiNO₃ compositions (wt.%) with bio-polymer material CA. The crystalline nature of the CA with LiNO₃ has been analyzed by X-ray diffraction (XRD) measurement. The bio-polymer-salt complex formation and the biopolymer-proton interactions have been investigated through Fourier transform infrared (FTIR) spectroscopy. Electrochemical impedance spectroscopy has been used to examine the ionic conductivity of the BPEs at room temperature (303 K). The highest ionic conductivity of 1.93 × 10^?3S/cm has been achieved for 50CA/50LiNO₃ polymer electrolyte. Electrochemical studies show that highest BPE has high electrochemical stability windows. The conducting species is found to be Li⁺ ion, which has been confirmed by transference number measurement (TNM). Primary lithium battery with discharge profile has been constructed for 50CA/50LiNO₃. This research will help to identify a new lithium ion membrane for battery technology and other electrochemical device applications.     

Aqua oxyhydroxycarbonate second phases at the surface of Ba/Sr‐based proton conducting perovskites: a source of confusion in the understanding of proton conduction

Ba/Sr‐based zirconates and cerates appear as potential proton conducting electrolytes for water electrolysers, hydrogen fuel cells and CO₂/syngas converters. Such application requires long lifetime of each components: a good chemical and thermal stability of the device core and a low reactivity of the electrolyte membrane. It has been recently revealed that the complex infrared (IR) and Raman signatures observed for series of zirconates, cerates and/or titanates, assigned by some authors to the bulk protonic species actually arose from the surface species in the form of second undesirable phases: the high dense proton conducting ceramics being free from such signatures. In order to contribute to a better characterization of the phases that can be formed on the surface of proton conducting ceramics, we analysed the IR and Raman spectra of Ba/SrO, Ba/Sr(OH)_2, Ba/SrCO₃ in their dry and hydrated/deuterated forms in combination with thermogravimetric analysis. The results allowed us to confirm the above claim and to re‐assign the vibrational spectra of perovskite materials wrongly attributed to the bulk protonic species. Since these second phases exhibit a high proton conductivity, their presence is very detrimental in the determination of intrinsic electrolyte bulk properties and interpretation of the conduction mechanisms. Copyright © 2012 John Wiley & Sons, Ltd.