Electrospun-sodiumtetrafluoroborate-polyethylene oxide membranes for solvent-free sodium ion transport in solid state sodium ion batteries

Freitag, Katharina; Walke, Patrick; Nilges, Tom; Kirchhain, Holger; Spranger, Robert J.; Wüllen, Leo van

doi:10.1016/j.jpowsour.2017.12.083

Cited by 48 publications

(31 citation statements)

References 34 publications

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“…This is due to the high crystallinity (up to 70%) for high molar-mass SPEs. [5][6][7]18,30] Thus, various approaches have been made to enhance to conductivity of SPEs such as addition of plasticizers [31][32][33] and fillers, [34][35][36][37][38][39][40] polymer blending, [4,26,[41][42][43] polymer hosts using copolymers [44][45][46][47][48] etc. Blending PEO with another component is one of the cost-effective and convenient ways for the enhancement of the conductivity of SPEs by compositional change of the blends.…”

Section: Introductionmentioning

confidence: 99%

Thermal Properties and Morphology of Poly(ethylene oxide)/Poly(n‐butyl methacrylate) Blends

Ramli

Chan

Ali

2018

Macromolecular Symposia

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From the thermodynamic point of view, most of the high molar‐mass binary polymer blends are immiscible due to the entropic contribution to the free energy of mixing is relatively small. The miscibility of the systems on the molecular scale can be assessed by the thermal properties such as quantities of glass transition temperature (Tg) and change in heat capacity (ΔCp) of the polymers. For a semi‐crystalline polymer such as poly(ethylene oxide) (PEO), the crystallinity (X*) and the melting temperature (Tm) can also give some hints on the miscibility. Apart from the thermal properties, additional scientific findings such as morphology of the blends are needed as supplementary evidences to support the results. We focus on the PEO as the polymer host, blends with poly(n‐butyl methacrylate) (PnBMA) which were prepared using solution casting technique. Thermal properties of PEO/PnBMA polymer blends were investigated by modulated differential scanning calorimeter (MDSC) on the isothermal crystallized samples at 25 °C. Tg of PEO in the blends do not show significant variation with addition of PnBMA for entire composition range while for Tg of PnBMA in the blends, it is challenging to be estimated under the experimental condition due to the overlapping of the Tg of PnBMA and melting endotherm of PEO. Constancy of quantity Tg of PEO and ΔCp of PEO corresponding to the content of PEO in the blends suggest that PEO and PnBMA are immiscible for entire blend composition. X* and Tm of PEO in the blends show insignificant variation in PEO/PnBMA blends, when PEO as major component. This implies that these blends are immiscible under the experimental conditions as agreed with results of Tg and ΔCp. Spherulitic morphologies of PEO in the blends were studied by polarized optical microscopy (POM). PnBMA phase disperses randomly in PEO matrix when PEO in excess. The absence of significant change for the fibrillar spherulitic structures of PEO spherulites with addition of PnBMA (when PEO is the major component) suggests that immiscibility of PEO and PnBMA. Besides, the crystalline structure of PEO in PEO/PnBMA blends using X‐ray diffraction (XRD) reveals that the crystalline structure of PEO is not disturbed with the addition of PnBMA when PEO is in excess as the two distinct peaks of PEO do not shift as compared to neat PEO. Impedance spectroscopy (IS) studies show that the ionic conductivities (σDC) of the polymer blends at room temperature slightly increase with increasing of PEO with the order of magnitude of 10−11–10−10 S cm−1. This system serves as a potential polymer host as solid polymer electrolytes when added with inorganic salt.

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Section: Introductionmentioning

confidence: 99%

Thermal Properties and Morphology of Poly(ethylene oxide)/Poly(n‐butyl methacrylate) Blends

Ramli

Chan

Ali

2018

Macromolecular Symposia

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“…It is prepared by sandwiching a Na + ion conducting solid electrolyte between anode and cathode materials. Till now, a number of PEO x ‐NaX electrolytes have been investigated, where NaX stands for an inorganic salt . In this study, we have used the synthesized organic salt, DST (C 6 H 4 [COONa] 2 ) providing an organic anion with two Na + ions per molecule.…”

