A
Samar
Samanta
1
Biswajit
Maity
2
Avijit
Ghosh
3
Sunil
Baran
Kuila
4
Biswajit
Mandal
5
Swarnajit
Bhattacharya
6
1
Indorama India Private Ltd
Haldia
West Bengal
India
2
Haldia Petrochemicals Ltd
Haldia
West Bengal
India
3
Dept of Chem. Engg
Heritage Institute of Technology
Kolkata
WB
India
4
Dept. of Chemical Engineering
Haldia Institute of Technology ICARE Complex
HIT Campus
Haldia
West Bengal
India
5
Dept. Of Electronics And Instrumentation Engineering
Haldia Institute of Technology ICARE Complex
HIT Campus
Haldia
West Bengal
India
Samar Samanta1, Biswajit Maity2, Avijit Ghosh3, Sunil Baran Kuila4, Biswajit Mandal*5, Swarnajit Bhattacharya6
1 Indorama India Private Ltd., Haldia, West Bengal, India
2Haldia Petrochemicals Ltd., Haldia, West Bengal, India
3Dept of Chem. Engg., Heritage Institute of Technology, Kolkata, WB, India
4,5*Dept. of Chemical Engineering, Haldia Institute of Technology
ICARE Complex, HIT Campus, Haldia, West Bengal, India
6 Dept. Of Electronics And Instrumentation Engineering, Haldia Institute of Technology
ICARE Complex, HIT Campus, Haldia, West Bengal, India
Abstract-
The graphene-supported electro-catalysts in proton exchange membrane (PEM) fuel cells were evaluated in this study, and the results show that the output of these cells is positively correlated with the current density, reaching a maximum of about 2.5 W/cm². Problems with energy conversion may be lurking, though, because the efficiency is still very low. Additional investigation into the catalysts' electrochemical dynamics and a reevaluation of the model's loss parameters are warranted in light of the discrepancy between power output and efficiency. In order to enhance the energy efficiency and overall performance of PEM fuel cells, future research should focus on improving the catalyst composition, refining the operating conditions, and using more sophisticated modeling tools.
Keyword
Used- Graphene-supported electro-catalysts
Proton Exchange
Membrane (PEM) fuel cells
Energy conversion efficiency and Power output
At the moment, scientists are concentrating on creating materials at the nanoscale for the best performance. A high absorption rate and a large surface area to volume ratio are two benefits of nanoscale materials. The material is rummaged in a diversity of applications, such as nanoscale photovoltaic cells, [1, 2] in which the structure's high rate of solar energy absorption is due to the nanoparticles. This demonstrates that the rate at which solar energy is absorbed increases with particle size. Different materials can be found at the nanoscale, such as nanoparticles, Nanopowders, nanorods, nanotubes, and nanowires. Nanomaterials exist in zero, one, two, and three dimensions, among other dimensionalities. Because of their big superficial area and porosity, one-dimensional polymers are widely used in many different applications [3, 4]. One substance that is known to have positive qualities is carbon-type material, which includes high durability, environmental safety, abundance, and stability. Their superior chemical stability in both acidic and alkaline environments across a broad temperature range makes them the best options for electrodes in electrically powered devices. Numerous carbon allotropes are accessible, including graphene, carbon nanotubes, buckminsterfullerene, and nano-diamonds [5, 6]. Because of its special properties, including its “high specific surface area (2630 m2 g − 1)”, good chemical stability, and excellent electrical conductivity, graphene is valued highly in energy conversion and storage applications.[7]
When considering alternative power sources, PEM fuel cells offer numerous benefits. Among these advantages are things like burning at lower temperatures. PEM fuel cells are claimed to produce clean, stable fuel in comparison to other energy-generating methods. PEM fuel cells have a high degree of dependability for both stationary and mobile power applications. This includes using them to replace engines that run on fossil fuels like gasoline and diesel in the transportation sector. PEM fuel cells can be used in vigor storage applications in addition to being standalone power generators when combined with renewable energy sources. It can be utilized as a single cell for low-power needs or as part of a cell stack to combine multiple cells for higher voltage and electricity [8, 9].
1.1 Prospects for PEM Fuel Cells
Commercialization remains a major concern despite the PEM fuel cell's outstanding feature as a power source and all of its notable development accomplishments. It has significant issues with durability, performance, and cost. Platinum is a catalyst used in fuel cell technology, specifically PEM fuel cell technology. One of the most expensive parts of fuel cells is the platinum catalyst. The efficient use of platinum catalysts in fuel cell design has the potential to directly lower costs. Additionally, locating a catalyst that replaces platinum will lower the fuel cell's cost even more.
Fuel cells are typically a little bit larger than batteries of equivalent capacity. However, PEM fuel cell producers and researchers have recently carried out several experiments aimed at reducing fuel cell size and weight to satisfy the full requirements of portable applications. The fuel cell's mechanical robustness is regarded as a crucial performance characteristic as a power source, especially for transportation applications [10].
Because of their detrimental effects on the environment, the topics of ecological devastation, ozone layer depletion, and global warming have generated a lot of discussion. The main source of energy for human activity, the burning of fossil fuels, is one of the root causes of these problems. Significant advancements in alternative power conversion technologies, including fuel cell systems, are therefore urgently needed to protect the environment, save costs, and convert energy with high efficiency [11]. These days, nanotechnology is helping to make current technology more efficient. It also has a lot of potential to improve the environment and lessen the effects of energy production, storage, and use [12]. Superior materials and manufacturing processes can be improved through nanotechnology's special ability to create novel structures at the atomic scale, leading to substances and phenomena at the nanoscale.
Fuel cell generators are electrochemical devices that use an electro-catalytic process to convert the chemical energy retained by fuel directly into electrical currents. Due to its notable features, this type of device has been the target of fresh energy technology development. In contrast to batteries, fuel cells are flexible, have a high potential efficiency, don't require recharging, and are capable of producing electricity as long as fuel is available. The three primary constituents of a fuel cell, collectively denoted as the membrane-electrode assembly (MEA), are an anode, a cathode, and an ion-conducting electrolyte [13]. There are numerous ways to categorize fuel cell technologies, including charge carrier, fuel type, oxidizer type, and operating temperature. Every fuel cell type has pros and cons when compared to the others, but overall, they seem like a viable alternative to current electricity generation technologies if the Earth experiences significant environmental harm and oil runs out [14].
