Sulfonated poly(arylene ether sulfone) nanocomposite electrolyte membrane for fuel cell applications: A review

Polymer electrolyte membrane (PEM) fuel cells are considered a promising technology for generating power with water as a byproduct. Recently, sulfonated poly(arylene ether sulfone) (SPAES) has emerged as a most suitable alternative for PEM applications because of its high proton conductivity, high CO tolerance, and low fuel crossover. However, the existing SPAES polymeric membrane materials have poor chemical reactivity, mechanical processability, and thermal usability. Thus, the effects of mixing inorganic nanomaterials with SPAES polymers on proton conductivity, power density, fuel crossover, thermal and chemical stability, and durability are discussed in this review. Further, the progress in preparation methods and fuel cell characteristics by the addition of silica, clay, heteropolyacids (HPA), and carbon nanotubes (CNTs) in polymer membrane materials for PEM applications is also discussed.     

Recent progress and prospective of medium and high temperatures thermal energy storage materials

开发中高温储热材料及其制备方法是储热技术发展的关键之一.本文结合中高温储热材料的分类,特点,应用及存在的问题对中高温储热材料的研究进展进行了综述,主要包括显热储热材料,热化学储热材料以及潜热储热材料.探讨了复合结构储热材料及其制备工艺,进一步介绍了其最新研究进展,并对中高温储热材料的下一步研究进行了展望,提出开发高性能纳微复合结构储热材料是未来研究的重点.     

Enhancement of thermal interface material properties using carbon nanotubes through simple electrophoretic deposition method

The industrial revolution development of electronic technologies has turned the electronic system into a complicated integration of high-power density and smart design. The complex integrated design has contributed to the excessive heat generation in electronic devices. Consequently, heat management devices have become crucial in prolonging the lives of devices and components and maintaining their optimal performance. Therefore, the passive heat management treatment through thermal interface materials (TIMs) in the devices is among the best options to remove heat from electronic devices. Carbon nanotubes (CNTs) with high-thermal conductivity was employed in this study for TIM development by using the simple electrophoretic deposition (EPD) method. The CNTs were synthesized and purified before TIM development. Several analyses, including transmission electron microscopy, thermogravimetric analysis, Raman spectroscopy, and Fourier-transform infrared, were conducted. Analysis results showed that only 0.03 wt% was retained and carbon content increased up to 97.84% after purification. The purified CNTs were dissolved in a suspension medium with a ratio of 0.5 mg/mL to achieve suspension stability, and a Zetasizer was used for verification. The following three operating parameters of EPD were investigated: (a) range of applied voltage (100-200 V), (b) deposition time (1-20 min), and (c) gap between electrodes (10-20 mm). On the basis of the characterization results, the optimum process condition of EPD was achieved at 175 V, 10 minutes, and 10 mm with 1.6 mg of CNT deposition and 14.14 μm of CNT thickness. The maximum thickness of deposited CNTs was 56.95 μm, producing 27.08 W/m∙K and 2.09 mm²/s of thermal conductivity and diffusivity, respectively. These results indicate the high potential of CNTs in facilitating efficient heat removal in TIM fabrication.     

Recent progress in carbon nanotubes support materials for Pt-based cathode catalysts in PEM fuel cells

Support materials have a significant impact on catalytic activity, stability, and performance of catalysts toward the oxygen reduction reaction (ORR). The properties of carbon-based materials have made them an excellent alternative for use as support for nanosized catalysts. Recently, carbon nanotubes (CNTs) have been explored as catalyst support materials, and their properties make them a promissory alternative. Furthermore, catalysts supported on CNTs exhibit higher resistance to electrochemical oxidation, better catalytic performance, and higher durability than catalysts supported on carbon black. In recent years, CNTs have acquired great relevance as catalysts support materials for ORR in acid media. This review addresses the most relevant studies on CNTs modification using methods such as functionalization, doping, and hybrid supports (CNTs-metal oxide) used as supports for Pt-based cathode catalysts in proton exchange membrane fuel cells.     

