Synthesis and properties of new sulfonated naphthalenic polyimides as proton exchange membrane for fuel cell applications

e-Polymers ◽  
2008 ◽  
Vol 8 (1) ◽  
Author(s):  
L. Zhao ◽  
Y.D. Huang ◽  
Y.M. Piao
Keyword(s):  
Proton Conductivity ◽  
Proton Exchange Membrane ◽  
Mechanical Stability ◽  
Decomposition Temperature ◽  
Proton Exchange ◽  
Molar Ratio ◽  
Dimensional Changes ◽  
Polyimide Membrane ◽  
Sulfonated Polyimide ◽  
Sulfonated Polyimides

AbstractThe diamine monomer, 5-amino-2-(p-aminophenyl)benzoxazole(ABO), was successfully synthesized and a series of new naphthalenic sulfonated polyimides (SPIs) were prepared from 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA), 2,2’-benzidinedisulfonic acid (BDSA), ABO and 1,10- diaminedecane (DADE) using one-step high temperature polymerization method. Their structures were characterized by FTIR, 1HNMR and TG-DSC. The sulfonated degree of the SPI copolymers was controlled through varying the molar ratio of BDSA to the non-sulfonated diamines. Tough and transparent membranes with the typical polyimide brown colour were prepared by casting from the polymer solution. They showed clear anisotropic membrane swelling in water with larger dimensional changes in the thickness direction of membrane. The sulfonated polyimide membrane containing 20mol% benzoxazole moieties (SPI-20) showed desirable thermal stability with the decomposition temperature of 272°C and mechanical stability with the maximum stress of 42 MPa. The proton conductivity (6.2×10-3S/cm) of SPI-20 membrane was comparable to that of Nafion®117 membrane measured under the same condition (9.8×10-3 S/cm). The effects of temperature on the proton conductivity, and highly anisotropic proton conductivity in the thickness and plane direction were also investigated.

Influence of Sulfonationity of Epoxy-Based Semi-Interpenetrating Polymer Networks of Sulfonated Polyimides as Proton Exchange Membranes on the Performance of Fuel Cell Application

2010 ◽  
Vol 7 (2) ◽  
Author(s):  
Yen-Zen Wang ◽  
Ko-Shan Ho ◽  
Shinn-Dar Wu ◽  
Kuo-Huang Hsieh ◽  
Chi-Hung Lee
Keyword(s):  
Water Uptake ◽  
Proton Exchange Membrane ◽  
Water Clusters ◽  
Polymer Networks ◽  
Interpenetrating Polymer Networks ◽  
Proton Exchange ◽  
Molar Ratio ◽  
Good Thermal Stability ◽  
Sulfonated Polyimide ◽  
Sulfonated Polyimides

A novel epoxy-based semi-interpenetrating polymer networks membrane (SPIX-EP40) as the proton exchange membrane was prepared by a flexible epoxy network with sulfonated polyimide. A series of sulfonated polyamic acid (SPAA) were prepared from 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,2-benzidinedisulfonic acid (BDSA) and nonsulfonated diamines, such as 4,4′-diaminodiphenyl sulfone. Solid-state C13 nuclear magnetic resonance spectra and Fourier transform infrared spectroscopy were used to verify the synchronization of the imidization of SPAA and the crosslinking reactions of epoxy. The sulfonationity of the copolymers was regulated through a variation in the molar ratio of BDSA to diamine. These membranes owned a good thermal stability and exhibited high proton conductivity that was measured as a function of temperature. The resulting SPI0.7-EP40 and SPI0.8-EP40, at 100% relative humidity, displayed proton conductivities higher than those of Nafion® 117. The membranes displayed higher conductivities than Nafion® membranes because of owning higher activational energies and higher ion exchange capacities. An isotropic swelling phenomenon in water was found for the membrane. From the results of water uptake and the microstructure analyses using transmission electron microscopy (TEM) on different sulfonated levels, it was found that the number of water clusters in SPIX-EP40 membranes increased as the increasing water uptake and the size of water cluster were changed with the sulfonation levels. TEM confirmed the widespread and well-connected hydrophilic domains, demonstrating the presence of the favorable proton-transporting performances of the SPIX-EP40 membrane.

