Enhanced Thermal Stability and Electrochemical Performance of Polyacrylonitrile/Cellulose Acetate-Electrospun Fiber Membrane by Boehmite Nanoparticles: Application to High-Performance Lithium-Ion Batteries

In this study, polyacrylonitrile/cellulose acetate (PAN/CA) composite nanofiber membranes with different boehmite contents are prepared by electrospinning. The physical and electrochemical properties of the composite nanofiber membrane as a separator in lithium batteries are investigated. In contrast to commercial polypropylene membrane (PP), the nanocomposite fiber membrane has a 3D network structure, higher porosity, higher thermal stability, higher electrolyte absorptivity, higher ionic conductivity, and better cycling performance. The PAN/CA composite membrane with 12 wt% boehmite has the highest ionic conductivity (1.694 mS cm⁻¹); the specific discharge capacity is 160 mAh g⁻¹ at 0.2 C discharge density and the highest capacity retention rate is 99.3% after 100 cycles. The cycle rate at 2 C has a higher capacity retention rate (88.75%). These results indicate that the PAN/CA/AlOOH composite nanofiber membrane can be expected to replace the commercial polyolefin membrane and behave as a high-performance separator for lithium-ion batteries.     

Synthesis of uniform polycrystalline tin dioxide nanofibers and electrochemical application in lithium-ion batteries

Under optimized synthesis conditions, very large area uniform SnO₂ nanofibers consisting of orderly bonded nanoparticles have been obtained for the first time by thermal pyrolysis and oxidization of electrospun tin(II)2-ethylhexanoate/polyacrylonitrile (PAN) polymer nanofibers in air. The structure and morphology were elaborated by X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). The SnO₂ nanofibers delivered a reversible capacity of 446 mAh g⁻¹ after 50 cycles at the 100 mA g⁻¹ rate and excellent rate capability of 477.7 mAh g⁻¹ at 10.0 C. Owing to the improved electrochemical performance, this electrospun SnO₂ nanofiber could be one of the most promising candidate anode materials for the lithium-ion battery.     

Effects of poly (vinyl alcohol) (PVA) content on preparation of novel thiol-functionalized mesoporous PVA/SiO2 composite nanofiber membranes and their application for adsorption of heavy metal ions from aqueous solution

Thiol-functionalized mesoporous poly (vinyl alcohol)/SiO₂ composite nanofiber membranes and pure PVA nanofiber membranes were synthesized by electrospinning. The results of Fourier transform infrared (FTIR) indicated that the PVA/SiO₂ composite nanofibers were functionalized by mercapto groups via the hydrolysis polycondensation. The surface areas of the PVA/SiO₂ composite nanofiber membranes were >290 m²/g. The surface areas, pore diameters and pore volumes of PVA/SiO₂ composite nanofibers decreased as the PVA content increased. The adsorption capacities of the thiol-functionalized mesoporous PVA/SiO₂ composite nanofiber membranes were greater than the pure PVA nanofiber membranes. The largest adsorption capacity was 489.12 mg/g at 303 K. The mesoporous PVA/SiO₂ composite nanofiber membranes exhibited higher Cu²⁺ ion adsorption capacity than other reported nanofiber membranes. Furthermore, the adsorption capacity of the PVA/SiO₂ composite nanofiber membranes was maintained through six recycling processes. Consequently, these membranes can be promising materials for removing, and recovering, heavy metal ions in water.     

Sorption of malachite green on vinyl-modified mesoporous poly(acrylic acid)/SiO2 composite nanofiber membranes