An overview of proton exchange membranes for fuel cells: Materials and manufacturing

Due to their efficient and cleaner operation nature, proton exchange membrane fuel cells are considered energy conversion devices for various applications including transportation. However, the high manufacturing cost of the fuel cell system components remains the main barrier to their general acceptance and commercialization. The main strategy for lowering the cost of fuel cells which is critical for their general acceptance as alternative energy sources in a variety of applications is to lower the cost of the electrolyte and catalyst. An electrolyte is one of the most important components in the fuel cell and a major contributor to the cost (>$500/m² for commercial Nafion® series). Nafion is widely used as an electrolyte in PEMs, but it has some limitations in addition to high costs such as low proton conductivity, high-temperature performance degradation, and high fuel crossover. Therefore, the development and manufacturing of low-cost and high-performance electrolyte membranes with higher conductivity (～0.1 S·cm ^?1) at a wider temperature range is a top priority in the scientific community. Recent years have seen extensive research on the preparation, modification, and properties of PEMs such as non-Nafion membranes (SPI, PBI, polystyrene, polyphosphazene, SPAEK, SPEEK, SPAS, SPEN), and their composites by incorporating functionalized CNTs, GO as fillers to overcome their drawbacks. This paper provides a comprehensive review of membrane materials and manufacturing with a focus on PEMs. In particular, the review brings out the basic mechanism involved in proton conduction, important requirements, historical background, contending technologies, types, advantages and disadvantages, current developments, future goals, and directions design aspects related to thermodynamic and electrochemical principles, system assessment parameters, and the prospects and outlook.     

Simultaneously enhanced hydroxide conductivity and mechanical properties of quaternized chitosan/functionalized carbon nanotubes composite anion exchange membranes

Low-cost biopolymer chitosan has received considerable attention in the field of anion exchange membranes (AEMs) because it can be easily quaternized and avoids the carcinogenic chloromethylation step. Simultaneously increasing the ionic conductivity and improving mechanical properties of quaternized chitosan (QCS) is key for its high-performance application. In this study, new composite AEMs consisting of QCS and functionalized carbon nanotubes (CNTs) were prepared. CNTs were coated with a thick silica layer onto which high-density quaternary ammonium groups were then grafted. The insulator silica coating effectively prohibits electron conduction among nanotubes and the grafted –NR₃⁺ provides new OH⁻ conductive sites. Incorporating 5 wt% functionalized CNTs into the matrix enhanced ionic conductivity to 42.7 mS cm⁻¹ (80 °C) which was approximately 2 times higher than that of pure QCS. The effective dispersion of CNTs and appropriate interfacial bonding between nanofiller and QCS improved the mechanical properties of AEMs, including both the strength and toughness of the composite membranes. An alkaline direct methanol fuel cell equipped with the composite membrane (5% functionalized CNTs loading) produced an maximum power density of 80.8 mW cm⁻² (60 °C), which was 57% higher than that of pure QCS (51.5 mW cm⁻²). This study broadens the application of natural polymers and provides a new way to design and fabricate composite AEMs with both improved mechanical properties and electrochemical performance.     

ZnMn2O4/milk-derived Carbon hybrids with enhanced Lithium storage capability

One of the effective ways to improve the conductivity and structural stability of binary metal oxide nanostructures is to tightly composite them with nano-carbon materials with excellent conductivity. However, the introduction of low density carbon materials also reduces the energy density of batteries. Therefore, we provides a new idea to enhance the lithium storage performance of carbon/binary transition metal oxide anode materials by multi-element co-doping carbon. ZnMn₂O₄ provides high lithium storage capacity; non-metallic heteroatoms in milk-derived carbon greatly improve the conductivity of carbon materials; metal heteroatoms in milk-derived carbon increase the density of carbon materials. Multicomponent co-doping carbon can build up the mass specific capacity, ratio performance, cyclic life and mechanical properties of binary metal oxides/porous carbon nanocomposites. As the anode materials of lithium-ion batteries, the ZnMn₂O₄/MC (milk-derived carbon) hybrids deliver a high reversible capacity of 1352 mAh g⁻¹ after 400 cycles at 0.1 A g⁻¹, and a remarkable long-term cyclability with 635 mAh g⁻¹ after 300 cycles at 1.0 A g⁻¹.     

