A review of advanced separators for rechargeable batteries

Sodium-ion battery is a potential application system for large-scale energy storage due to the advantage of higher nature abundance and lower production cost of sodium-based materials. However, there exist inevitably the safety problems such as flammability due to the use of the same type of organic liquid electrolyte with lithium-ion battery. Gel polymer electrolytes are being considered as an effective solution to replace conventional organic liquid electrolytes for building safer sodium-ion batteries. In this review paper, the authors present a comprehensive overview of the research progress in electrochemical and physical properties of the gel polymer electrolyte-based sodium batteries. The gel polymer electrolytes based on different polymer hosts namely poly(ethylene oxide), poly(acrylonitrile), poly(methyl methacrylate), poly(vinylidene fluoride), poly(vinylidene fluoride-hexafluoro propylene), and other new polymer networks are summarized. The ionic conductivity, ion transference number, electrochemical window, thermal stability, mechanical property, and interfacial issue with electrodes of gel polymer electrolytes, and the corresponding influence factors are described in detail. Furthermore, the ion transport pathway and ion conduction mechanism are analyzed and discussed. In addition, the advanced gel polymer electrolyte systems including flame-retardant polymer electrolytes, composite gel polymer electrolytes, copolymerization, single-ion conducting polymer electrolytes, etc. with more superior and functional performance are classified and summarized. Finally, the application prospects, development opportunities, remaining challenges, and possible solutions are discussed. 

https://onlinelibrary.wiley.com/doi/pdfdirect/10.1002/eem2.12422

Progress in Gel Polymer Electrolytes for Sodium‐Ion Batteries

Ionic liquid electrolytes for sodium-ion batteries to control thermal runaway

The paper reports effect of dispersion of titanium dioxide (TiO2) nanofiller on the sodium ion conducting nanocomposite polymer electrolyte membranes consisting of TiO2 dispersed membranes of poly(vinylidenedifluoride-co-hexafluoropropylene) (PVdF-HFP) soaked in a liquid electrolyte of sodium hexafluorophosphate (NaPF6) in ethylene carbonate (EC) and propylene carbonate (PC). The TiO2 dispersed membranes have been prepared by phase inversion technique. The structural and morphological properties of the polymer electrolyte membranes have been investigated using x-ray diffraction, Fourier transform infrared spectroscopy, and scanning electron microscopy. The membranes have been found to be highly porous with maximum porosity ~ 72% and liquid electrolyte uptake ~ 270%. Ionic conductivity of the electrolyte membranes containing different concentrations of TiO2 has been measured by complex impedance spectroscopy. The maximum room temperature ionic conductivity has been found to be ~ 1.3 × 10−3 S cm−1. The ionic conductivity measured with temperature has been found to follow VTF behavior. The ion transport numbers of the membranes have been studied using dc polarization, complex impedance, and cyclic voltammetry. The membranes have been found to be predominantly ionically conducting with Na+ transport number ~ 0.31. The electrochemical stability window of the membranes has also been measured using cyclic voltammetry and found to be 3.5 V.

Sodium ion conducting nanocomposite polymer electrolyte membrane for sodium ion batteries

We report a trimethyl phosphate (TMP) based sodium ion conducting flame-retardant gel polymer electrolyte for safer electrochemical applications. The physical investigations reveal superior amorphicity and thermal stability of electrolyte utilizing TMP solvent as compared to the conventionally used binary mixture of ethylene carbonate (EC) and propylene carbonate (PC). The TMP based electrolyte membrane displays better ionic conductivity (∼ 1.40 mS cm−1) as compared to the membrane with EC:PC solvent mixture (∼ 0.72 mS cm−1) at 30°C with higher electrochemical stability window of ∼ 4.5 V and superior Na+ transport characteristics. The TMP based electrolyte has been utilized for proto-type sodium battery and EDLC application. The proto-type Na battery displays an open circuit potential of ∼ 2.3 V and specific discharge capacity of ∼ 225 mA h g−1. The electric double layer capacitor (EDLC) fabricated using the TMP based electrolyte and activated carbon electrodes shows specific capacitance of ∼100 F g−1 and is stable up to 4000 charge–discharge cycles. 

Sodium ion conducting flame-retardant gel polymer electrolyte for sodium batteries and electric double layer capacitors (EDLCs)

A nanocomposite gel polymer electrolyte system comprising porous membrane of poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP)/TiO2 immobilizing a liquid electrolyte of sodium trifluoromethanesulfonate (NaCF3SO3) in 1-butyl-3-methylimidazolium trifluoromethanesulfonate (BMImCF3SO3) ionic liquid is reported in the paper. The porous gel polymer electrolyte membranes are prepared by phase-inversion technique. The electrolyte membranes are characterized by various physical and electrochemical techniques. The TiO2 nanoparticles display interaction with the anion (CF3SO3−) of the liquid electrolyte and enhance amorphicity in the polymer network. The optimized membrane displays maximum room temperature ionic conductivity as ~0.4 mS cm−1 with improved electrochemical stability window of ~4.3 V and Na+ ion transport number as ~0.27. A proto-type sodium battery using the optimized membrane is fabricated and characterized. The battery delivers a stable open circuit potential of ~2.2 V and shows a discharge capacity ~200 mA h g−1 at 25 mA g−1 drain current.