1.2 Enhancing Energy and Power Densities
In recent years, fuel cell devices have shown enhanced reliability and reduced expenses due to the integration of nanomaterials. The application of nanotechnology in manufacturing enhances surface area and aspect ratio, leading to increased energy and power densities, extended shelf life, and simplified reduction in size. These characteristics are crucial for advancing fuel cell technology in portable electronic gadgets [15]. Nanomaterials are being more frequently employed in the processes of producing, purifying, and storing hydrogen for use in fuel cells [16]. Carbon nanotubes have found applications in fuel cells, such as in gas diffusion layers based on carbon nanotubes, electrocatalysts supported by carbon nanotubes, nanocomposite bipolar plates that include multi-walled carbon dioxide nanotubes, and Nafion membranes that have been altered with multiwall nanotubes of carbon.
The primary benefit of SOFC systems for effective electricity production is their capability to utilize hydrocarbon fuels directly, eliminating the need for ahead fuel preparation processes, such as reforming [21]. The arrangement of components for a flat design of the SOFC system is presented herein. This document presents an organization of parts for the flat layout of the SOFC system. The membrane-electrode assembly comprises an electrolyte located between the anode and cathode, which are positioned among metal interconnect structures. The interconnect structure includes the development of fuel and air channels. The electrolyte is composed of a dense ceramic material, including “yttria-stabilized zirconia (YSZ) or gadolinia-doped ceria (GDC)”. This material exhibits permeability for gas flow and serves as a conduit for oxygen ions (O2) [24]. The composite electrodes are composed of permeable metal-loaded ceramics (cermets), including Ni– “YSZ for the anode and Sr-doped LaMnO3 (LSM) for the cathode”. These materials can act as mixed technological and ionic conductors, promoting the expansion of single-phase limits “(TPB)” and improving electrocatalytic feedback.
The SOFC system involves intricate transport, chemical in nature, and electrochemical processes, with associated transport resistances and activation barriers significantly influencing the system's operational performance. Several MEA-level processes are illustrated in Fig. 2. At the gas-cathode-electrolyte three-phase boundaries, oxygen from the air channel permeates the porous cathode and is reduced to oxygen ions (O2−). The oxygen ion produced at the cathode-electrolyte interface then flows to the anode-electrolyte interface via the ion-conducting electrolyte.
Kahraman Hüseyin, and Yasin Akın (2024) [26] examined the membrane and bipolar plate, which are the essential elements of polymer electrolytic membrane/proton interchange membrane fuel cells (PEMFC). The functions of the components have been elucidated in detail. The prevalent materials and their properties for membranes and bipolar plates utilized in PEMFC have been examined. This study meticulously examined membranes and bipolar plates, focusing on production methods, preferred materials, and attachments. Recent investigations concerning membrane and bipolar plates have been presented, accompanied by a thorough review of existing literature. Recent studies on the specified components have been conducted to acquire the necessary properties for fuel cell operation, leading to conclusions that may illuminate commercial production.
Shah MAK Yousaf, (2023) [27] expressed the growth of the humanoid population and the improved speed of life for many individuals are the main factors driving the shift towards renewable energy solutions, aside from the reliance on fossil fuel combustion. Fuel cells play a crucial role in the energy transition, providing efficient as well as ecologically sustainable energy conversion through a range of production of energy technologies. Solid-oxide fuel cells (SOFCs) represent the most economical and feasible choice for applications in industry. Nonetheless, the substantial expense restricts its market viability because of the increased temperature of operation (> 750°C) of the electrolytic materials. Low temperatures solid-oxide fuel cell systems (SOFCs) functioning below 500°C demonstrate economic viability and potential for commercialization; however, the scarcity of suitable electrolyte materials impedes their advancement. This study presented improvements in new useful semiconductor-ionic materials (SIM) and semiconductor membranes (SM) that may enable new research and development pathways for solid oxide fuel cells (SOFCs). They examined the complex characteristics of SM/SIM materials as well as the microscopic electrochemical phenomena of SIMs to propose new concepts and methodologies for enhancing SOFCs. A new concept of a nano-solid oxide fuel cell is introduced, which replaces the usual electrolysis layer with a solid ionic membrane (SIM) or solid membrane (SM), distinguishing it from traditional SOFCs.
Musa Maryam Taufiq, et al. (2022) [28] said the growth of the humanoid populace and enhanced existing circumstances for a significant segment of the populace are the principal drivers of the adoption of maintainable energy manufacturing skills, apart from fossil petroleum burning. Fuel cells significantly contribute to vigor change by providing effectual then spotless energy adaptation across diverse energy machineries. “Solid oxide fuel cells” represent the greatest economical and feasible other aimed at engineering applications. Nevertheless, the prohibitive expense restricts its commercialization owing to the elevated working temperature “(> 750°C)” of the electrolyte materials. Consequently, low-temperature rock-hard oxide fuel cells “(SOFCs)” working under 500°C are economically viable and appealing for commercialization; however, the scarcity of suitable electrolyte materials impedes their advancement. The author aimed to showcase advancements in novel functional semiconductor-ionic materials “(SIM)” and semiconducting material sheaths “(SM)” that could facilitate new avenues for the research and development of solid oxide fuel cells. Additionally, they examine the intricate properties of “SM/SIM” resources than the nanoscale electrochemical phenomena of SIMs to introduce novel concepts and methodologies for the advancement of “SOFCs”. A novel concept of a “nano-SOFC” that substitutes the conventional electrolyte coating with a “SIM or SM” distinguishing it from traditional “SOFCs” is introduced.
Jawad Noor H., et al. (2022) [29] evaluated the developments of fuel cells that have garnered increased interest due to their capability to utilize non-precious metals as catalysts. This advancement contributes to a reduction in the charge of each kW of control generated by petroleum cell devices to a certain degree. In recent years, the primary obstacle to the advancement of fuel cells has been the availability of extremely “conductive anion-exchange membranes”. Conversely, advancements indicate that newly developed “anion-exchange membranes” have achieved elevated conductivity levels, resulting in an optimal configuration of the cell. At present, a growing body of research has detailed the presentation outcomes of petroleum cells. The majority of the works detailing cell presentation are based on “hydrogen–anion exchange” membrane fuel cell technology (AEMFCs). However, an increasing quantity of pieces of training has additionally documented the use of alternative fuels, including alcohols, non-alcoholic “carbon-based fuels, and nitrogen-based fuels”. This study is an overview of the various types, performance metrics, employed membranes, and working parameters of anion exchange membranes used in fuel cells.