Green electricity production with living plants and bacteria in a fuel cell

The world needs sustainable, efficient, and renewable energy production. We present the plant microbial fuel cell (plant-MFC), a concept that exploits a bioenergy source in situ. In the plant-MFC, plants and bacteria were present to convert solar energy into green electricity. The principal idea is that plants produce rhizodeposits, mostly in the form of carbohydrates, and the bacteria convert these rhizodeposits into electrical energy via the fuel cell. Here, we demonstrated the proof of principle using Reed mannagrass. We achieved a maximal electrical power production of 67 mW m⁻² anode surface. This system was characterized by: (1) nondestructive, in situ harvesting of bioenergy; (2) potential implementation in wetlands and poor soils without competition to food or conventional bioenergy production, which makes it an additional bioenergy supply; (3) an estimated potential electricity production of 21 GJ ha⁻¹ year⁻¹ (5800 kWh ha⁻¹ year⁻¹) in Europe; and (4) carbon neutral and combustion emission-free operation. Copyright © 2008 John Wiley & Sons, Ltd.     

A critical review on improving hydrogen storage properties of metal hydride via nanostructuring and integrating carbonaceous materials

Hydrogen-based economy has a great potential for addressing the world's environmental concerns by using hydrogen as its future energy carrier. Hydrogen can be stored in gaseous, liquid and solid-state form, but among all solid-state hydrogen storage materials (metal hydrides) have the highest energy density. However, hydrogen accessibility is a challenging step in metal hydride-based materials. To improve the hydrogen storage kinetics, effects of functionalized catalysts/dopants on metal atoms have been extensively studied. The nanostructuring of metal hydrides is a new focus and has enhanced hydrogen storage properties by allowing higher surface area and thus reversibility, hydrogen storage density, faster and tunable kinetics, lower absorption and desorption temperatures, and durability. The effect of incorporating nanoparticles of carbon-based materials (graphene, C60, carbon nanotubes (CNTs), carbon black, and carbon aerogel) showed improved hydrogen storage characteristics of metal hydrides. In this critical review, the effects of various carbon-based materials, catalysts, and dopants are summarized in terms of hydrogen-storage capacity and kinetics. This review also highlights the effects of carbon nanomaterials on metal hydrides along with advanced synthesis routes, and analysis techniques to explore the effects of encapsulated metal hydrides and carbon particles. In addition, effects of carbon composites in polymeric composites for improved hydrogen storage properties in solid-state forms, and new characterization techniques are also discussed. As is known, the nanomaterials have extremely higher surface area (100–1000 time more surface area in m²/g) when compared to the bulk scale materials; thus, hydrogen absorption and desorption can be tuned in nanoscale structures for various industrial applications. The nanoscale tailoring of metal hydrides with carbon materials is a promising strategy for the next generation of solid-state hydrogen storage systems for different industries.     

A review of quaternized polyvinyl alcohol as an alternative polymeric membrane in DMFCs and DEFCs

Direct methanol fuel cells (DMFCs) and direct ethanol fuel cells (DEFCs) have emerged as alternative power generators for portable devices and household appliances because of their easy and fast production of electricity, as well as high energy conversion to provide high-power density. However, several critical factors limit the commercialization of DMFCs and DEFCs, particularly issues related to polymer electrolyte membranes, including the high-cost production of Nafion membranes and cell degradation caused by high fuel crossover and dehydration. This review paper provides an overview of the current status and challenges in quaternized polyvinyl alcohol (QPVA)-based membranes as an alternative polymer electrolyte membrane for DMFCs and DEFCs. The main advantages of using QPVA-based membranes in fuel cells are reduced cost production of membrane, fuel-crossover minimization, and competitive conductivity with Nafion membrane. The effects of modifying the QPVA-based membrane, especially on conductivity properties, fuel crossover, uptake condition, mechanical, thermal, and chemical properties, and single-cell performance are comprehensively discussed. The best performances of DMFCs and DEFCs with utilizing QPVA-based membrane are reported as 272 and 144 mW cm⁻², respectively. This paper is the first to highlight the current status and challenges of QPVA-based membranes for DMFCs and DEFCs applications.     