Vinyl-modified mesoporous poly(acrylic acid)/SiO₂ (PAA/SiO₂) composite nanofiber membranes were prepared through a sol-gel electrospinning process. The sorption behavior of malachite green on the membranes was studied. Fourier transform infrared (FTIR) results demonstrated that vinyl groups were grafted onto the silica skeleton. Transmission electron microscopy (TEM) images confirmed the formation of mesopores on the electrospun nanofibers and the pore size was 3.8 nm based on the Barrett-Joyner-Halenda (BJH) model. According to Brunauer-Emmett-Teller (BET) method, the specific surface area of the membranes was 523.84 m²/g. Three widely used isotherms, the Freundlich, Langmuir, and Redlich-Peterson isotherms, were used to model the experimental data of malachite green adsorption on PAA/SiO₂ nanofiber membranes. The best fit was found to be Redlich-Peterson isotherm and the equilibrium adsorption capacity was 220.49 mg/g. The adsorption kinetics followed a pseudo-second-order model. The removal of malachite green from the aqueous phase reached 98.8% in 240 min. The membranes can be regenerated by treated with alcohol solution and reused for multiple cycles, which is beneficial for practical application.     

Electrostatic heterocoagulation of carbon nanotubes and LiCoO2 particles for a high-performance Li-ion cell

Nanotubes were coated on the surface of active LiCoO₂ particles using electrostatic heterocoagulation to enhance the electrochemical properties of a Li-ion battery. Only 0.5 wt% of multiwalled carbon nanotubes (MWCNTs) was added as a conducting agent into the LiCoO₂ cathode, which had a density of 4.0 g cm⁻³. We found that our electrode that was prepared using heterocoagulation with 0.5 wt% of thin MWCNTs maintained a volumetric capacitance of 403 mAh cm⁻¹ after 40 cycles from the initial 624 mAh cm⁻¹, compared with previous result of 310 mAh cm⁻¹ obtained from simple mixing with 3 wt% MWCNTs. The high volumetric capacity with smaller swelling using less amount of MWCNTs was attributed to the self-assembled nanotube network formed between active particles during coagulation, which was maintained with volume expansion during cycle testing.     

Electrodeposition of iron oxide nanorods on carbon nanofiber scaffolds as an anode material for lithium-ion batteries

Iron oxide film with spaced radial nanorods is formed on the VGCF (vapor-grown carbon nanofiber) scaffolds by means of anodic electrodeposition. X-ray diffraction, scanning electron microscopy, and transmission electron microscopy show that the iron oxide film deposited on the VGCF surface is α-Fe₂O₃ and consists of spaced radial nanorods having 16-21 nm in diameter after annealing at 400 °C. Galvanostatic charge/discharge results indicate that the α-Fe₂O₃/VGCF anode (970 mAh g⁻¹) has higher capacity than bare α-Fe₂O₃ anode (680 mAh g⁻¹) at 10 C current discharge. VGCF scaffolds fabricated by electrophoretic deposition favor the electron conduction, and the spaced radial nanorods on VGCFs facilitate the migration of lithium ion from the electrolyte. Electrochemical reactions between α-Fe₂O₃ and lithium ion are therefore improved significantly by this tailored architecture.     

A polymer electrolyte membrane for high temperature fuel cells to fit vehicle applications

Poly(tetrafluoroethylene) PTFE/PBI composite membranes doped with H₃PO₄ were fabricated to improve the performance of high temperature polymer electrolyte membrane fuel cells (HT-PEMFC). The composite membranes were fabricated by immobilising polybenzimidazole (PBI) solution into a hydrophobic porous PTFE membrane. The mechanical strength of the membrane was good exhibiting a maximum load of 35.19 MPa. After doping with the phosphoric acid, the composite membrane had a larger proton conductivity than that of PBI doped with phosphoric acid. The PTFE/PBI membrane conductivity was greater than 0.3 S cm⁻¹ at a relative humidity 8.4% and temperature of 180 °C with a 300% H₃PO₄ doping level. Use of the membrane in a fuel cell with oxygen, at 1 bar overpressure gave a peak power density of 1.2 W cm⁻² at cell voltages >0.4 V and current densities of 3.0 A cm⁻². The PTFE/PBI/H₃PO₄ composite membrane did not exhibit significant degradation after 50 h of intermittent operation at 150 °C. These results indicate that the composite membrane is a promising material for vehicles driven by high temperature PEMFCs.     