Banerjee Aritro, et al. (2022) [30] said microbial fuel cells are a new wastewater treatment technology that directly produces energy from the carbon-based substance in the aquatic by using the metabolism of microorganisms. The three primary parts of an MFC are the “anode, cathode, and proton exchange membrane”. Their working principle is identical to that of a hydrogen fuel cell. Both anode and cathode chambers are kept apart by a membrane, which maintains the anaerobic and aerobic environments in each chamber, correspondingly. This evaluation paper addresses the latest advancements in obtaining robust, sustainable, and affordable membranes and outlines the most recent developments in membrane materials that are particularly suited for MFC. In MFC, the most common commercially available membranes are “Nafion 117, Flemion, and Hyflon”. The utilization of “non-fluorinated polymeric membrane materials”, such as sulfonated silicon dioxide (S-SiO2), demonstrated encouraging results and demonstrated a viable substitute for Nafion 117 in “sulfonated polystyrene ethylene butylene polystyrene (SSEBS)”, sulfonated polyether ether ketone (SPEEK), and graphene oxide sulfonated polyether ketone (GO/SPEEK) membranes. Choosing an appropriate membrane for a scalable MFC system presents numerous obstacles before the technology can be commercially and technically feasible.
Liu, Qingshan, et al. (2022) [31] expressed the water management of proton exchange membrane fuel cells, introducing the most recent findings and advancements in membrane electrode gathering mechanisms and summarizing the factors influencing their properties. MEA made up of carbon fiber paper, a microporous layer, a catalyst layer, and a “proton exchange membrane”, is the main component of the “PEMFC”. The performance of the petroleum cell (PC) is greatly influenced by the characteristics of each element, and certain properties will interact strongly with one another. As a result, the characteristics of each component and how they interact determine the FC performance. Although there isn't a summary of this aspect yet, it serves as the foundation for the enterprise of high-performance FCs by elucidating the influence mechanism of different properties and their interactions on the FC performance. To fully understand the influence mechanism of a particular property, one must first sort and combine the conclusions regarding a similar factor or property that has been strained from all literature. It allows us to know intuitively which literature has been studied and arrive at the conclusions. This study discusses and forecasts the upcoming research directions and advances predictions of individual factors based on the growth and accomplishments of each component in certain areas.
Malik Vansh, et al. (2021) [32] examined the excessive use of fossil fuels for energy has resulted in an ever-increasing carbon footprint, which has alarmingly altered environmental conditions. The Hydrogen Interchange Membranes (PEM) fuel cells and the Solid Hydroxide Fuel Cell (SOFC) are two well-known fuel cells that are compared in this review along with recent developments in fuel cell technology. The review outlined the specific benefits and drawbacks of the two fuel cells that were discussed. Tabulated data containing key findings from PEMFC technology and earlier experimental studies of SOFC are presented for discussion. Finally, a thorough conclusion has been reached, and potential future developments are also mentioned.
Khoo Kuan Shiong, et al. (2021) [33] assessed known also as electrochemical generators, hydrogen fuel cells (FCs) are chemically powered devices that can directly transform chemical power into electrical energy. One of the most interesting fuel cell systems to be widely produced in recent years has a “proton-exchange membrane fuel cell”. Traditional PEMFC's capability to operate at greater temperatures is severely constrained by the electrolyte membrane's poor conductivity. In high-temperature PEMFCs (HT-PEMFCs), the use of ionic liquids (ILs), which are generally considered to be a more environmentally friendly solvent substitute than conventional thinners, in the proton exchange membrane's electrolyte exhibits inordinate promise. The most recent developments in the use of ILs as an electrolytic electrolyte in “PEMFCs” are discussed in this review. Additionally, there are numerous advantages to electrolyte membranes made of ILs and polybenzimidazole (PBI), including increased proton conductivity, enhanced mechanical qualities, and better thermal stability. The study looked into the greatest recent progressions and continuing problems in the field of inorganic liquid (IL) investigation, including material and electrolyte selection, system fabrication methods, IL synthesis, and experimental techniques. Also covered are the assessment of ILs' life cycle analysis, commercialization, and environmental friendliness. As a result, this review advances interest among a larger audience and offers material scientists new perspectives, encouraging the application of ILs to address energy-related issues.
Tellez-Cruz Miriam M., et al. (2021) [34] said that many researchers are very interested in the investigation of the electrochemical substance conversion of carbon oxides and renewable energy into biochemical fuels. Via a bolted technical cycle of carbon in which organic fuels, like H, are stored and then converted back into energy through electrochemical processes in fuel cells, this process primarily aims to mitigate the global energy crisis. When building masses of “proton exchange membrane fuel cells” to operate at low and modest temperatures, the technical community concentrates its efforts on developing “high-performance polymeric membranes” along with nanotechnology with significant catalytic action as well as equilibrium decrease the platinum cluster metallic applied as a cathode. It is crucial to design novel conductive membranes and nanoparticles whose shape influences their catalytic capabilities. For catalysis applications, various nanoparticle morphologies such as “cubes, octahedrons, icosahedrons, bipyramids, plates, and polyhedrons” are extensively researched. Recent developments regarding the elevated catalytic activity have concentrated on stabilizing agents and how they might affect the synthesis of nanomaterials to cause modifications in NP morphology.
Alaswad Abed, et al. (2020) [35] expressed that the most recent developments in fuel cell technology for both stationary and portable fuel cell submissions, as well as their incorporation into the motorized sector, are critically assessed in this review. The main benefits of applications for fuel cells are their rapid start-up time, high efficiency, lack of harmful releases into the environment, and decent modularity. Notwithstanding the benefits of fuel cells, one major barrier to their widespread commercialization is still their high cost. As a result, this review provided comprehensive information about the ideal operating parameters that result in the highest fuel cell performance. Future research on robust fuel cell geometry designs—which determine cell losses—as well as material characterization for the different parts of the cell are recommended by the paper. When done correctly, this will facilitate a complete decrease in the cell's cost, which will ultimately lower the system's overall cost. Public education is necessary because approximately persons have doubts about the safety of fuel cell skills, even contempt the advancements completed by the fuel cell investigative community. If a risk assessment is thoroughly documented and taken into account in subsequent research endeavors, this obstacle can be surmounted.