Organic-inorganic backbone with high contents of proton conducting groups: A newly designed high performance proton conductor

To prepare new high temperature organic-inorganic proton conductor for applications in proton exchange membrane fuel cells (PEMFC), 2,4,6-triphosphono-1,3,5-triazine (TPT) was synthesized and reacted with three different types of metal ions (Ce, Zr and Fe) in varied molar ratios. In each TPT molecule, three phosphonic acid groups were introduced into the triazine ring to obtain an organic compound with high content of proton conducting groups, which was then reacted with metal ions to ensure the insolubility in water aiming to avoid leaking during PEMFC operation. CeTPT(1:2) exhibited good thermal stability up to 200 °C and showed crystalline phase. MTPT exhibited high ion exchange capacity (IEC, 1.53–2.12 meq. g⁻¹). CeTPT(1:2) exhibited highest proton conductivity among all samples, which reached 0.116, 0.070 and 0.034 S cm⁻¹ at 100% relative humidity (RH), 50% RH and anhydrous conditions at 180 °C, respectively. The corresponding activation energy for proton conduction was 14.5, 16.0 and 21.5 kJ mol⁻¹ at 100% RH, 50% RH and anhydrous conditions, respectively. The mechanism for proton conduction was proposed according to the activation energy. The proton conductor can find promising applications in fuel cells, corrosion inhibition and water desalination due to its good thermal stability and high IEC.     

Design of a solar hydrogen refuelling station following the development of the first Croatian fuel cell powered bicycle to boost hydrogen urban mobility

Hydrogen refuelling stations are important for achieving sustainable hydrogen economy in low carbon transport and fuel cell electric vehicles. The solution presented in this paper provides us with a technology for producing carbon dioxide free hydrogen, which is an approach that goes beyond the existing large-scale hydrogen production technologies that use fossil fuel reforming. Hence, the main goal of this work was to design a hydrogen refuelling station to secure the autonomy of a hydrogen powered bicycle. The bicycle hydrogen system is equipped with a proton exchange membrane fuel cell stack of 300 W, a DC/DC converter, and a metal hydride storage tank of 350 NL of hydrogen. The hydrogen power system was made of readily available commercial components. The hydrogen station was designed as an off-grid system in which the installed proton exchange membrane electrolyzer is supplied with electric energy by direct conversion using photovoltaic cells. With the hydrogen flow rate of 2000 cc min⁻¹ the hydrogen station is expected to supply at least 5 bicycles to be used in 20 km long city tourist routes.     

Interconnected NiS-nanosheets@porous carbon derived from Zeolitic-imidazolate frameworks (ZIFs) as electrode materials for high-performance hybrid supercapacitors

Nickel sulfide-based materials have shown great potential for electrode fabrication owing to their high theoretical specific capacitance but poor conductivity and morphological aggregation. A feasible strategy is to design hybrid structure by introducing highly-conductive porous carbon as the supporting matrix. Herein, we synthesized hybrid composites consisting of interconnected NiS-nanosheets and porous carbon (NiS@C) derived from Zeolitic-imidazolate frameworks (ZIFs) using a facile low-temperature water-bath method. When employed as electrode materials, the as-prepared NiS@C nanocomposites present remarkable electrochemical performance owing to the complex effect that is the combined advantages of double-layer capacitor-type porous carbon and pseudocapacitor-type interconnected-NiS nanosheets. Specifically, the NiS@C nanocomposites exhibit a high specific capacitance of 1827 F g⁻¹ at 1 A g⁻¹, and excellent cyclic stability with a capacity retention of 72% at a very high current density of 20 A g⁻¹ after 5000 cycles. Moreover, the fabricated hybrid supercapacitor delivers 21.6 Wh kg⁻¹ at 400 W kg⁻¹ with coulombic efficiency of 93.9%, and reaches 10.8 Wh kg⁻¹ at a high power density of 8000 W kg⁻¹, along with excellent cyclic stability of 84% at 5 A g⁻¹ after 5000 cycles. All results suggest that NiS@C nanocomposites are applicable to high-performance electrodes in hybrid supercapacitors and other energy-storage device applications.     

