Studies on a novel anion‐exchange membrane based on chitosan and ionized organic compounds with multiwalled carbon nanotubes for alkaline fuel cells

In this work, a novel hydroxyl‐anion‐conducting membrane composed of chitosan (CTS), an ionized organic compound ([QAIM]OH), and hydroxylated multiwalled carbon nanotubes (MWCNTs‐OH) has been fabricated through a blending‐casting method assisted by a glutaraldehyde (GA) crosslinking process that can improve the mechanical properties of the membrane effectively. Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy revealed that [QAIM]OH and MWCNTs‐OH were successfully introduced into the CTS matrix. A chemical crosslinking reaction between CTS and GA could be confirmed by FTIR, X‐ray photoelectron spectroscopy, and contact angle tests. By tuning the mass fraction of [QAIM]OH and MWCNTs‐OH in the membrane, the maximum OH^? conductivity (5.66 × 10^?3 S cm^?1 at room temperature) could be achieved for the composition CTS:[QAIM]OH (1:0.75 in mass) blend doped with 3% MWCNTs‐OH. At a current density of 59.9 mA cm^?2, a membrane electrode assembly fabricated with the CTS/[QAIM]OH/ MWCNTs‐OH membrane (1:0.5/3%) achieved a power density of 31.6 mW cm^?2 in a H₂/O₂ system at room temperature. Under the condition of intermediate temperature (100–140 °C) without water, the conductivities of the membranes increased with increasing temperature and the amount of [QAIM]OH, which acted as an ionic liquid in the membrane, indicating that the ionic transport behaviors could still be occurring. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46323.     

Improved specific capacity of sulfur/starch‐based activated carbon spheres composites by polyaniline‐based carbon encapsulation strategy

Lithium‐sulfur battery is one of the most promising electrochemical energy storage systems because of its high theoretical specific capacity and energy density. When carbon materials are used for immobilizing sulfur, the technical challenge is designing their framework to relieve the shuttle effect of polysulfides intermediates and the volume change of sulfur, and to improve the conductivity of sulfur. Herein, polyaniline‐based carbon (PANI‐C) coated corn starch‐based activated carbon spheres (ACS@PANI‐C) was prepared and used as hosts of sulfur, which can effectively combine the advantages of physical entrapment and chemical binding interactions of sulfur species. The results of electrochemical performance test indicate that S/ACS@PANI‐C composites exhibit much better electrochemical performance than S/ACS composites. Its reversible capacities at 320, 480, 800 and 1600 mA g^?1 are 687, 582, 504 and 393 mAh g^?1, respectively. The improved electrochemical performance can be attributed to the PANI‐C which can also act as a flexible cushion to accommodate volume changes of sulfur cathode as well as a barrier to trap soluble polysulfide intermediates during the charge–discharge process. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46544.     

Preparation of pseudocapacitor electrodes via electrodeposition of polyaniline on nonwoven carbon fiber fabrics

Aniline has been polymerized via electrodeposition onto various nonwoven carbon fiber fabric (CFF) substrates for use as a pseudocapacitive electrochemical capacitor. Four types of CFF were initially tested for double layer capacitance before polyaniline deposition, and again for specific capacitance after deposition. A binder‐free CFF was selected for further analysis due to its high capacitance change following PANI deposition (three orders of magnitude). The aniline monomer concentration, deposition potential, and deposition time were varied and resulting materials were characterized using chrono‐potentiometry, cyclic voltammetry, and scanning electron microscopy. The deposition potential range yielding highest capacitance was found to be between 0.744 and 0.777 V. A solution concentration of 0.5M aniline at a 20 min deposition time resulted in the highest specific capacitance (>80 F/g based on total electrode mass and >300 F/g based on PANI mass) within this study. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43315.     