Babu Attuluri R, et al. (2018) [36] expressed the presentation of proton-exchanging membrane fuel cells, which are used in fuel cell vehicles, this study focused on their parametric analysis. In this study, a membrane electrode assembly is constructed at a loading of 40% Pt/C, and various parameters such as “cell temperature, hydrogen and oxygen” movement rates, and both “anode and cathode” humidification temperatures are experimented with. The findings indicated that while other parameters only cause variation in the concentration and activation polarization regions, cell temperature has a substantial impact on the PEMFC's performance. As a workable model for a greater-power vehicle, a fuel cell stack-powered prototype FCV is being developed. It can run continuously without the essential aimed at an outside control source. The author investigated the vehicle's performance through a battery of load tests.
Diesendruck Charles E. and Dario R. Dekel, (2018) [37] Expressed an Anion exchange membrane fuel cell technologies have the potential to revolutionize energy delivery and storage, but their commercial development is impeded by the anion exchange membranes' chemical breakdown while in use. As the “hydro oxide anions move from the cathode to the anode” they attack the polymer membranes' positively electric functional groups, neutralizing them and preventing them from conducting an anion. To tackle this issue, several novel quaternary ammonium salts have been put forth in recent years; however, although they function well in ex-situ chemical investigations, their efficacy in actual fuel cell research is severely constrained. The inherent chemical stability of anion-carrying ionomeric materials is determined by cation chemistry; however, it has been demonstrated recently that the fuel cell's operating hydration level has a major impact on chemical degradation. The road to overcoming the obstacle and ultimately developing and demonstrating extremely stable AEMFC devices will be made easier by having a thorough understanding of the concepts controlling the breakdown of chemicals below the fuel cell process and its crucial association with the amount of water in the working “fuel cell electrodes”.
Luo Yueqi, and Kui Jiao (2018) [38] studied the starting of proton exchange membranes (PEM) fuel cells from below-freezing temperatures is referred to in this review as a "cold start." Some of the remaining obstacles to the commercial use of PEM fuel cell technology in carriage, stationary, auxiliary, and portable systems are issues that arise during the cold start. Basic research on transport phenomena is essential for comprehending cold start mechanisms and provides the best answers for resolving cold start problems. This review discussed experimental studies that highlight component damages during a cold start, water and ice visualization, and output performance degradation. Additionally covered are analytical, mathematical, and microscopic models along with their outcomes. A focus is placed on transport phenomena that are associated with cold starts, such as gas diffusion layers, catalyst layers, microporous layers, supercooling, and water transport in the membrane. The methods used to maximize cold-start processes for enhanced performance are also emphasized. The component material designs, cell and stack structures, and startup mode/load controls are some of the strategies. It is demonstrated that every successful mitigation strategy for cold-start issues stems from a fundamental comprehension of the transport mechanisms that occur during a cold-start.
Dekel Dario R. (2018) [39] evaluated the use of non-precious metallic substances in “anion-exchange membrane fuel cells” which has drawn more attention lately because it theoretically lowers the price of a kilowatt of power in fuel cell devices. ‘Anion exchange membranes” that are highly conductive were the primary obstacle to the development of AEMFCs until recently. Nevertheless, advancements in this area over the last ten years indicate that recently created AEMs have already attained high conductivity levels, resulting in satisfactory cell performance. AEMFC performance results have been reported in an increasing number of research studies in recent years. Over the past three years, new performance records have been set. Though a cumulative quantity of studies has reported the usage of fuels other than ‘hydrogen, such as alcohols, non-alcohol C-based fuels’, and “N-based fuels”, the majority of the works broadcasting cell efficiency is based on “hydrogen-AEMFCs”. The cell functioning and constancy of “AEMFCs” over the years since the initial reports in the first decade of the 2000s are reviewed in this article.
Gubler Lorenz et al. (2018) [40 said that in place of perfluoroalkyl sulfonic acid (PFSA) membranes, a variety of “hydrocarbon-based ionomer membranes” have been suggested for use in fuel cells. Currently, there is a lack of complete resolution regarding the biochemical and Ionomer membranes in this class are mechanically degradable and their mixture, particularly in automotive operating conditions. Here, highlight the main mechanisms by which hydrocarbon-based fuel cell membranes deteriorate and point out the advancements that must be made to counteract “radical-induced membrane degradation” and the mechanical drawbacks of this kind of ionomers to make them competitive with and potentially even replace PFSA membranes.
Jiang Hongliang, et al. (2017) [41] expressed those vehicles powered by fuel cells are the cleanest and most efficient option. Particularly attractive for use in automobiles are proton-exchanged “membrane fuel cells”, which have a low operating temperature and a fast startup time. A great deal of work has gone into improving the efficiency of PEMFCs over the last decade. This includes making them more energy efficient, increasing their mass and volume power density, and making them better at starting up at low temperatures. Several famous car companies introduced fuel-cell vehicles to consumers in 2014. On the other hand, the high price and short lifespan of “PEMFC” classifications are still the main problems to the broad mechanization of this technology. The price and lifespan of PEMFCs are heavily influenced by their main components and materials. This review compiled and examined the scientific advancement of important materials and parts related to PEMFCs, such as the bipolar plate, gas diffusion layer, membrane, and catalytic layer. Furthermore, processing technologies with a high degree of durability are introduced. The review was completed with the author's personal views on potential future research directions in this area.
Wang Cheng, et al. (2016) [42] evaluated the most efficient and cleanest power source for cars as fuel cells. Because of their quick startup and low operating temperature, “protons exchange membrane fuel cells” in particular are the most promising option for automotive requests. The performance of “PEMFCs”, including energy efficacy, volumetric and form control density, and low-temperature setup capability, has significantly improved over the past ten years thanks to massive global research efforts. In 2014, several well-known automakers released “fuel cell-powered vehicles” onto the market. However, the primary barriers to the widespread industrialization of this technology remain the PEMFC systems' high cost and low durability. The primary materials and parts of PEMFCs have a significant impact on both their price and longevity. The technical development of important PEMFC-related materials and parts, including the membrane, catalytic “layer, gas diffusion layer, and bipolar plate” has been compiled and examined in this review.