Lithium-polymer battery based on an ionic liquid-polymer electrolyte composite for room temperature applications

A lithium-polymer battery based on an ionic liquid-polymer electrolyte (IL-PE) composite membrane operating at room temperature is described. Utilizing a polypyrrole coated LiV₃O₈ cathode material, the cell delivers >200 mAh g⁻¹ with respect to the mass of the cathode material. Discharge capacity is slightly higher than those observed for this cathode material in standard aprotic electrolytes; it is thought that this is the result of a lower solubility of the LiV₃O₈ material in the IL-PE composite membrane.     

Synthesis and electrochemical performance of Li2FeSiO4/carbon/carbon nano-tubes for lithium ion battery

Li₂FeSiO₄/carbon/carbon nano-tubes (Li₂FeSiO₄/C/CNTs) and Li₂FeSiO₄/carbon (Li₂FeSiO₄/C) composites were synthesized by a traditional solid-state reaction method and characterized comparatively by X-ray diffraction, scanning electron microscopy, BET surface area measurement, galvanostatic charge-discharge and AC impedance spectroscopy, respectively. The results revealed that the Li₂FeSiO₄/C/CNT composite exhibited much better rate performance in comparison with the Li₂FeSiO₄/C composite. At 0.2 C, 5 C and 10 C, the former composite electrode delivered a discharge capacity of 142 mAh g⁻¹, 95 mAh g⁻¹, 80 mAh g⁻¹, respectively, and after 100 cycles at 1 C, the discharge capacity remained 95.1% of its initial value.     

Increasing ionic conductivity and mechanical strength of a plastic electrolyte by inclusion of a polymer

In this contribution we present a soft matter solid electrolyte which was obtained by inclusion of a polymer (polyacrylonitrile, PAN) in LiClO₄/LiTFSI-succinonitrile (SN), a semi-solid organic plastic electrolyte. Addition of the polymer resulted in considerable enhancement in ionic conductivity as well as mechanical strength of LiX-SN (X = ClO₄, TFSI) plastic electrolyte. Ionic conductivity of 92.5%-[1 M LiClO₄-SN]:7.5%-PAN (PAN amount as per SN weight) composite at 25 °C recorded a remarkably high value of 7 × 10⁻³ Ω⁻¹ cm⁻¹, higher by few tens of order in magnitude compared to 1 M LiClO₄-SN. Composite conductivity at sub-ambient temperature is also quite high. At −20 °C, the ionic conductivity of (100 − x)%-[1 M LiClO₄-SN]:x%-PAN composites are in the range 3 × 10⁻⁵-4.5 × 10⁻⁴ Ω⁻¹ cm⁻¹, approximately one to two orders of magnitude higher with respect to 1 M LiClO₄-SN electrolyte conductivity. Addition of PAN resulted in an increase of the Young's modulus (Y) from Y → 0 for LiClO₄-SN to a maximum of 0.4 MPa for the composites. Microstructural studies based on X-ray diffraction, differential scanning calorimetry and Fourier transform infrared spectroscopy suggest that enhancement in composite ionic conductivity is a combined effect of decrease in crystallinity and enhanced trans conformer concentration.     

Inorganic-organic hybrid membranes with anhydrous proton conduction prepared from tetramethoxysilane/methyl-trimethoxysilane/trimethylphosphate and 1-ethyl-3-methylimidazolium-bis (trifluoromethanesulfonyl) imide for H2/O2 fuel cells