Centrifugally spun carbon fibers prepared from aqueous poly(vinylpyrrolidone) solutions as binder-free anodes in lithium-ion batteries

Aqueous solutions of poly(vinylpyrrolidone) (PVP) of various concentrations (20, 25, and 28 wt%) were successfully spun into fibers by centrifugal spinning. The pristine PVP fibers were annealed and carbonized to produce flexible carbon fibers for use as binder-free anodes in lithium-ion batteries. These flexible carbon fibers were prepared by developing a novel three-step heat treatment to reduce the residual stresses in the pristine PVP precursor fibers, and to prevent fiber degradation during carbonization. The thermogravimetric analysis data showed that the annealed fibers yielded a residual mass percentage of 36.0% while the pristine PVP fibers suffered a higher mass loss and only retained 26.5% of original mass above 450 °C (under nitrogen). The electrochemical performance of the carbon-fiber anodes was evaluated by conducting galvanostatic charge/discharge, rate performance, and cycle voltammetry experiments. The 20, 25, and 28 wt% derived binder-free anodes delivered specific charge capacities of 205, 189, and 275 mAh g⁻¹, respectively, after the first cycle at a current density of 100 mA g⁻¹. The results obtained in this work indicate that a feasible pathway towards a large-scale production of carbon-fiber anodes from a 100% aqueous solution can be achieved via centrifugal spinning and subsequent heat treatment.     

Phosphorous,nitrogen co‐doped carbon from spent coffee grounds for fuel cell applications

Spent coffee grounds, which represents the vast solid residual matter generated from consumed coffee beans, requires proper reutilization. This work represents the production of an alternate material from spent coffee grounds to replace expensive metal based catalysts currently used as electrodes in fuel cells. A novel microwave assisted technique which is easy, rapid, and economical is utilized for the synthesis of Phosphorous, Nitrogen co‐doped carbon (PNDC) from spent coffee grounds and ammonium polyphosphate. SEM analysis revealed that PNDC is composed of distinct, spherical shaped particles. PNDC has a BET surface area of ～507 m² g^?1 and is predominantly mesoporous. XPS reveals that PNDC contains about 1.90% N and 3.02% P besides C and O. PNDC exhibits good O₂ reduction response in 0.1M KOH, which was found to be comparable to that of 20% Pt/C. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41948.     

The unique morphology role of thorn surface in determining electrochemical performance of polyaniline nano‐fibers via one‐step method

Polyaniline nano‐fibers with thorn surface morphology (T‐PANI) were synthesized by one‐step polymerization with adding additional aniline at later stage of chemical oxidation synthesis. In order to investigate the morphology role in determining electrochemical performance, the nano‐fibers PANI without thorn (PANI) was synthesized by the same polymerization process but at different time to add additional aniline. Material structures were characterized by field emission scanning electron microscope and Brunauer‐Emmett‐Teller method, and electrochemical performance was tested through cyclic voltammograms, galvanostatic charge‐discharge and electrochemical impedance spectroscopy. The data showed that the specific capacitance of T‐PANI was 443 F g^?1 at 5 mA cm^?2, which was much more than that of PANI (338 F g^?1 at 5 mA cm^?2). The solution resistance, charge transfer resistance, and diffuse resistance of T‐PANI were also lower than these of PANI. The results indicate that the thorn surface structure plays an important role in determining the electrochemical performance of polyaniline, which attribute to the improvements in pore size, pore distribution, special surface area, and conductivity. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42266.     

Comparative study of composite membranes from nano‐metal‐oxide‐incorporated polymer electrolytes for direct methanol alkaline membrane fuel cells

A series of six composite membranes was prepared with two polymer electrolytes and three inorganic fillers, namely, silica, titania, and zirconia by a solution casting method. Two polymer electrolytes, that is, anion‐exchange membranes, were prepared from polystyrene‐block‐poly(ethylene‐ran‐butylene)‐block‐polystyrene (PSEBS) and polysulfone by chloromethylation and quaternization. A preliminary characterization of the ionic conductivity, methanol permeability, and selectivity ratio was done for all of the prepared composite membranes to check their suitability to work in direct methanol alkaline membrane fuel cells (DMAMFCs). The DMAMFC performance was analyzed with an in‐house fabricated single cell unit with a 25‐cm² area. Maximum performance was achieved for the composite membrane quaternized PSEBS/7.5% TiO₂ and was 74.5 mW/cm² at 60°C. For the comparison purposes, a commercially available anion‐exchange membrane (Anion Membrane International‐7001) was also investigated throughout the study. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Sulfur/PAN/acetylene black composite prepared by a solution processing technique for lithium–sulfur batteries