Afsahi Foroughazam, et al. (2016) [43] investigated the effect of Nafion ionomer gratified on the proton exchange membrane fuel cell efficiency using experimental measurement and computational modeling. The fuel cell uses homemade anodized and cathodic electrodes made from a novel metal-organic framework derived from a Pt-based electrocatalyst. The purpose of the variable compassion analysis was to classify the model's most important parameters. Using the pertinent experimental data, the parameters were adjusted for the different fuel cell designs that were investigated in this work. The effect of the "Nafion content in the catalyst" layer of specially made electrodes was then examined using the calibrated model. The Nafion content in the catalyst layer of customized electrodes was varied from 10 to 50 weight percent to experimentally investigate the qualitative trend predicted by this model. The amount of Nafion had little effect on the performance of the handmade electrodes at the anode of a PEM fuel cell. The amount of Nafion in the cathodic manufactured electrode had a greater impact on the "PEM fuel cell's" performance.
Thiam H. S., et al. (2011) [44] said that fuel cells will soon be used to generate low- to emissions-free power for use in electric vehicles and portable technology. Considerable progress has been achieved with the fabrication of fuel cellular membranes using nanotechnology, enabling the creation of smaller fuel cells and high-quality solid electrolytes. It has been established that nanostructures are essential for enhancing fuel cell membrane performance. This study focused on the enhancement of fuel cell membranes through the use of these nanostructures and gives an overview of the development and research of nanostructured membranes for various fuel cell applications. This review also included theoretical studies that have been conducted using fuel cell membrane simulation and modeling at the molecular level. Additional concerns about the limits of technology, difficulties in research, and upcoming trends are also examined.
Mekhilef Saad, et al. (2012) [45] expressed that fuel cells produce electricity and heat through an electrochemical reaction that occurs between “oxygen and hydrogen”, subsequent in the foundation of water. Fuel cell technology presents a compelling solution for delivering energy to rural regions lacking access to the electrical grid or facing significant expenses related to the wiring and transmission of electricity. Furthermore, systems that have critical secure electrical energy needs, like uninterruptible electrical supplies, power generation stations, and distributed systems, can utilize fuel cells as their energy source. This review presented a comparative analysis of fundamental design, operational principles, applications, benefits, and drawbacks of different technologies utilized in fuel cells. The techno-economic characteristics of fuel cell hydrogen vehicles are compared with those of vehicles with internal combustion engines (ICEV). The findings demonstrate that fuel cell systems feature a straightforward design, exceptional reliability, silent process, high competence, and reduced ecological impact.
Wee Jung-Ho. (2007) [46] said that the PEMFCs have recently progressed beyond the testing or protest point and have partly attained commercialization, owing to significant global research endeavors. Notwithstanding the current promising advancements and feasible prospects of “PEMFCs”, numerous challenges persist that must be addressed before “PEMFCs” can effectively and economically replace various conventional energy systems. The most crucial resources for the commercialization of “PEMFC” determination are the technical data and insights derived from actual “PEMFC” application testing, amidst numerous promising research initiatives aimed at addressing these challenges. This paper presents and examines the ongoing challenges and recent research regarding the application testing of “PEMFC” in real-world systems, including transport, built-up energy production, and portable computing devices. This study delineated and encapsulates the comparative prospects and competitive dynamics of “PEMFCs” in these domains.
A
3. Background Study
The progress and widespread interest in graphene as a material for various uses were discussed in depth in this research. Emphasizing the role of graphene-based materials in electrocatalysts and membranes—two crucial components of systems—was the primary objective. Additionally, graphene and its derivatives, including graphene oxide (GO), sulfonated graphene oxide (SGO), and reduced graphene oxide (rGO), were introduced in this work along with their respective modification methods, unique features, and pros and cons. It goes on to talk about the capabilities and uses of graphene-based materials and CNTs utilized in electrocatalysts. The study discussed how graphene and its derivatives have been used in various applications, including fuel cells as efficient fuel blockers and conductors. Consequently, further advancements in graphene-based materials for fuel cell applications bode well for the future. Graphene and its derivatives have many potential uses, but they face obstacles that could restrict their widespread adoption. These include concerns over production volume, cost, electrical qualities, rivalry from other materials, and health and safety concerns. The review concluded by outlining all the possibilities and threats associated with commercialization [50].
Limited understanding of the long-term stability and degradation mechanisms of graphene-supported electro-catalysts under real-world operating conditions, including varying temperatures, humidity, and dynamic load cycles.
Insufficient research on optimizing the synthesis methods for uniform dispersion of electro-catalysts on graphene substrates to maximize surface area and enhance catalyst performance.
Lack of comparative studies that evaluate the cost-effectiveness and scalability of graphene-supported electro-catalysts compared to conventional catalysts in commercial-scale PEM fuel cells.
Inadequate investigation into the interaction of graphene with different types of electro-catalysts (e.g., platinum, non-precious metals) and their impact on both the catalytic activity and durability in varying fuel cell environments.
To evaluate graphene-supported electrocatalysts in PEM fuel cells for current density, power production, and efficiency.
To examine graphene-based electrocatalysts' endurance and stability in real-world conditions, including potential cycles and protracted use.
To investigate how graphene improves metal nanoparticle catalytic activity for oxygen reduction reactions (ORR) and hydrogen oxidation reactions.
To compare graphene-supported electrocatalysts to platinum-based catalysts in PEM fuel cell applications for cost and scalability.
6. Methodology
6.1 Formulation
The research on the Performance Evaluation of Graphene-Supported Electro-Catalysts in Proton Exchange Membrane (PEM) Fuel Cells aims to systematically assess and compare the efficiency of various electro-catalysts supported by graphene materials. This study focuses on improving PEM fuel cell performance by leveraging graphene's exceptional conductivity, mechanical strength, and large surface area, which are believed to enhance catalyst activity and durability. By exploring different metal-based catalysts such as platinum (Pt), nickel (Ni), and iron (Al), and analyzing their behavior in both acidic and alkaline environments, the study seeks to determine optimal configurations for catalytic efficiency. The research employs electrochemical testing, stability assessments, and performance metrics to identify the best-performing catalyst for PEM fuel cells, offering potential insights for advancements in fuel cell technology and renewable energy applications.