A Study of the Nitrogen-Containing Heterocycles on Copolyimide Properties for Proton Exchange Membranes

2013 ◽  
Vol 401-403 ◽  
pp. 563-566 ◽  
Author(s):  
Yu Han Li ◽  
Wei Jian Wang ◽  
Yu Fei Chen ◽  
Lei Wang
Keyword(s):  
Mechanical Properties ◽  
Thermal Stability ◽  
Proton Conductivity ◽  
Water Uptake ◽  
Main Chain ◽  
Proton Exchange Membranes ◽  
Proton Exchange ◽  
Membrane Properties ◽  
Dimensional Changes ◽  
Sulfonated Polyimide

Containing pyrimidine and pyridine monomers were incorporated respectively into the main chain of a sulfonated polyimide in order to investigate the effect of nitrogen-containing heterocycles on membrane properties such as water uptake and proton conductivity. With increasing content of the nitrogen-containing heterocycles, water uptake of membranes and dimensional changes remarkable decrease. The copolymer showed higher thermal stability (desulfonation temperature up to 330 °C) and reasonable good mechanical properties. These membranes also showed higher proton conductivity, which was comparable or even higher than Nafion 117.

scholarly journals Hybrid Composite Membrane of Phosphorylated Chitosan/Poly (Vinyl Alcohol)/Silica as a Proton Exchange Membrane

Membranes ◽  
2021 ◽  
Vol 11 (9) ◽  
pp. 675
Author(s):  
Nur Adiera Hanna Rosli ◽  
Kee Shyuan Loh ◽  
Wai Yin Wong ◽  
Tian Khoon Lee ◽  
Azizan Ahmad
Keyword(s):  
Proton Conductivity ◽  
Composite Membrane ◽  
Vinyl Alcohol ◽  
Proton Exchange Membrane ◽  
Mechanical Stability ◽  
Composite Membranes ◽  
Proton Exchange ◽  
Inorganic Filler ◽  
Poly Vinyl Alcohol ◽  
Filler Concentration

Chitosan is one of the natural biopolymers that has been studied as an alternative material to replace Nafion membranes as proton change membranes. Nevertheless, unmodified chitosan membranes have limitations including low proton conductivity and mechanical stability. The aim of this work is to study the effect of modifying chitosan through polymer blending with different compositions and the addition of inorganic filler on the microstructure and physical properties of N-methylene phosphonic chitosan/poly (vinyl alcohol) (NMPC/PVA) composite membranes. In this work, the NMPC biopolymer and PVA polymer are used as host polymers to produce NMPC/PVA composite membranes with different compositions (30–70% NMPC content). Increasing NMPC content in the membranes increases their proton conductivity, and as NMPC/PVA-50 composite membrane demonstrates the highest conductivity (8.76 × 10−5 S cm−1 at room temperature), it is chosen to be the base membrane for modification by adding hygroscopic silicon dioxide (SiO2) filler into its membrane matrix. The loading of SiO2 filler is varied (0.5–10 wt.%) to study the influence of filler concentration on temperature-dependent proton conductivity of membranes. NMPC/PVA-SiO2 (4 wt.%) exhibits the highest proton conductivity of 5.08 × 10−4 S cm−1 at 100 °C. In conclusion, the study shows that chitosan can be modified to produce proton exchange membranes that demonstrate enhanced properties and performance with the addition of PVA and SiO2.

CHARACTERIZATION OF TITANIUM PHOSPHATE AS ELECTROLYTES IN FUEL CELLS

2006 ◽  
Vol 20 (25n27) ◽  
pp. 4147-4152 ◽  
Author(s):  
A. T. T. TRAN ◽  
M. C. DUKE ◽  
P. G. GRAY ◽  
J. C. DINIZ DA COSTA
Keyword(s):  
Fuel Cells ◽  
Relative Humidity ◽  
Proton Conductivity ◽  
Proton Exchange Membrane ◽  
Sol Gel ◽  
Proton Exchange ◽  
Titanium Phosphate ◽  
Molar Ratio ◽  
Oh Groups ◽  
Surface Areas

Titanium phosphate is currently a promising material for proton exchange membrane fuel cells applications (PEMFC) allowing for operation at high temperature conditions. In this work, titanium phosphate was synthesized from tetra iso-propoxide (TTIP) and orthophosphoric acid ( H 3 PO 4) in different ratios by a sol gel method. High BET surface areas of 271 m2.g-1 were obtained for equimolar Ti:P samples whilst reduced surface areas were observed by varying the molar ratio either way. Highest proton conductivity of 5.4×10-2 S . cm -1 was measured at 20°C and 93% relative humidity (RH). However, no correlation was observed between surface area and proton conductivity. High proton conductivity was directly attributed to hydrogen bonding in P - OH groups and the water molecules retained in the sample structure. The proton conductivity increased with relative humidity, indicating that the Grotthuss mechanism governed proton transport. Further, sample Ti/P with 1:9 molar ratio showed proton conductivity in the order of 10-1 S.cm-1 (5% RH) and ~1.6×10-2 S . cm -1 (anhydrous condition) at 200°C. These proton conductivities were mainly attributed to excess acid locked into the functionalized TiP structure, thus forming ionisable protons.

scholarly journals Preparation and Characterization of a Novel Sulfonated Titanium Oxide Incorporated Chitosan Nanocomposite Membranes for Fuel Cell Application