A sulfur/poly(acrylonitrile)–PAN/acetylene black–AB composite, comprising sulfur and PAN encapsulated in the pores of AB was prepared by a solution‐based technique with dimethyl sulfoxide as the solvent. The composite was characterized by TGA, X‐ray diffraction, FTIR, Raman, SEM, TEM, and BET studies. The composite exhibited a high discharge capacity of 1330 mAh/g in the first cycle. The AB additive plays multiple roles in the composite, acting as a conducting matrix for electron transport and as a porous framework that adsorbs and retains electrolyte. The presence of PAN along with the porous carbon matrix in the composite provides the necessary resilience to absorb strains due to volume expansion during cycling. The observed improved performance of the composite is primarily attributed to the small size and homogeneous distribution of sulfur in the composite. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46598.     

Synthesis and characterization of LiFePO4–carbon nanofiber–carbon nanotube composites prepared by electrospinning and thermal treatment as a cathode material for lithium‐ion batteries

Binder‐free LiFePO₄–carbon nanofiber (CNF)–multiwalled carbon nanotube (MWCNT) composites were prepared by electrospinning and thermal treatment to form a freestanding conductive web that could be used directly as a battery cathode without addition of a conductive material and polymer binder. The thermal decomposition behavior of the electrospun LiFePO₄ precursor–polyacrylonitrile (PAN) and LiFePO₄ precursor–PAN–MWCNT composites before and after stabilization were studied with thermogravimetric analysis (TGA)/differential scanning calorimetry and TGA/differential thermal analysis, respectively. The structure, morphology, and carbon content of the LiFePO₄–CNF and LiFePO₄–CNF–MWCNT composites were determined by X‐ray diffraction, high‐resolution transmission electron microscopy, Raman spectroscopy, scanning electron microscopy, and elemental analysis. The electrochemical properties of the LiFePO₄–CNF and LiFePO₄–CNF–MWCNT composite cathodes were measured by charge–discharge tests and electrochemical impedance spectroscopy. The synthesized composites with MWCNTs exhibited better rate performances and more stable cycle performances than the LiFePO₄–CNF composites; this was due to the increase in electron transfer and lithium‐ion diffusion within the composites loaded with MWCNTs. The composites containing 0.15 wt % MWCNTs delivered a proper initial discharge capacity of 156.7 mA h g^?1 at 0.5 C rate and a stable cycle ability on the basis of the weight of the active material, LiFePO₄. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43001.     

Composite sodium p‐toluene sulfonate–polypyrrole–iron anode for a lithium‐ion battery

In this study, p‐toluene sulfonate (TsONa) doped polypyrrole (PPy) was synthesized for an anode in a lithium‐ion battery via a one‐step facile electropolymerization on Fe foil. The obtained TsONa–PPy–Fe composite electrode was investigated with scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, Fourier transform infrared spectroscopy, and galvanostatic charge–discharge profiling. As expected, many irregular microspherical particles of TsONa‐doped PPy formed and combined tightly with the surface of Fe foil. Furthermore, the obtained TsONa–PPy–Fe anode also delivered satisfactory electrochemical performances. For example, the reversible capacity was still about 105–115 mAh/g, even after at least 50 cycles. The high lithium storage activity of PPy and the high conductivity of the TsONa‐doped PPy jointly contributed into the satisfactory electrochemical performances. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44935.     