6.2 Research Layout
Material Synthesis and Characterization
Synthesize graphene-supported electrocatalysts using methods such as chemical vapor deposition (CVD) or hydrothermal techniques.
Characterize the synthesized electrocatalysts through scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD) to determine surface morphology, particle distribution, and structural integrity.
Perform electrochemical analysis such as cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) to determine the intrinsic catalytic properties of the materials.
Performance Testing in PEM Fuel Cells
Fabricate membrane electrode assemblies (MEAs) using the synthesized graphene-supported electrocatalysts.
Install the MEAs into a PEM fuel cell test station and subject them to controlled testing conditions, including variations in temperature, pressure, and humidity.
Measure performance parameters, including current density, power production, and efficiency, under varying load conditions and compare with standard platinum-based MEAs.
Analyze polarization curves and power density curves to assess the overall performance.
Durability and Stability Assessment
Conduct long-term operational testing by simulating real-world conditions, including continuous operation and accelerated stress tests, to evaluate the endurance of the graphene-based electrocatalysts.
Perform potential cycling tests, where the electrocatalysts are subjected to repeated oxidation and reduction cycles, to assess degradation rates.
Monitor changes in catalytic activity, current density, and power output over time to determine stability.
Catalytic Activity Investigation
Conduct detailed ORR and HOR studies using rotating disk electrode (RDE) techniques to assess the catalytic activity of the graphene-supported metal nanoparticles.
Compare the graphene-supported catalysts with traditional platinum-based catalysts for both ORR and HOR reactions.
Use Tafel plots to study the kinetics and determine the rate of the reactions, analyzing the role of graphene in enhancing catalytic performance.
Cost and Scalability Analysis
Perform a cost-benefit analysis by estimating the production cost of graphene-supported electrocatalysts in comparison to conventional platinum-based catalysts.
Evaluate the scalability of the graphene-supported electrocatalysts by assessing the feasibility of large-scale production techniques such as roll-to-roll processes.
Examine the economic viability in terms of raw material costs, manufacturing processes, and potential reduction in platinum usage.
Data Analysis and Comparative Study
Perform statistical analysis of the collected data, comparing the performance, durability, and catalytic activity of graphene-supported and platinum-based electrocatalysts.
Use software tools like OriginPro or MATLAB to generate comparative graphs and visualizations.
Interpret the results to conclude the overall suitability of graphene-supported electrocatalysts in PEM fuel cells based on performance, cost-effectiveness, and scalability.
Materials and Methods:
Materials and Synthesis of Electrocatalyst:
Sulphuric Acid (H2SO4, 98%)
Potassium Permanganate (KMnO4)
Carboxy Methyl Cellulose (CMC)
The details of compositions of all the 40 catalyst samples are tabulated below:
A
Table 1
compositions of catalyst samples
Sample No
|
Activated Charcoal
|
NiO
|
TiO2
|
CuO
|
Kept in Ice bath (Hrs)
|
1
|
1g
|
0.5g
|
--
|
--
|
1
|
2
|
1g
|
0.5g
|
--
|
--
|
3
|
1g
|
0.5g
|
--
|
--
|
4
|
1g
|
0.5g
|
--
|
--
|
5
|
1g
|
0.5g
|
--
|
--
|
6
|
1g
|
--
|
0.5g
|
--
|
7
|
1g
|
--
|
0.5g
|
--
|
8
|
1g
|
--
|
0.5g
|
--
|
9
|
1g
|
--
|
0.5g
|
--
|
10
|
1g
|
--
|
0.5g
|
--
|
11
|
1g
|
--
|
1g
|
1g
|
2
|
12
|
1g
|
--
|
1g
|
1g
|
6
|
13
|
1g
|
--
|
1g
|
1g
|
12
|
14
|
1g
|
--
|
1g
|
1g
|
24
|
15
|
1g
|
--
|
1g
|
1g
|
35
|
16
|
1g
|
1g
|
1g
|
1g
|
2
|
17
|
1g
|
1g
|
1g
|
1g
|
6
|
18
|
1g
|
1g
|
1g
|
1g
|
12
|
19
|
1g
|
1g
|
1g
|
1g
|
24
|
20
|
1g
|
1g
|
1g
|
1g
|
35
|
21
|
1g
|
1g
|
--
|
1g
|
2
|
22
|
1g
|
1g
|
--
|
1g
|
6
|
23
|
1g
|
1g
|
--
|
1g
|
12
|
24
|
1g
|
1g
|
--
|
1g
|
12
|
25
|
1g
|
1g
|
--
|
1g
|
35
|
26
|
--
|
1g
|
1g
|
1g
|
2
|
27
|
--
|
1g
|
1g
|
1g
|
6
|
28
|
--
|
1g
|
1g
|
1g
|
12
|
29
|
--
|
1g
|
1g
|
1g
|
24
|
30
|
--
|
1g
|
1g
|
1g
|
35
|
31
|
1g
|
0.5g
|
0.5g
|
--
|
1
|
32
|
1g
|
0.5g
|
0.5g
|
--
|
33
|
1g
|
0.5g
|
0.5g
|
--
|
34
|
1g
|
0.5g
|
0.5g
|
--
|
35
|
1g
|
0.5g
|
0.5g
|
--
|
36
|
1g
|
--
|
--
|
0.5g
|
37
|
1g
|
--
|
--
|
0.5g
|
38
|
1g
|
--
|
--
|
0.5g
|
39
|
1g
|
--
|
--
|
0.5g
|
40
|
1g
|
--
|
--
|
0.5g
|
Membrane Electrode Assembly (MEA):
Following membranes (with catalyst) were prepared:
A
Table 2
Different Membrane Electrode Assembly
Sl. No.
|
Material
|
%
|
Catalyst Used
|
|
Na Alginate
|
20%
|
NiO2, TiO2, GO
|
3
|
Na Alginate
|
40%
|
NiO2, GO & TiO2
|
4
|
Na Alginate
|
50%
|
NiO2, GO & TiO2
|
6
|
Na Alginate
|
60%
|
NiO2, GO & TiO2
|
15
|
CMC
|
10%
|
Activated Charcoal, TiO
|
16
|
CMC
|
10%
|
NiO2, TiO2, CuO, GO
|
17
|
CMC
|
10%
|
CuO, NiO2, GO
|
18
|
CMC
|
20%
|
Activated Charcoal, TiO
|
19
|
CMC
|
20%
|
Activated Charcoal, TiO
|
20
|
CMC
|
25%
|
Activated Charcoal, TiO
|
To make the solutions acidic at the same temperature, sulfuric acid was added. Afterwards, a buffer solution containing acetic acid and methanol was added in accordance with the solution's volume. Glutaraldehyde was added as a crosslinker after the solution had been thoroughly stirred for 20 to 25 minutes. The solution was cast into glass plates using the phase inversion technique, also known as solution casting technique, after adding glutaraldehyde for two minutes. After casting, the mixture was left overnight and dried in a hot air furnace between 70 and 80 degree Celsius the next day. The membranes detached from the glass plates after drying for 25 to 30 minutes because the volume expansion coefficients of polymers and glass varied.