Membranes ◽  
2021 ◽  
Vol 11 (6) ◽  
pp. 450
Author(s):  
Saad Ahmed ◽  
Tasleem Arshad ◽  
Amir Zada ◽  
Annum Afzal ◽  
Muhammad Khan ◽  
...  
Keyword(s):  
Fuel Cell ◽  
Proton Conductivity ◽  
Proton Exchange Membrane ◽  
Mechanical Stability ◽  
Exchange Capacity ◽  
Proton Exchange ◽  
Nanocomposite Membranes ◽  
Nano Tio2 ◽  
Proton Conducting ◽  
Exchange Membrane

In this study, nano-TiO2 sulfonated with 1,3-propane sultone (STiO2) was incorporated into the chitosan (CS) matrix for the preparation of CS/STiO2 nanocomposite membranes for fuel cell applications. The grafting of sulfonic acid (–SO3H) groups was confirmed by Fourier transform infrared spectroscopy, thermogravimetric analysis and energy-dispersive X-ray spectroscopy. The physicochemical properties of these prepared membranes, such as water uptake, swelling ratio, thermal and mechanical stability, ion exchange capacity and proton conductivity, were determined. The proton conducting groups on the surface of nano-TiO2 can form continuous proton conducting pathways along the CS/STiO2 interface and thus improve the proton conductivity of CS/STiO2 nanocomposite membranes. The CS/STiO2 nanocomposite membrane with 5 wt% of sulfonated TiO2 showed a proton conductivity (0.035 S·cm−1) equal to that of commercial Nafion 117 membrane (0.033 S·cm−1). The thermal and mechanical stability of the nanocomposite membranes were improved because the interfacial interaction between the -SO3H group of TiO2 and the –NH2 group of CS can restrict the mobility of CS chains to enhance the thermal and mechanical stability of the nanocomposite membranes. These CS/STiO2 nanocomposite membranes have promising applications in proton exchange membrane fuel cells.

scholarly journals Preparation and characterization of a novel sulfonated titanium oxide incorporated Chitosan nanocomposite membranes for fuel cell application

2021 ◽  
Author(s):  
Saad Ahmed ◽  
Amjad Hussain ◽  
Tasleem Arshad ◽  
Muhammad Khan ◽  
Amir Zada ◽  
...  
Keyword(s):  
Proton Conductivity ◽  
Proton Exchange Membrane ◽  
Mechanical Stability ◽  
Exchange Capacity ◽  
Proton Exchange ◽  
Hydroxyl Group ◽  
Gravimetric Analysis ◽  
Nanocomposite Membranes ◽  
Chitosan Matrix ◽  
Exchange Membrane

Abstract In this study, nano-TiO2 sulfonated (STiO2) with 1,3-propanesultone was incorporated into the chitosan matrix for the fabrication of chitosan/STiO2 (C/STiO2) nanocomposite membranes. The grafting of sulfonic acid (–SO3H) groups was confirmed with Fourier transform infrared spectroscopy, thermos-gravimetric analysis and energy-dispersive X-ray spectroscopy. The physicochemical properties such as water uptake, swelling ratio, thermal and mechanical stability, ion exchange capacity and proton conductivity of the as prepared membranes were measured. The proton groups on the surface of TiO2 can form continuous proton conducting pathways along the C/STiO2 interface resulting in the improvement of proton conductivity of C/STiO2 nanocomposite membranes. The nanocomposite membrane with 5 % sulfonated TiO2 showed higher proton conductivity (0.035 S·cm-1) than commercial Nafion-117 membrane (0.033 S·cm-1) due to the strong interfacial interactions between -SO3H group of acid and hydroxyl group of TiO2. Further, the –NH2 groups of chitosan restrict the mobility of chitosan chains to enhance the thermal and mechanical stability of the nanocomposite membranes. These C/STiO2 nanocomposite membranes have promising applications in proton exchange membrane fuel cells.

Synthesis and Characterization of Sulfonated Polyimide Based Membranes for Proton Exchange Membrane Fuel Cells

2013 ◽  
Vol 10 (4) ◽  
Author(s):  
Sabit Adanur ◽  
Hai Zheng
Keyword(s):  
Fuel Cells ◽  
Proton Exchange Membrane ◽  
Mechanical Stability ◽  
Exchange Capacity ◽  
Proton Exchange ◽  
Membrane Electrode ◽  
Scanning Calorimetry ◽  
Hydrogen Flow ◽  
Sulfonated Polyimide ◽  
Exchange Membrane