Enhanced proton conductivities of chitosan-based membranes by inorganic solid superacid SO42−–TiO2 coated carbon nanotubes

To increase proton conductivity of chitosan (CS) based polymer electrolyte membranes, a novel nanofiller-solid superacide SO₄^2--TiO₂ (STi) coated carbon nanotubes (STi@CNTs) are introduced into CS matrix to fabricate membranes for polymer electrolyte membrane fuel cells (PEMFCs). Owing to the STi coating, the dispersion ability of CNTs and interfacial bonding are obviously improved, hence, CNTs can more fully play their reinforcing role, which makes the CS/STi@CNTs composite membranes exhibit better mechanical properties than that of pure CS membrane. More importantly, STi possesses excellent proton transport ability and may create facile proton transport channels in the membranes with the help of high aspect ratio of CNTs. Particularly, the CS/STi@CNTs-1 membrane (1 wt% STi@CNTs loading) obtains the highest proton conductivity of 4.2 × 10⁻² S cm^–1 at 80 °C, enhancing by 80% when compared with that of pure CS membrane. In addition, the STi@CNTs also confer the composite membranes low methanol crossover and outstanding cell performance. The maximum power density of the CS/STi@CNTs-1 membrane is 60.7 mW cm⁻² (5 M methanol concentration, 70 °C), while pure CS membrane produces the peak power density of only 39.8 mW cm⁻².     

Metal phthalocyanine-linked conjugated microporous polymer hybridized with carbon nanotubes as a high-performance flexible electrode for supercapacitors

Metal phthalocyanine-linked conjugated microporous polymers (MPc-CMPs) have huge potential applications in energy conversion and storage systems. However, the inherent low conductivity limits their practical application. Herein, the MPc-CMPs are hybridized with highly conductive carbon nanotubes (CNTs) via the easy vacuum filtration method. Interestingly, the composite (denoted as CoPc-CMP/CNTs) shows the flexible feature, which can be served as the flexible binder-free electrode for supercapacitors (SCs). As expected, the flexible CoPc-CMP/CNTs exhibits a high specific capacitance of 289.1 F g⁻¹ at a current density of 1 A g⁻¹ and good capacity retention of 82.4% over 1350 cycles at a high current density of 10 A g⁻¹. Furthermore, First-principle calculations are used to elucidate the superiority of CoPc-CMP to other analogues. The good electrochemical performance could be attributed to the synergistic effect from the high pseudocapacitance and good conductivity of CoPc-CMP as well as the capacitive contribution and good conductivity of CNTs. Our strategy provides a new avenue to develop the high-performance SCs via rational integration of MPc-CMPs with highly conductive CNTs.     

A polymer electrolyte fuel cell life test: 3 years of continuous operation

Implementation of polymer electrolyte fuel cells (PEMFCs) for stationary power applications requires the demonstration of reliable fuel cell stack life. One of the most critical components in the stack and that most likely to ultimately dictate stack life is the membrane electrode assembly (MEA). This publication reports the results of a 26,300 h single cell life test operated with a commercial MEA at conditions relevant to stationary fuel cell applications. In this experiment, the ultimate MEA life was dictated by failure of the membrane. In addition, the performance degradation rate of the cell was determined to be between 4 and 6 μV h⁻¹, at the operating current density of 800 mA cm⁻². AC impedance analysis and DC electrochemical tests (cyclic voltammetry and polarization curves) were performed as diagnostics during and on completion the test, to understand materials changes occurring during the test. Post mortem analyses of the fuel cell components were also performed.     