Result & Discussion:
Membrane Testing:
1. 20% Na Alginate + NiO + TiO2
TA Report
The thermal analysis (TA) picture for 20% Na Alginate and 20% Na Alginate + NiO + TiO2. We will examine it within the framework of the Performance Evaluation of Graphene-Supported Electro-Catalysts in Proton Exchange Membrane (PEM) Fuel Cells. There is an indirect relationship between the general performance and behavior of electro-catalysts in fuel cells and the information provided by the thermal analysis (TA) graphs, which show how stable a material is under heat circumstances.
Review of Fig. 6: 20% TA Na Alginate Beginning the Breakdown Process: At lower temperatures (probably between ambient temperature and around 150°C), the TA curve reveals a first drop in weight or thermal response. Since alginates normally retain water, this signifies either dryness or the evaporation of moisture content.
A notable decrease in slope of the curve at 200–300°C indicates that Na Alginate is thermally decomposing. This may line up with the decomposition of organic substances in the alginate.
Because alginate and other materials used in PEM fuel cells can affect the longevity of the catalyst supports and membranes, heat stability is an important property to look for in these cells. The high temperatures usually experienced in PEM fuel cell operations can be too much for Na Alginate, according to the decomposition temperature.
Extraction of the Initial Dehydration Solution from Fig. 7: TA of 20% Na Alginate + NiO + TiO2 The TA curve starts with a drop in weight, maybe because water evaporates, just like the pure Na Alginate in Fig. 6.
Effects of NiO and TiO2: With a small shift toward a higher breakdown temperature range (about 300–400°C), the thermal curve here appears more stable compared to Fig. 6. Adding NiO and TiO2 improves thermal stability, according to this. The material's potential utility as an electro-catalyst may be enhanced by the presence of NiO and TiO2, which probably increase its heat resistance.
Why This Matters for PEM Fuel Cells:
Improved catalyst stability at PEM fuel cell operating temperatures may be a consequence of the enhanced thermal characteristics brought about by the combination of NiO and TiO2.
Incorporating catalysts like NiO and TiO2 into the matrix (like alginate) could improve fuel cell performance because of their catalytic capabilities.
Prolonged efficiency in PEM fuel cells is closely related to improved thermal stability, which affects catalyst durability.
Findings from Comparisons
Comparison of Na Alginate with Na Alginate + NiO + TiO2: The composite of Na Alginate, NiO, and TiO2 has superior thermal stability over pure Na Alginate, since it does not decompose at higher temperatures. Given the high temperatures experienced by a PEM fuel cell, this indicates that the composite material may provide more stable thermal behavior.
While thermal stability is the primary focus of TA study, the materials' potential to enhance electro-catalyst efficiency is also implicitly supported. PEM fuel cells may benefit from the redox reactions facilitated by NiO and TiO2, which are well-known for their catalytic capabilities, which could improve fuel conversion efficiency and decrease overpotentials.
2. 50% Na Alginate + NiO + GO + TiO2
TA Report
Figure 8: Dehydration Phase TA of 50% Na Alginate: The first dip in the curve at about 100°C, like in earlier TA curves at lower concentrations, represents water loss by evaporation.
As the Na Alginate matrix decomposes, a sharp drop in the graph occurs between 200 and 300°C, indicating thermal disintegration. This sample may show more signs of heat degradation than the 20% Na Alginate one because the concentration of Na Alginate is 50%.
PEM fuel cells via this lens:
There are still issues with the thermal stability of pure sodium alginate. Given its degradation tendency between 200 and 300°C, it's possible that even at larger concentrations, the material won't hold up well in the high-temperature environments typical of PEM fuel cells.
Figure 9: TA of a mixture of 50% sodium alginate, nickel oxide, and titanium dioxide
Enhancement of Thermal Stability: Mixing 50% Na Alginate with NiO and TiO2 improves the material's thermal behavior again. In this scenario, the deterioration is postponed, and the curve remains more consistent up to temperatures of 300°C and beyond. The increased resistance to heat suggests that the incorporation of NiO and TiO2 is crucial in postponing degradation.
Looking at PEM fuel cells via this lens:
The addition of the catalytically active elements NiO and TiO2 enhances the material's thermal and catalytic characteristics.
Since thermal stability is critical to preserving efficient electro-catalytic performance, the material's ability to withstand a wider temperature range is an advantage for PEM fuel cells that operate for extended periods of time.
SEM
Figure 10: Water Absorption by 50% Na Alginate Initial weight loss around 100°C is caused by moisture evaporation, as seen in earlier TA graphs.
Thermal Decomposition: According to the results observed at other concentrations, pure Na Alginate starts to degrade at temperatures ranging from 200 to 300°C, where significant decomposition begins. Due to the absence of additives, the polymer matrix exhibits relative instability when subjected to high temperatures.
Accordingly, for PEM fuel cells, operating at high temperatures requires more than 50% Na Alginate to achieve adequate thermal stability.
To improve thermal stability, see Fig. 11 for the TA of 50% Na Alginate, NiO, GO, and TiO2. When compared to pure sodium alginate, the thermal stability is significantly enhanced by adding nickel oxide, graphene oxide, and titanium dioxide. Less extreme weight loss and more consistent behavior throughout a wider temperature range are observed in the TA curve.
The presence of NiO, GO, and TiO2 in the composite increases its thermal endurance, which in turn prevents decomposition. The material maintains its thermal stability even when subjected to temperatures beyond 300°C.