Studies on ionic liquid based nanocomposite gel polymer electrolyte and its application in sodium battery

A mechanically stable porous polymer membrane of Poly(vinylidene fluoride-hexafluoropropylene) has been prepared by phase inversion technique using steam as a non-solvent. The membrane possesses semicrystalline network with enhanced amorphicity as observed by X-ray diffraction. The membrane has been soaked in an electrolyte solution of 0.5M NaPF6 in Ethylene Carbonate/Propylene Carbonate (1:1) to obtain the gel polymer electrolyte. The porosity and electrolyte uptake of the membrane have been found to be 67% and 220% respectively. The room temperature ionic conductivity of the membrane has been obtained as ∼ 0.3 mS cm−1. The conductivity follows Arrhenius behavior with temperature and gives activation energy as 0.8 eV. The membrane has been found to possess significantly large electrochemical stability window of 5.0 V.A mechanically stable porous polymer membrane of Poly(vinylidene fluoride-hexafluoropropylene) has been prepared by phase inversion technique using steam as a non-solvent. The membrane possesses semicrystalline network with enhanced amorphicity as observed by X-ray diffraction. The membrane has been soaked in an electrolyte solution of 0.5M NaPF6 in Ethylene Carbonate/Propylene Carbonate (1:1) to obtain the gel polymer electrolyte. The porosity and electrolyte uptake of the membrane have been found to be 67% and 220% respectively. The room temperature ionic conductivity of the membrane has been obtained as ∼ 0.3 mS cm−1. The conductivity follows Arrhenius behavior with temperature and gives activation energy as 0.8 eV. The membrane has been found to possess significantly large electrochemical stability window of 5.0 V.

Sodium ion conducting polymer electrolyte membrane prepared by phase inversion technique

A sodium ion conducting gel polymer electrolyte membrane comprising polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) immobilizing a liquid electrolyte of sodium hexa fluorophosphate (NaPF6) in a junk of ethylene carbonate (EC) and propylene carbonate (PC) is composed by solution cast technique. The membrane has been characterized by impedance spectroscopy and linear sweap voltammetry. The electrolyte membrane possesses ionic conductivity of ∼3.5 mS cm−1 and an electrochemical stability window of ∼4V.A sodium ion conducting gel polymer electrolyte membrane comprising polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) immobilizing a liquid electrolyte of sodium hexa fluorophosphate (NaPF6) in a junk of ethylene carbonate (EC) and propylene carbonate (PC) is composed by solution cast technique. The membrane has been characterized by impedance spectroscopy and linear sweap voltammetry. The electrolyte membrane possesses ionic conductivity of ∼3.5 mS cm−1 and an electrochemical stability window of ∼4V.

Electro-chemical studies on sodium ion conducting gel polymer electrolyte of PVdF-HFP+NaPF6

Abstract In this paper, experimental studies on blend gel polymer electrolyte membranes comprising of poly(vinylidene fluoride) (PVDF) and poly(methyl methacrylate) (PMMA) saturated with 0.1 M liquid electrolyte of sodium tetrafluoroborate (NaBF4) in the mixture of ethylene carbonate (EC) and diethyl carbonate (DEC) are presented. Membranes are prepared by phase inversion technique. The effect of blending on the ionic conductivity, electrochemical stability window, ionic transference number, and cation transport number has been investigated using complex impedance spectroscopy, linear sweep voltammetry and DC polarization technique. Ion dynamics in the electrolyte membranes has also been investigated using dielectric studies. The optimized electrolyte membrane with composition PVDF:PMMA (95:5) + 0.1 M NaBF4 + EC + DEC shows highest ionic conductivity of 0.6 mS cm−1 which follows Vogel–Tamman–Fulcher (VTF) behavior with temperature. The membrane shows an electrochemical stability window of 3.5 V and sodium ion transport number as ∼0.33.

Effect of polymer blending on the electrochemical properties of porous PVDF/PMMA membrane immobilized with organic solvent based liquid electrolyte

Gel polymer electrolyte membranes are prepared by immobilizing two different liquid electrolytes of NaBF4 salt in porous Poly(vinylidene fluoride) PVdF membrane. The liquid electrolytes are prepared in two different solvents, 1-butyl-3-methylimidazolium tetrafluoroborate (BMIMBF4) ionic liquid and binary mixture of ethylene carbonate (EC) and diethyl carbonate (DEC). The effect of solvents is investigated using electrochemical impedance spectroscopy, linear sweep voltammetry and dc polarization technique. The ionic conductivity of the electrolyte membrane with ionic liquid solvent is observed better (∼ 4.1 × 10-4 S cm-1) with better electrochemical stability window of ∼4.8 V.

A comparative study of ionic liquid and organic solvent based porous polymer electrolytes

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