Sulfonated polyimide (SPI) based membranes for proton exchange membrane fuel cells (PEMFC) have been synthesized by using a one-step high temperature polymerization method. The membranes were characterized with Fourier transform infrared spectra (FTIR), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC); water uptake, ion-exchange capacity, proton conductivity and mechanical stability were tested. The results showed that the membranes had good thermal and mechanical stability and exhibited good performance when they were assembled into membrane electrode assemblies (MEAs). Fuel cell testing was performed. The SPI copolymer based MEA was tested under different hydrogen flow rates to compare with the commercially available Nafion® based MEA.

scholarly journals Synthesis and Characterization of Partially Renewable Oleic Acid-Based Ionomers for Proton Exchange Membranes

Polymers ◽  
2020 ◽  
Vol 13 (1) ◽  
pp. 130
Author(s):  
Carlos Corona-García ◽  
Alejandro Onchi ◽  
Arlette A. Santiago ◽  
Araceli Martínez ◽  
Daniella Esperanza Pacheco-Catalán ◽  
...  
Keyword(s):  
Oleic Acid ◽  
Proton Conductivity ◽  
Electrochemical Impedance ◽  
Proton Exchange Membranes ◽  
Proton Exchange ◽  
Molar Ratio ◽  
Aromatic Diamines ◽  
Chemical Structures ◽  
Long Chain

The future availability of synthetic polymers is compromised due to the continuous depletion of fossil reserves; thus, the quest for sustainable and eco-friendly specialty polymers is of the utmost importance to ensure our lifestyle. In this regard, this study reports on the use of oleic acid as a renewable source to develop new ionomers intended for proton exchange membranes. Firstly, the cross-metathesis of oleic acid was conducted to yield a renewable and unsaturated long-chain aliphatic dicarboxylic acid, which was further subjected to polycondensation reactions with two aromatic diamines, 4,4′-(hexafluoroisopropylidene)bis(p-phenyleneoxy)dianiline and 4,4′-diamino-2,2′-stilbenedisulfonic acid, as comonomers for the synthesis of a series of partially renewable aromatic-aliphatic polyamides with an increasing degree of sulfonation (DS). The polymer chemical structures were confirmed by Fourier transform infrared (FTIR) and nuclear magnetic resonance (1H, 13C, and 19F NMR) spectroscopy, which revealed that the DS was effectively tailored by adjusting the feed molar ratio of the diamines. Next, we performed a study involving the ion exchange capacity, the water uptake, and the proton conductivity in membranes prepared from these partially renewable long-chain polyamides, along with a thorough characterization of the thermomechanical and physical properties. The highest value of the proton conductivity determined by electrochemical impedance spectroscopy (EIS) was found to be 1.55 mS cm−1 at 30 °C after activation of the polymer membrane.

scholarly journals Sulfonated Binaphthyl-Containing Poly(arylene ether ketone)s with Rigid Backbone and Excellent Film-Forming Capability for Proton Exchange Membranes

Polymers ◽  
2018 ◽  
Vol 10 (11) ◽  
pp. 1287 ◽  
Author(s):  
Wenmeng Zhang ◽  
Shaoyun Chen ◽  
Dongyang Chen ◽  
Zhuoliang Ye
Keyword(s):  
Mechanical Properties ◽  
Proton Conductivity ◽  
Proton Exchange Membrane ◽  
Proton Exchange ◽  
Thermal Stabilities ◽  
Chemical Structures ◽  
Arylene Ether ◽  
Film Forming ◽  
Ether Ketone ◽  
Microscopic Morphology

Sterically hindered (S)-1,1′-binaphthyl-2,2′-diol had been successfully copolymerized with 4,4′-sulfonyldiphenol and 4,4′-difluorobenzophenone to yield fibrous poly(arylene ether ketone)s (PAEKs) containing various amounts of binaphthyl unit, which was then selectively and efficiently sulfonated using ClSO3H to yield sulfonated poly(arylene ether ketone)s (SPAEKs) with ion exchange capacities (IECs) ranging from 1.40 to 1.89 mmol·g−1. The chemical structures of the polymers were confirmed by 2D 1H–1H COSY NMR and FT-IR. The thermal properties, water uptake, swelling ratio, proton conductivity, oxidative stability and mechanical properties of SPAEKs were investigated in detail. It was found that the conjugated but non-coplanar structure of binaphthyl unit endorsed excellent solubility and film-forming capability to SPAEKs. The SPAEK-50 with an IEC of 1.89 mmol·g−1 exhibited a proton conductivity of 102 mS·cm−1 at 30 °C, much higher than that of the state-of-the-art Nafion N212 membrane and those of many previously reported aromatic analogs, which may be attributed to the likely large intrinsic free volume of SPAEKs created by the highly twisted chain structures and the desirable microscopic morphology. Along with the remarkable water affinity, thermal stabilities and mechanical properties, the SPAEKs were demonstrated to be promising proton exchange membrane (PEM) candidates for potential membrane separations.

Sign in / Sign up

Export Citation Format

Share Document