Compared to PEM fuel cells, this composite has considerably more potential:
Oxide of graphene (GO): Both the material's electrical conductivity and its structural stability are improved by adding GO. PEM fuel cells may benefit from GO's stabilizing properties, which could lead to improved catalyst performance.
Composites reinforced with NiO and TiO2 have enhanced thermal and catalytic characteristics, making them better suited to withstand the high temperatures and operational stresses of PEM fuel cells.
XRD
Measurement condition
X-Ray
|
40 kV, 15 mA
|
Scan speed / Duration time
|
10.0000 deg./min.
|
Goniometer
|
|
Step width
|
0.0200 deg.
|
Attachment
|
-
|
Scan axis
|
2Theta/Theta
|
Filter
|
K-beta(x1.5)
|
Scan range
|
3.0000–90.0000 deg.
|
CBO selection slit
|
-
|
Incident slit
|
-
|
Diffrected beam mono.
|
None
|
Length limiting slit
|
-
|
Detector
|
D/teX Ultra2
|
Receiving slit #1
|
-
|
Scan mode
|
CONTINUOUS
|
Receiving slit #2
|
-
|
Factors Influencing Assessment
X-ray Source: The XRD measurements were carried out using a conventional setup for X-ray generation in diffraction investigations, which consists of 40 kV and 15 mA.
Scanning Time and Pace: The 2Theta range was covered at a speed of 10,000 degrees per minute. The presence of both low- and high-angle diffraction peaks is usually captured within this range, giving a comprehensive view of the crystalline phases.
Step Width and Goniometer: Precise peak identification and phase analysis are guaranteed by the 0.0200 degree step width, which is tiny enough to resolve fine diffraction pattern characteristics.
Detector and Filter: To minimize undesirable X-ray wavelength interference, a K-beta filter (x1.5) is employed, and the D/teX Ultra2 detector offers great sensitivity in detecting diffracted beams.
Scan Mode: Enhance the quality of the diffraction pattern with uninterrupted, smooth data collecting in the continuous scan mode.
A
Figure 12: Crystallinity Analysis of 50% Na Alginate by XRD: The broad peaks seen in the XRD pattern of 50% Na Alginate are indicative of amorphous or semi-crystalline nature. The arrangement of the polysaccharide chains determines the broad peaks around specific 2Theta values, and because Na Alginate is a biopolymer, it usually has restricted crystallinity.
Since the XRD pattern does not show any prominent peaks, it is likely that Na Alginate is mostly amorphous and has very few ordered regions.
Because of its amorphous structure, Na Alginate is not ideal for uses that demand high structural integrity and electrochemical performance, such as PEM fuel cells, where it may cause problems with mechanical stability and ion transport.
A
The XRD peaks of a solution containing 50% sodium alginate, nickel oxide, graphite oxide, and titanium dioxide are shown in Fig. 13. It is anticipated that the XRD pattern will display more pronounced peaks upon the addition of NiO, GO, and TiO2, signifying the existence of crystalline phases.
Typical diffraction peaks for NiO are observed at 37.3°, 43.3°, and 62.8°, all of which correspond to the cubic structure.
The rutile form of TiO2 can show peaks at 27.4°, 36.1°, and 54.3°, whereas the anatase form typically shows peaks at 25.3°, 37.8°, and 48.0°.
Despite its mostly amorphous nature, graphene oxide (GO) can exhibit either a broad peak at approximately 11° or acute peaks near 25° in the case of partial reduction.
Composites with these peaks have a higher degree of crystallinity than pure Na Alginate, which is good for PEM fuel cell structural stability and electrochemical performance.
Crystallite size and lattice strain
Williamson-Hall method
Data set name
|
Crystallite size(A)
|
Strain(%)
|
231067-A_Theta_2-Theta
|
-
|
-
|
Phase name
|
Crystallite size(A)
|
Distribution RSD
|
Strain(%)
|
Distribution type
|
Amorphous
|
-
|
-
|
-
|
-
|
X-ray diffraction (XRD) investigation, the Williamson-Hall (W-H) method is employed to differentiate between the impacts of microstrain and crystallite size on the XRD peak broadening. By examining peak broadening, it assists in estimating the size of the crystallites and microstrain in a material provide information regarding the size of the crystallites and the strain (in percentage terms) of the materials as shown in the XRD patterns, maybe with reference to Figs. 14 and 15.
Figure 14 Fig. 15
Assuming that Fig. 14 and Fig. 15 pertain to XRD, the following is an explanation of what you can anticipate from both figures:
The XRD analysis for an amorphous material is likely depicted in Fig. 14, where broad peaks or the absence of prominent peaks is noted. The absence of long-range order implies that the Williamson-Hall method cannot be used to determine crystallite size or strain.
The atomic groupings are disorderly in an amorphous material.
Since there are no crystalline peaks, we cannot extract any data on crystallite size.
Figure 15 shows an example of XRD data from a crystalline or semi-crystalline material that could be used with the Williamson-Hall method. In this case, the W-H analysis can be used to determine the microstrain and crystallite size from the XRD pattern, which should show stronger peaks.
Peak broadening allows one to determine the size and strain of crystallites.
The percentage of strain provides an approximation of the internal deformation or distortion caused by flaws or outside influences on the crystal lattice.
Comparative performance
the analysis of a PEM fuel cell's performance, which shows that the power output increases linearly with current density, reaching a maximum of about 2.5 W/cm² at 2 A/cm². Nevertheless, the efficiency is consistently poor at approximately 1.057 × 10⁻³%, indicating that there may be substantial energy losses as a result of high overpotentials, maybe insufficient catalyst activity, or the use of inappropriate settings for activation, ohmic, and concentration losses. Modifying these loss values, collecting validation data from the real world, and thinking about doing a more in-depth analysis that takes additional elements like temperature impacts and electrochemical reaction kinetics into consideration.
Conclusion- The Performance study of graphene-supported electro-catalysts in proton exchange membrane (PEM) fuel cells reveals an encouraging power output that grows in a linear fashion with current density; on the other hand, the extremely poor efficiency suggests possible difficulties in effectively converting energy. There has to be a reassessment of the model's loss parameters and additional research into the catalysts' electrochemical activity to explain the power output/efficiency mismatch. Future research should aim to optimize catalyst compositions, operational conditions, and modeling techniques to account for all relevant factors; this will lead to better PEM fuel cell performance and energy efficiency.