Anhydrous proton-conducting inorganic-organic hybrid membranes were prepared by sol-gel process with tetramethoxysilane/methyl-trimethoxysilane/trimethylphosphate and 1-ethyl-3-methylimidazolium-bis (trifluoromethanesulfonyl) imide [EMI][TFSI] ionic liquid as precursors. These hybrid membranes were studied with respect to their structural, thermal, proton conductivity, and hydrogen permeability properties. The Fourier transform infrared spectroscopy (FT-IR) and ³¹P, ¹H, and ¹³C nuclear magnetic resonance (NMR) measurements have shown good chemical stability, and complexation of PO(OCH₃)₃ with [EMI][TFSI] ionic liquid in the studied hybrid membranes. Thermal analysis including TG and DTA confirmed that the membranes were thermally stable up to 330 °C. Thermal stability of the hybrid membranes was significantly enhanced by the presence of inorganic SiO₂ framework and high stability of [TFSI] anion. The effect of [EMI][TFSI] ionic liquid addition on the microstructure of the membranes was studied by scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX) micrographs and no phase separation at the surfaces of the prepared membranes was observed and also homogeneous distribution of all elements was confirmed. Proton conductivity of all the prepared membranes was measured from −20 °C to 150 °C, and high conductivity of 5.4 × 10⁻³ S/cm was obtained for 40 wt% [EMI][TFSI] doped 40TMOS-50MTMOS-10PO(OCH₃)₃ (mol%) hybrid membrane, at 150 °C under anhydrous conditions. The hydrogen permeability was found to decrease from 1.61 × 10⁻¹¹ to 1.39 × 10⁻¹² mol/cm s Pa for 40 wt% [EMI][TFSI] doped hybrid membrane as the temperature increases from 20 °C to 150 °C. For 40 wt% [EMI][TFSI] doped hybrid membrane, membrane electrode assemblies were prepared and a maximum power density value of 0.22 mW/cm² at 0.47 mA/cm² as well as a current density of 0.76 mA/cm² were obtained at 150 °C under non-humidified conditions when utilized in a H₂/O₂ fuel cell.     

Synthesis and characterization of high-density LiFePO4/C composites as cathode materials for lithium-ion batteries

To achieve a high-energy-density lithium electrode, high-density LiFePO₄/C composite cathode material for a lithium-ion battery was synthesized using self-produced high-density FePO₄ as a precursor, glucose as a C source, and Li₂CO₃ as a Li source, in a pipe furnace under an atmosphere of 5% H₂-95% N₂. The structure of the synthesized material was analyzed and characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). The electrochemical properties of the synthesized LiFePO₄/carbon composite were investigated by cyclic voltammetry (CV) and the charge/discharge process. The tap-density of the synthesized LiFePO₄/carbon composite powder with a carbon content of 7% reached 1.80 g m⁻³. The charge/discharge tests show that the cathode material has initial charge/discharge capacities of 190.5 and 167.0 mAh g⁻¹, respectively, with a volume capacity of 300.6 mAh cm⁻³, at a 0.1C rate. At a rate of 5C, the LiFePO₄/carbon composite shows a high discharge capacity of 98.3 mAh g⁻¹ and a volume capacity of 176.94 mAh cm⁻³.     

A novel micro-spherical CoSn2/Sn alloy composite as high capacity anode materials for Li-ion rechargeable batteries

Micro-scaled spherical CoSn₂/Sn alloy powders synthesized from oxides of Sn and Co via carbothermal reduction at 800 °C were examined for use as anode materials in Li-ion battery. The phase composition and particle morphology of the CoSn₂/Sn alloy composite powders were investigated by XRD, SEM and TEM. The prepared CoSn₂/Sn alloy composite electrode exhibits a low initial irreversible capacity of ca. 140 mAh g⁻¹, a high specific capacity of ca. 600 mAh g⁻¹ at constant current density of 50 mA g⁻¹, and a good rate capability. The stable discharge capacities of 500-515 mAh g⁻¹ and the columbic efficiencies of 95.8-98.1% were obtained at current density of 500 mA g⁻¹. The relatively large particle size of CoSn₂/Sn alloy composite powder is apparently favorable for the lowering of initial capacity loss of electrode, while the loose particle structural characteristic and the Co addition in Sn matrix should be responsible for the improvement of cycling stability of CoSn₂/Sn electrode.     