Resin-silica composite nanoparticle grafted polyethylene membranes for lithium ion batteries

To avoid the peeling-off of ceramic nanoparticles (NPs) from polyolefin membranes usually occurred in commercially available ceramic NPs coated polyolefin separators for lithium batteries, we propose a simple one-pot in-situ reaction method to modify commercial polyethylene (PE) separators by surface grafting 3-Aminophenol/formaldehyde (AF)/silica (SiO₂) composite NPs. The AF/SiO₂ composite NPs form self-supporting connected pores on the modified layer of the separator surface, which ensures the transportation of Li⁺. Moreover, the PE@AF/SiO₂ separators has higher electrolyte wettability and compatibility than neat PE separators attributed to the plentiful polar functional groups in the AF/SiO₂ layer and AF/SiO₂ composite NPs, resulting in higher lithium ion transference number (= 0.62) and ionic conductivity (σ = 0.722 mS cm⁻¹). More importantly, the discharge capacity, capacity retention rate and coulombic efficiency (136.2 mA h g⁻¹, 87.9% and 99%, respectively) after 200 cycles of Li|NMC half batteries with PE@AF/SiO₂ separators, are all more excellent than that with the pure PE separator (125 mA h g⁻¹, 83.1% and 85%, respectively). Our results show that the PE@AF/SiO₂ separators obtained by this modification method have higher electrochemical stability in the lithium battery system.     

Study of poly(organic palygorskite-methyl methacrylate)/poly(ethylene oxide) blended gel polymer electrolyte for lithium-ion batteries

In this study, the composite polymer was prepared by blending poly(ethylene oxide) (PEO) and POPM (the copolymer of methyl methacrylate [MMA] and organically modified palygorskite), and then the composite polymer based membrane was obtained by phase-inversion method. The scanning electron microscopy results showed that the composite polymer membrane has a three-dimensional network structure. X-ray diffraction results indicated that the crystalline region of PEO is disappeared when introduction of a certain amount of the PEO. Meanwhile, the elongation of composite polymer membrane increased when increasing PEO concentration, but the value of tensile strength of PEO-POPM membrane decreased. When the mass fraction of PEO was 24%, the porosity and maximum value of ionic conductivity of the composite polymer membrane were 54% and 2.41 mS/cm, respectively. The electrochemical stability window of Li/gel composite polymer electrolyte/stainless steel batteries was close to 5.3 V (vs. Li⁺/Li), and the battery of Li/gel composite polymer electrolyte/LiFePO₄ showed good cycling performance and the discharge capacity of the battery were between 169.8 and 155 mAh/g. Meanwhile, the Coulombic efficiency of the battery maintained over 95% during the 80 cycles.     

Partially lithiated ternary graft copolymer with enhanced elasticity as aqueous binder for Si anode

Partially lithiated ternary graft copolymers were synthesized through free radical graft polymerization of acrylic acid (AA), lithium acrylate (LiAA) and hydroxyethyl acrylate (HEA) onto polyvinyl alcohol (PVA). With optimized feeding molar ratio of AA/LiAA/HEA (2:1:2), the ternary graft copolymer with partial lithiation shows the best flexibility, elasticity and adhesion strength comparing to PVA-g-PAA and PVA-g-P(AA-HEA) when used as aqueous binder for Si anode. The Si anode using PVA-g-P(AA-LiAA-HEA) with the optimized molar ratio of AA-LiAA-HEA exhibits better cycling stability and rate performance, delivering a capacity of 2265 mAh g⁻¹ with a capacity retention of 82.4% after 200 cycles at 1A g⁻¹. Even at a high current of 10 A g⁻¹, the Si electrode still obtained a high capacity of 1300 mAh g⁻¹.     

