Polypropylene-supported and nano-Al2O3 doped poly(ethylene oxide)-poly(vinylidene fluoride-hexafluoropropylene)-based gel electrolyte for lithium ion batteries

A new gel polymer electrolyte (GPE) is reported in this paper. In this GPE, blending polymer of poly(ethylene oxide) (PEO) with poly(vinylidene fluoride-hexafluoropropylene) (P(VdF-HFP)), doped with nano-Al₂O₃ and supported by polypropylene (PP), is used as polymer matrix, namely PEO-P(VdF-HFP)-Al₂O₃/PP. The performances of the PEO-P(VdF-HFP)-Al₂O₃/PP membrane and the corresponding GPE are characterized with mechanical test, CA, EIS, TGA and charge-discharge test. It is found that the performances of the membrane and the GPE depend to a great extent on the content of doped nano-Al₂O₃. With doping 10 wt.% nano-Al₂O₃ in PEO-P(VdF-HFP), the mechanical strength from 9.3 MPa to 14.3 MPa, the porosity of the membrane increases from 42% to 49%, the electrolyte uptake from 176% to 273%, the thermal decomposition temperature from 225 °C to 355 °C, and the ionic conductivity of corresponding GPE is improved from 2.7 × 10⁻³ S cm⁻¹ to 3.8 × 10⁻³ S cm⁻¹. The lithium ion battery using this GPE exhibits good rate and cycle performances.     

Hydrothermal synthesis of MoO3 nanobelts utilizing poly(ethylene glycol)

Metal oxide nanostructures hold enormous potential for electrochemical applications. While thin films of polymer-modified metal oxide electrodes have been widely investigated, there have been a few studies on polymer-modified nanopowders. We report the synthesis of pure molybdenum trioxide (MoO₃), pristine and aged nanobelts using hydrothermal method with poly(ethylene glycol) (PEG). Scanning electron microscope (SEM) images reveal the nanobelts to have dimensions of 1–5 μm in length and 100–600 nm in diameter. The electrochemical measurements show that PEG-used aged MoO₃ nanobelts have higher specific charge capacity than the PEG-free MoO₃ and PEG-used pristine MoO₃ nanobelts.     

Quasi-solid state dye-sensitized solar cells based on gel polymer electrolyte with poly(acrylonitrile-co-styrene)/NaI+I2

Gel polymer electrolyte based on poly(acrylonitrile-co-styrene)/NaI+I₂ and binary solvent mixture was prepared. When the system contains 0.5 M NaI and 0.05 M I₂, the maximum ionic conductivity (at 30 °C) of 2.37 mS cm⁻¹ was achieved. Based on a gel polymer electrolyte with 0.5 M NaI, 0.05 M I₂ and 0.5 M 4-tert-butylpyridine, a quasi-solid state dye-sensitized solar cell was fabricated and its overall energy conversion efficiency of light-to-electricity of 2.75% was achieved under irradiation of 60 mW cm⁻².     

Interfacial properties between LiFePO4 and poly(ethylene oxide)-Li(CF3SO2)2N polymer electrolyte

The interface resistance between Li_xFePO₄ and poly(ethylene oxide) (PEO)-Li(CF₃SO₂)₂N (LiTFSI) was examined by AC impedance measurement of a Li_xFePO₄/PEO-LiTFSI/Li_xFePO₄ cell in the temperature range of 30-60 °C. Four types of resistance, R0, R1, R2 and R3 were proposed according to analysis of the cell impedance using an equivalent circuit. The sum of R0 and R1 in the high frequency range is consistent with the resistance of the PEO electrolyte. R2 in the middle frequency range is related to lithium ion transport to an active point for charge transfer inside the composite electrode, and R3 in the low frequency range is considered to be the charge transfer resistance. The activation energy for R2 was affected by the thickness and composition of the electrode, whereas that for R3 was not.     

Tri(ethylene glycol)-substituted trimethylsilane/lithium bis(oxalate)borate electrolyte for LiMn2O4/graphite system

Silane-based electrolyte is a promising candidate for safer electrochemical energy storage devices because it is thermally and electrochemical stable, less flammable and environmental benign. In this paper, electrochemical properties of one of the silane-based electrolytes, tri(ethylene glycol)-substituted trimethylsilane (1NM3)-lithium bis(oxalate)borate (LiBOB) was studied using LiMn₂O₄ as cathode and MAG graphite as anode. When combined with LiBOB as lithium salt, the 1NM3-LiBOB electrolyte can provide solid electrolyte interface (SEI) formation due to the reductive decomposition of LiBOB at first charging cycle. Compared to the electrolyte used in the conventional lithium-ion batteries, 1NM3-LiBOB electrolyte showed compatible battery performance in LiMn₂O₄/MAG chemistry. The AC impedance measurement indicates that the activation energy (E_a) obtained from the charge transfer impedance for 1NM3-LiBOB was higher than that of the state-of-the-art electrolyte. Due to its low conductivity, the rate capability of 1NM3-LiBOB electrolyte needs to be improved.     