Hybrid proton-conducting membranes for polymer electrolyte fuel cells: Phosphomolybdic acid doped poly(2,5-benzimidazole)—(ABPBI-H3PMo12O40)

The synthesis and characterization of a novel hybrid organic-inorganic material formed by phosphomolybdic acid H₃PMo₁₂O₄₀ (PMo₁₂) and poly(2,5-benzimidazole) (ABPBI) is reported. This material, composed of two proton-conducting components, can be cast in the form of membranes from methanesulfonic acid (MSA) solutions. Upon impregnation with phosphoric acid, the hybrid membranes present higher conductivity than the best ABPBI polymer membranes impregnated in the same conditions. These electrolyte membranes are stable up to 200 °C, and have a proton conductivity of 3 × 10⁻² S cm⁻¹ at 185 °C without humidification. These properties make them very good candidates as membranes for polymer electrolyte membrane fuel cells (PEMFC) at temperatures of 100-200 °C.     

Characterisation of a re-cast composite Nafion 1100 series of proton exchange membranes incorporating inert inorganic oxide particles

A series of cation exchange membranes was produced by impregnating and coating both sides of a quartz web with a Nafion^® solution (1100 EW, 10%wt in water). Inert filler particles (SiO₂, ZrO₂ or TiO₂; 5-20%wt) were incorporated into the aqueous Nafion^® solution to produce robust, composite membranes. Ion-exchange capacity/equivalent weight, water take-up, thickness change on hydration and ionic and electrical conductivity were measured in 1 mol dm⁻³ sulfuric acid at 298 K. The TiO₂ filler significantly impacted on these properties, producing higher water take-up and increased conductivity. Such membranes may be beneficial for proton exchange membrane (PEM) fuel cell operation at low humidification. The PEM fuel cell performance of the composite membranes containing SiO₂ fillers was examined in a Ballard Mark 5E unit cell. While the use of composite membranes offers a cost reduction, the unit cell performance was reduced, in practice, due to drying of the ionomer at the cathode.     

Preparation and characterization of PVDF-montmorillonite mixed matrix hollow fiber membrane for gas–liquid contacting process

Porous PVDF-hydrophobic montmorillonite (MMT) mixed matrix membranes (MMMs) were fabricated via wet spinning method and used in membrane gas absorption process. The effects of hydrophobic MMT nano-clay loadings (1, 3 and 5 wt% of polymer) on the structure and performance were investigated. The fabricated membranes showed both finger-like and sponge-like structure with an increase in the length of finger-like pores in their cross-section, which resulted in higher permeability and lower mass transfer resistance compared to plain PVDF membrane. Also, significant improvements for surface hydrophobicity, critical entry pressure of water and porosity with the addition of filler were observed. The CO₂ absorption test was conducted through the gas–liquid membrane contactor and demonstrated a significant improvement in the CO₂ flux with MMT loading and the membrane with 5 wt% MMT presented highest performance. For example, at the liquid water velocity of 0.5 m s⁻¹, CO₂ flux of the MMM with 5 wt% MMT of 9.73 × 10⁻⁴ mol m⁻² s⁻¹ was approximately 56% higher than the PVDF membrane without nano-filler. In conclusion, MMMs with improved absorption properties can be a promising candidate for CO₂ absorption and separation processes through membrane contactors.     

Rechargeable lithium/sulfur battery with suitable mixed liquid electrolytes

The suitability of some single/binary liquid electrolytes and polymer electrolytes with a 1 M solution of LiCF₃SO₃ was evaluated for discharge capacity and cycle performance of Li/S cells at room temperature. The liquid electrolyte content in the cell was found to have a profound influence on the first discharge capacity and cycle property. The optimum, stable cycle performance at about 450 mAh g⁻¹ was obtained with a medium content (12 μl) of electrolyte. Comparison of cycle performance of cells with tetra(ethylene glycol)dimethyl ether (TEGDME), TEGDME/1,3-dioxolane (DIOX) (1:1, v/v) and 1,2-dimethoxyethane (DME)/di(ethylene glycol)dimethyl ether (DEGDME) (1:1, v/v) showed better results with the mixed electrolytes based on TEGDME. The addition of 5 vol.% of toluene in TEGDME had a remarkable effect of increasing the initial discharge capacity from 386 to 736 mAh g⁻¹ (by >90%) and stabilizing the cycle properties, attributed to the reduced lithium metal interfacial resistance obtained for the system. Polymer electrolyte based on microporous poly(vinylidene fluoride) (PVdF) membrane and TEGDME/DIOX was evaluated for ionic conductivity at room temperature, lithium metal interfacial resistance and cycle performance in room-temperature Li/S cells. A comparison of the liquid electrolyte and polymer electrolyte showed a better performance of the former.     