PEDOT solid-state polymer supercapacitor assembled with a KI-doped gel polymer electrolyte

Solid-state polymer supercapacitors (SSP-SCs) have vast potential for future development due to their compact, safe, environment-friendly, and facile designing. Thus, prevalent researches have been explored in this area. In this article, poly(3,4-ethylenedioxythiophene) (PEDOT) SSP-SCs were assembled by using poly(3,4-ethylenedioxythiophene)/carbon paper (PEDOT/CP) as electrodes and polyvinyl alcohol/sulfuric acid/potassium iodide (PVA/H₂SO₄/KI) as the gel polymer electrolyte. The effect of KI content on the electrochemical performance of the SC was studied by cyclic voltammetry, galvanostatic charge–discharge measurements (GCD), and electrochemical impedance spectroscopy. The results indicated that the PEDOT SSP-SC has excellent electrochemical properties when KI doping amount was 60 wt %. The introduction of KI increased the specific capacitance due to the improved ionic conductivity and additional pseudocapacitance reaction at the electrode–electrolyte interface. The PEDOT SSP-SC showed high energy and power densities of 451.32 Wh kg⁻¹ and 13.29 kW kg⁻¹, respectively, as well as a specific capacitance of 352.59 F g⁻¹ for a discharge current of 1 mA cm⁻². In addition, after 1000 GCD cycles, the PVA/H₂SO₄/KI-based PEDOT SSP-SC showed capacitance retention of 74.08%. Therefore, the SC exhibits outstanding energy and power density and good cycle stability and has great potential to be used in high-energy density equipment. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48723.     

Electropolymerization and energy storage of poly[Ni(salphen)]/MWCNT composite materials for supercapacitors

Ni(salphen), a Schiff base ligand compound, was synthesized and electropolymerized on multiwalled carbon nanotube (MWCNT) electrodes in an acetonitrile solution via the pulse potentiostatic method and then applied as a supercapacitor electrode material. The polymerization mode was investigated through methyl replacement in the para‐position of phenyl rings in the Ni(salphen) monomer, and it was found that the Ni(salphen) monomers would polymerize by the generation of C? C bonds between the phenyl rings in the para‐position of the phenol moieties. The optimum condition for polymerization was evaluated, and when the polymerization time was 8 min, poly[Ni(salphen)] exhibited a specific capacitance up to 200 F g^?1 at a current density of 0.1 mA cm^?2, and the capacitance remains at 164 F g^?1 at 20 mA cm^?2. The energy density of the poly[Ni(salphen)] electrode reached 40 Wh kg^?1 at 0.1 mA cm^?2, about eight times greater than for a pure MWCNT electrode. Electrochemical performances were investigated, and the composites showed good redox property and ion transfer capability. This work showed that Ni(salphen) may be an attractive material in supercapacitors© 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44464.     

Molecular dynamics simulation of physical vapor deposition of metals onto a vertically aligned single-walled carbon nanotube surface

Behaviors of nickel and gold clusters deposited onto a vertically aligned single-walled carbon nanotube film (VA-SWCNT) were investigated by molecular dynamics simulation methods. Brenner potential was applied for carbon–carbon, and bond-order potential was applied for metal–metal and carbon–metal interactions. Their parameters of gold–gold and carbon–gold were derived by density functional theory calculations. After metal clusters were fully annealed, they were deposited onto the flat nanotube surface with small evaporation energy. Nickel clusters spread over the surface; on the other hand, the gold clusters sometimes formed a grain-like structure, especially when they formed a large cluster before arriving at the surface. When another CNT was placed on the vertically aligned surface, nickel clusters spread and formed a smooth surface, as in the case of a VA-SWCNT film; however, gold clusters could not spread but formed a grain-like structure. This result is in good agreement with the experimental and indicates the mechanism for forming a grain-like structure on a VA-SWCNT. To avoid the formation of a grain-like structure on the surface of a SWCNT, the deposition should be carried out under a high vacuum condition and at a low deposition rate for preventing clustering as it obstructs formation of a flat surface.     