Electrochemical stability of lithium bis(oxatlato) borate containing solid polymer electrolyte for lithium ion batteries

The electrochemical stability of lithium bis(oxatlato) borate (LiBOB) containing solid polymer electrolyte has been evaluated both by inert electrode and real cathodes. Enhanced intrinsic anodic stability and decreased interface impedance, are obtained by addition of nano-sized MgO to PEO₂₀-LiBOB. It is also found that the LiBOB-containing SPEs exhibit prominent kinetic stability between 3.0 and 4.5 V. For cells using SPEs as the separators, good cycling performance is obtained for real 4 V class cathodes material LiNi_1/3Co_1/3Mn_1/3O₂ and LiCoO₂. The Li|PEO₂₀-LiBOB|LiNi_1/3Co_1/3Mn_1/3O₂ cell takes an initial capacity of 156.8 mAh g⁻¹, with retention of 142.5 mAh g⁻¹ after 20 cycles at 0.2C-rate. The cell also works well up to 1C-rate. The addition of nano-sized MgO into PEO₂₀-LiBOB readily reduces the irreversible capacity per cycle, both for LiNi_1/3Co_1/3Mn_1/3O₂ and LiCoO₂ cathodes. In addition, the critical role of LiBOB in obtaining kinetic stability and passivating ability towards cathodes are specially discussed.     

Discharge properties of all-solid sodium–sulfur battery using poly (ethylene oxide) electrolyte

An all-solid sodium/sulfur battery using poly (ethylene oxide) (PEO) polymer electrolyte are prepared and tested at 90 °C. Each battery is composed of a solid sulfur electrode, a sodium metal electrode, and a solid PEO polymer electrolyte. During the first discharge, the battery shows plateau potentials at 2.27 and at 1.76 V. The first discharge capacity is 505 mAh g⁻¹ sulfur at 90 °C. The capacity drastically decreases by repeated on charge–discharge cycling but remains at 166 mAh g⁻¹ sulfur after 10 cycles. The latter value is higher than that reported for a Na/poly (vinylidene difluoride)/S battery at room temperature.     

Inorganic-organic polymer electrolytes based on poly(vinyl alcohol) and borane/poly(ethylene glycol) monomethyl ether for Li-ion batteries

In this study, poly(vinyl alcohol) (PVA) was modified with poly(ethylene glycol) monomethyl ether (PEGME) using borane-tetrahydrofuran (BH₃/THF) complex. Molecular weights of both PVA and PEGME were varied prior to reaction. Boron containing comb-branched copolymers were produced and abbreviated as PVA1PEGMEX and PVA2PEGMEX. Then polymer electrolytes were successfully prepared by doping of the host matrix with CF₃SO₃Li at several stoichiomeric ratios with respect to EO to Li. The materials were characterized via nuclear magnetic resonance (¹H NMR and ¹¹B NMR), Fourier transform infrared spectroscopy (FT-IR), Thermogravimetry (TG) and differential scanning calorimeter (DSC). The ionic conductivity of these novel polymer electrolytes were studied by dielectric-impedance spectroscopy. Li-ion conductivity of these polymer electrolytes depends on the length of the side units as well as the doping ratio. Such electrolytes possess satisfactory ambient temperature ionic conductivity (>10⁻⁴ S cm⁻¹). Cyclic voltammetry results illustrated that the electrochemical stability domain extends over 4 V.     

Boosting the performance of poly(ethylene oxide)-based solid polymer electrolytes by blending with poly(vinylidene fluoride-co-hexafluoropropylene) for solid-state lithium-ion batteries

To seek a solid polymer electrolyte (SPE) with excellent performance, a novel poly(ethylene oxide) (PEO) based SPE is prepared by blending an appropriate amount of microcrystalline poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) with PEO using a universal solution casting method. Field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD) and differential scanning calorimetry (DSC) are utilized to analyse the samples. The crystallinity of the blend solid polymer electrolyte is significantly lower than that of the neat PEO-based SPE. The addition of the PVDF-HFP disrupts the segment structure of the PEO crystal region and increases the proportion of the amorphous region, thus boosting the migration of lithium ions. The results show that the electrochemical stability window of the blend solid polymer electrolyte reaches as high as 4.8 V. The initial discharge specific capacity of the solid-state LiFePO₄/SPE/Li battery is 131 mAh g⁻¹ at 0.5 C and 60°C, and the discharge specific capacity is still 110.5 mAh g⁻¹ after 100 cycles. On the basis of the results, the novel SPE has a widespread application prospects in solid-state lithium-ion batteries.     