Section: Resultsmentioning

confidence: 99%

“…In the past, a number of Na + ion conducting PEO x ‐NaX polymer electrolytes has been investigated, where NaX is an inorganic salt and X stands for an anion such as I, SCN, Br, ClO 4 , NO 3 , PF 6 , PO 3 , BF 4 , YF 4 , CF 3 SO 3 , (CF 3 SO 2 ) 2 N, and (FSO 2 ) 2 N . The abbreviation, PEO corresponds to a high‐molecular‐weight poly(ethylene oxide) and x is the [O]/[Na + ] molar ratio.…”

Section: Introductionmentioning

confidence: 99%

Utilization of poly(ethylene terephthalate) waste for preparing disodium terephthalate and its application in a solid polymer electrolyte

Haq

Shakeel

Alanazi

et al. 2019

J of Applied Polymer Sci

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A widespread application and nonbiodegradability of the poly(ethylene terephthalate) (PET) have created a huge amount of waste, which is imposing a serious life-threatening environmental problem. In this study, we have utilized the PET waste to synthesize disodium terephthalate (DST), an organic salt having two Na + ions per molecule. The purity of the DST phase was confirmed by Fourier transform infrared spectroscopy, X-ray diffractometry (XRD), and thermogravimetric analysis (TGA). A new poly(ethylene oxide)-DST polymer electrolyte was synthesized for utilizing Na + ions of the DST. The electrical conductivity of the electrolyte was optimized by varying the [O]/[Na + ] mole ratio with temperature and the results were explained using the XRD and differential scanning calorimetry studies. The TGA study showed that the electrolyte is thermally stable up to 200 C.

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“…At least the coordination behavior of the Li ions in the PEO matrix seems to be not affected by the anion exchange, and the postulated mechanism of ion transport in PEO, where Li + is coordinated by oxygen of the PEO matrix and the Li ion transport is determined by an increased PEO chain mobility, is still valid. For a detailed discussion of the underlying mechanism, the reader is referred to check the literature , . An investigation of the local ion mobility's is discussed in the NMR Section later on.…”

Section: Resultsmentioning

confidence: 99%

“…Solution casting, dip coating, or hot pressing are common methods to realize ion conducting thin membranes. Recently, an alternative process to access thin membranes of conductive salts in polyethylene oxide (PEO), like LiBF 4 @PEO and NaBF 4 @PEO , has been reported. In this process, electrospinning was used to fabricate thin‐film membranes, which showed high conductivities up to 9 × 10 –4 S · cm –1 and reasonable stability against lithium and sodium metal.…”

Section: Introductionmentioning

confidence: 99%

Electrospun Li(TFSI)@Polyethylene Oxide Membranes as Solid Electrolytes

Walke

Freitag

Kirchhain

et al. 2018

Zeitschrift anorg allge chemie

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Thin membranes of lithium‐bis(trifluoromethan)sulfonimide@poly (ethylene oxide) (or Li(TFSI)@PEO) were fabricated by electrospinning from acetonitrile solutions of the starting materials at room temperature. Membranes were tested with and without succinonitrile (SN), acting as a plasticizer to enhance the ion mobility in the systems. Our experiments substantiate, that SN does influence the electrochemical performance and physical properties of the membranes. Homogeneous amorphous membranes were only realized for SN‐containing samples, while phase segregation and crystallization occurred for SN‐free representatives. Membranes of different compositions were tested and the optimum molar mixture of PEO:SN:Li(TFSI), in terms of membrane conductivity, was identified as 36:8:1. Conductivities up to up to 2.8 × 10–4 S·cm–1 were determined by impedance spectroscopy for this membrane. Used as solid electrolytes without the aid of any additional electrolyte in symmetric Li vs. Li cells, a reasonable stability upon Li cycling could be observed. Here we illustrate that electrospun plasticizer‐modified Li(TFSI)@PEO membranes show high conductivities at very low conductive salt concentrations, compared with solution casted or hot pressed representatives. This feature renders these materials as potential candidates for separators in all solid‐state batteries or related energy storage applications.

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Electrospun-sodiumtetrafluoroborate-polyethylene oxide membranes for solvent-free sodium ion transport in solid state sodium ion batteries

Cited by 48 publications

References 34 publications

Thermal Properties and Morphology of Poly(ethylene oxide)/Poly(n‐butyl methacrylate) Blends

Thermal Properties and Morphology of Poly(ethylene oxide)/Poly(n‐butyl methacrylate) Blends

Utilization of poly(ethylene terephthalate) waste for preparing disodium terephthalate and its application in a solid polymer electrolyte

Electrospun Li(TFSI)@Polyethylene Oxide Membranes as Solid Electrolytes

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