Preparation of polymer electrolytes based on the polymerized imidazolium ionic liquid and their applications in lithium batteries

The polymer electrolytes based on a polymerized ionic liquid (PIL) as polymer host and containing 1,2‐dimethyl‐3‐butylimidazolium bis(trifluoromethanesulfonyl)imide (BMMIM‐TFSI) ionic liquid, lithium TFSI salt, and nanosilica are prepared. The PIL electrolyte presents a high ionic conductivity, and it is 1.07 × 10^?3 S cm^?1 at 60°C, when the BMMIM‐TFSI content reaches 60% (the weight ratio of BMMIM‐TFSI/PIL). Furthermore, the electrolyte exhibits wide electrochemical stability window and good lithium stripping/plating performance. Preliminary battery tests show that Li/LiFePO₄ cells with the PIL electrolytes are capable to deliver above 146 mAh g^?1 at 60°C with very good capacity retention. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40928.     

ForceSpinning of polyacrylonitrile for mass production of lithium‐ion battery separators

We present results on the Forcespinning^® (FS) of Polyacrylonitrile (PAN) for mass production of polymer nanofiber membranes as separators for Lithium‐ion batteries (LIBs). Our results presented here show that uniform, highly fibrous mats from PAN produced using Forcespinning^®, exhibit improved electrochemical properties such as electrolyte uptake, low interfacial resistance, high oxidation limit, high ionic conductivity, and good cycling performance when used in lithium ion batteries compared to commercial PP separator materials. This article introduces ForceSpinning^®, a cost effective technique capable of mass producing high quality fibrous mats, which is completely different technology than the commonly used in‐house centrifugal method. This Forcespinning^® technology is thus the beginning of the nano/micro fiber revolution in large scale production for battery separator application. This is the first time to report results on the cycle performance of LIB‐based polymer nanofiber separators made by Forcespinning^® technology. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 132, 42847.     

Enhanced conductivity of polyaniline in the presence of nonionic amphiphilic polymers and their diverse morphologies

Poly(ethylene oxide) (PEO) and its copolymers have excellent affinity for protons and contribute to proton transfer. In the present study, PEO and its copolymers, poly[(ethylene oxide)₂₀‐(propylene oxide)₇₀‐(ethylene oxide)₂₀] (EO₂₀PO₇₀EO₂₀, P123) and poly[(ethylene oxide)₁₀₆‐(propylene oxide)₇₀‐(ethylene oxide)₁₀₆] (EO₁₀₆PO₇₀EO₁₀₆, F127), have been found to significantly enhance the conductivity of polyaniline (PANI). After introducing these polymers, the conductivity of PANI is markedly promoted more than two orders of magnitude compared to that of PANI without additives, from 5.2 to 667 S/m. The molecular weight of PEO affects the conductivity of PANI/PEO. The mechanism by which these amphiphilic polymers are beneficial to the conductivity of PANI is studied experimentally and theoretically. The PANI/P123 prepared in the presence of PEO block copolymer shows gradually varying morphologies containing leaflike sheets, rodlike particles, and uniform chestnutlike sphere particles. This is similar to the morphology change of micelles with surfactant concentration. PEO, P123, and F127 are further found to have a positive effect on PANI as a material for sensors or supercapacitors, since high specific capacity and fast response rate are desired qualities in sensors and supercapacitors. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45547.     

New all solid‐state polymer electrolyte based on epoxy resin and ionic liquid for high temperature applications

Flexible epoxy network loaded with high amount of ionic liquid (IL) 1‐decyl‐3‐methylimidazolium bromide ([DMIM]Br) has been reported by using a mixture of polyol amine as curing agent. The IL presents good electrochemical response even at 170 °C, as no evidence of redox reactions was observed. The incorporation of as high as 50 wt % of this IL within the epoxy matrix resulted in solid and flexible electrolyte with good thermal stability below 180 °C, as measured by thermogravimetric analysis and ionic conductivity of around 10^?6 S cm^?1 at room temperature and higher than 10^?3 S cm^?1 at high temperature. This electrolyte presented a prodigious potential for applications in electrochemical devices at high temperature like batteries and supercapacitors, and the flexibility of this solid electrolyte persist at low temperature because of its low glass transition temperature. Furthermore, leakage problems were not observed. Thereby, impedance spectroscopy and cyclic voltammetry were performed to characterize the electrochemical properties. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45838.