In situ ceramic fillers of electrospun thermoplastic polyurethane/poly(vinylidene fluoride) based gel polymer electrolytes for Li-ion batteries

Gel polymer electrolyte films based on thermoplastic polyurethane (TPU)/poly(vinylidene fluoride) (PVdF) with and without in situ ceramic fillers (SiO₂ and TiO₂) are prepared by electrospinning 9 wt% polymer solution at room temperature. The electrospun TPU-PVdF blending membrane with 3% in situ TiO₂ shows a highest ionic conductivity of 4.8 × 10⁻³ S cm⁻¹ with electrochemical stability up to 5.4 V versus Li⁺/Li at room temperature and has a high tensile strength (8.7 ± 0.3 MPa) and % elongation at break (110.3 ± 0.2). With the superior electrochemical and mechanical performance, it is very suitable for application in polymer lithium ion batteries.     

Solid-state photoelectrochemical device based on poly(3-hexylthiophene) and an ion conducting polymer electrolyte, amorphous poly(ethylene oxide) complexed with I3/I redox couple

The photoelectrochemical properties of a solid-state photoelectrochemical cell (PEC) based on poly(3-hexylthiophene), P3HT, and an ion-conducting polymer electrolyte, amorphous poly(ethylene oxide), POMOE, complexed with I₃⁻/I⁻ redox couple has been constructed and studied. The current–voltage characteristics in the dark and under white light illumination, transient photocurrent and photovoltage studies, photocurrent action spectra for front and back side illuminations and an open-circuit voltage and short-circuit current dependence on light intensity have been studied. An open-circuit voltage of 130 mV and a short-circuit current of 0.47 μA cm⁻² were obtained at light intensity of 100 mW/cm². IPCE% of 0.024% for front side illumination (ITO/PEDOT) and IPCE% of 0.003% for backside illumination (ITO/P3HT) were obtained.     

Effect of co-doping nano-silica filler and N-methyl-N-propylpiperidinium bis(trifluoromethanesulfonyl)imide into polymer electrolyte on Li dendrite formation in Li/poly(ethylene oxide)-Li(CF3SO2)2N/Li

Lithium metal dendrite growth in Li/poly (ethylene oxide)-lithium bis (trifluoromethanesulfonyl) imide (PEO₁₈LiTFSI), nano-silica, and N-methyl-N-propylpiperidinium bis(trifluoromethanesulfonyl)imide (PP13TFSI) composite solid polymer electrolyte/Li was investigated by direct in situ observation. The dendrite onset time decreased with increasing current density and deviated from Sand's law in the current density range of 0.1-0.5 mA cm⁻² at 60 °C. Lithium dendrite formation was not observed until 46 h of polarization at 0.5 mA cm⁻² and 60 °C, which is a significant improvement compared to that observed in Li/(PEO₁₈LiTFSI)/Li, where the dendrite formation was observed after 15 h polarization at 0.5 mA cm⁻² and 60 °C. The suppression of dendrite formation could be explained by the electrical conductivity enhancement and decrease of the interface resistance between Li and the polymer electrolyte by the introduction of both nano-SiO₂ and PP13TFSI into PEO₁₈LiTFSI. The electrical conductivity of 4.96 × 10⁻⁴ S cm⁻¹ at 60 °C was enhanced to 7.6 × 10⁻⁴ S cm⁻¹, and the interface resistance of Li/PEO₁₈LiTFSI/Li of 248 Ω cm² was decreased to 74 Ω cm² by the addition of both nano-SiO₂ and PP13TFSI into PEO₁₈LiTFSI.     

Direct methanol fuel cell based on poly(vinyl alcohol)/titanium oxide nanotubes/poly(styrene sulfonic acid) (PVA/nt-TiO2/PSSA) composite polymer membrane

The high performance poly(vinyl alcohol)/titanium oxide nanotubes/poly(styrene sulfonic acid) (PVA/nt-TiO₂/PSSA) proton-conducting composite membrane is prepared by a solution casting method. The characteristic properties of these blend composite membranes are investigated by thermal gravimetric analysis (TGA), scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDX), micro-Raman spectroscopy, dynamic mechanical analysis (DMA), methanol permeability measurement and AC impedance method. It is found that the peak power densities of the DMFC with 1, 2, and 4 M CH₃OH fuels are 12.85, 23.72, and 10.99 mW cm⁻², respectively, at room temperature and ambient air. Especially, among three methanol concentrations, the 2 M methanol shows the highest peak power density among three methanol concentrations. The results indicate that the air-breathing direct methanol fuel cell comprised of a novel PVA/nt-TiO₂/PSSA composite polymer membrane has excellent electrochemical performance and stands out as a viable candidate for applications in DMFC.