Structure and thermal properties of La0.6Sr0.4Co0.2Fe0.8O3−δ-SDC carbonate composite cathodes for intermediate- to low-temperature solid oxide fuel cells

The structure and thermal properties of La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ-SDC carbonate (LSCF-SDC carbonate) composite cathodes were investigated with respect to the calcination temperatures and the weight content of the samarium-doped ceria (SDC) carbonate electrolyte. The composite cathode powder has been prepared from La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ and SDC carbonate powders using the high-energy ball milling technique in air at room temperature. Different powder mixtures at 30 wt%, 40 wt% and 50 wt% of SDC carbonate were calcined at 750-900 °C. The findings indicated that the structure and thermal properties of the composite cathodes were responsive to the calcination temperature and the content of SDC carbonate. The absence of any new phases as confirmed via XRD analysis demonstrated the excellent compatibility between the cathode and electrolyte materials. The particle size of the composite cathode powder was ∼0.3-0.9 μm having a surface area of 4-15 m² g⁻¹. SEM investigation revealed the presence of large particles in the resultant powders resulting from the increased calcination temperature. The composite cathode containing 50 wt% SDC carbonate was found to exhibit the best thermal expansion compatibility with the electrolyte.     

Preparation and performance of a core-shell carbon/sulfur material for lithium/sulfur battery

The core-shell carbon/sulfur material with high performance is prepared by a facile and fast deposit method in an aqueous solution. As sulfur ratio is 85% (w/w) in the composite, scanning electron microscope (SEM) and transmission electron microscope (TEM) observation show that the moniliform particles with 10 nm sulfur shells preserve the morphology of carbon cores. Tested as the cathode material in a lithium cell with binary organic electrolyte at room temperature, the composite shows excellent electrochemical performance. It exhibits a specific capacity up to 1232.5 mAh g⁻¹ at the initial discharge and its specific capacity remained above 800 mAh g⁻¹ after 50 cycles. Meanwhile, the composite also exhibits the high-rate behavior at 800 mA g⁻¹ of current density. Assuming a complete reaction to the final product, Li₂S, the utilization of the electrochemically active sulfur is about 85% at the initial cycle. Electrochemical impedance spectroscopy (EIS) is introduced to understand the impact of the microstructure of composite on electrochemistry. According to our study, a novel core-shell structural carbon/sulfur material is proposed and the key factors of the preparation are discussed.     

The preparation of nano-sulfur/MWCNTs and its electrochemical performance

In this work, a novel nano-sulfur/MWCNTs composite with modified multi-wall carbon nano-tubes (MWCNTs) as sulfur-fixed matrix for Li/S battery is reported. Based on different solubility of sulfur in different solvents, nano-sulfur/MWCNTs composite was prepared by solvents exchange method. The composite was characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The modified MWCNTs are considered that not only acts as a conducting material, but also a matrix for sulfur. The electrochemical performance of the nano-sulfur/MWCNTs composite was tested. The results indicated that nano-sulfur/MWCNTs composite had the specific capacity of 1380 mAh g⁻¹, 1326 mAh g⁻¹ and 1210 mAh g⁻¹ in the initial cycle at 100 mA g⁻¹, 200 mA g⁻¹ and 300 mAh g⁻¹ discharge rates respectively, and remained a reversible capacity of 1020 mAh g⁻¹, 870 mAh g⁻¹ and 810 mAh g⁻¹ after 30 cycles. The electrochemical performances confirm that the modified MWCNTs as sulfur-fixed matrix show better ability than any other carbon in cathode of Li/S batteries that had been reported.