Citric acid functionalized carbon materials for fuel cell applications

Carbon materials can be easily functionalized using citric acid (CA) treatment. The CA modification of carbon materials is both simple and effective. It requires no prolonged heating, filtration and washing, and produces more functional groups such as carboxyl and hydroxide on CA-modified carbon nanotubes and XC72 carbon blacks than on HNO₃–H₂SO₄ oxidized carbon nanotubes and as-purchased XC72. Platinum nanoparticles are deposited on these functionalized carbon materials by means of a microwave-assisted polyol process. The investigations using TEM, XRD, FTIR and TGA indicate that CA modification creates more functional groups and thus deposits more Pt nanoparticles with smaller average particle size on the surface of carbon materials. Electrochemical studies of the Pt/C samples for methanol oxidation reveal higher activity for Pt on CA-modified carbon materials. It is therefore considered that this method can find important applications in reducing the cost and improving performance of proton-exchange membrane fuel cells.     

Synergistic effect of graphene oxide and carbon nanotubes on sulfonated poly(arylene ether nitrile)-based proton conducting membranes

A strategy to prepare graphene oxide (GO)/carbon nano-tubes (CNTs)/sulfonated poly(arylene ether nitrile) (SPEN) composite membranes aimed for the proton exchange membrane is presented herein. GO and CNTs were incorporated into SPEN to improve the performances of proton exchange membrane. To study the synergistic effect of GO and CNTs, GO/SPEN and CNTs/SPEN membranes were also fabricated. The influences of GO and CNTs upon the microstructures, including thermal and mechanical properties, water uptake, swelling, proton conductivity and methanol permeability of composite membranes were investigated in detail. The membranes combining GO and CNTs could effectively avoid the self-agglomeration of GO or CNTs. In such a way, efficient proton transport channels were constructed by homogeneous dispersion of GO and CNTs within SPEN, leading to enhancement of proton conductivity. The proton conductivity of GO/CNTs/SPEN composite membrane with the ratio of 2:2 achieved the highest value of 0.1197 S/cm at 20 °C. Meanwhile, low methanol permeability (2.015 × 10^?7 cm² s^?1) was still maintained. Consequently, the combination of CNTs and GO exhibited a favorable synergistic effect on the selectivity of proton exchange membrane, which is better than pure SPEN, Nafion 117, GO/SPEN, and CNTs/SPEN membranes. This feasibility study could provide an alternative approach to design GO/CNTs-based proton-conducting membranes for DMFC applications.     

Au/Porous silicon‐based sodium borohydride fuel cells

The Au/Porous silicon structure (Au/PS) was developed as hydrogen fuel cell. The use of a porous silicon filled with hydrochloric acid as a proton‐conducting membrane and thin gold film as a catalyst in Au/PS/Si fuel cell is demonstrated. The devices were fabricated by first creating 10–20 µm thick porous silicon layer by anodization etching in a standard silicon wafer and then depositing the gold catalyst film onto the porous silicon. Using sodium borohydride (NaBH₄) solution as the fuel, generation of the open‐circuit voltage of 0.55 V and the fuel cell peak power density of 13 mW cm⁻² at room temperature was achieved. Moreover production of hydrogen by evolution (out‐diffusion) of hydrogen from solid sodium borohydride during thermal annealing at 30–120°C was investigated. Data on the effective diffusion coefficient of the hydrogen in NaBH₄ were determined from intensity changes of infrared vibration peaks of B–H bond (2280 and 3280 cm⁻¹), as a result of thermal annealing of NaBH₄ samples. The relatively high values of the diffusion coefficient of hydrogen, increasing from 1×10⁻⁶ cm² s⁻¹ to 2×10⁻⁴ cm² s⁻¹ suggest that a thermo‐stimulated evolution process can be used for producing hydrogen from NaBH₄. Copyright © 2010 John Wiley & Sons, Ltd.