In recent decades, fuel cell technology has been undergoing revolutionary developments, with fundamental progress being the replacement of electrolyte solutions with polymer electrolytes, making the device more compact in size and higher in power density. Nowadays, acidic polymer electrolytes, typically Nafion, are widely used. Despite great success, fuel cells based on acidic polyelectrolyte still depend heavily on noble metal catalysts, predominantly platinum (Pt), thus increasing the cost and hampering the widespread application of fuel cells. Here, we report a type of polymer electrolyte fuel cells (PEFC) employing a hydroxide ionconductive polymer, quaternary ammonium polysulphone, as alkaline electrolyte and nonprecious metals, chromium-decorated nickel and silver, as the catalyst for the negative and positive electrodes, respectively. In addition to the development of a high-performance alkaline polymer electrolyte particularly suitable for fuel cells, key progress has been achieved in catalyst tailoring: The surface electronic structure of nickel has been tuned to suppress selectively the surface oxidative passivation with retained activity toward hydrogen oxidation. This report of a H2-O2 PEFC completely free from noble metal catalysts in both the positive and negative electrodes represents an important advancement in the research and development of fuel cells.nonprecious metals ͉ hydrogen oxidation ͉ oxygen reduction F uel cells have been recognized as an alternative powergeneration technique for the future in both mobile and stationary uses (1, 2). After decades of evolution, fuel cells of various types have been developed (2), such as alkaline fuel cell (AFC), phosphoric acid fuel cell (PAFC), molten carbonate fuel cell (MCFC), solid oxide fuel cell (SOFC), and polymer electrolyte fuel cell (PEFC). Among them, PEFC has been the most developed one in the past 2 decades (3), featuring rapid startup and high power density particularly suitable for vehicle applications (1-3).Compared with the aqueous electrolytes traditionally used in low-temperature fuel cells, polymer electrolytes completely eliminate the problems caused by electrolyte leakage and can effectively separate the fuels (such as hydrogen) and the oxidant (oxygen) with a thin film of a few tens of microns in thickness. For decades, the commonly used polymer electrolytes have been limited to proton exchange membranes, typically Nafion . Nowadays, many Nafion-based fuel cell systems of different sizes are being demonstrated or tested on a variety of applications across the world. Although they are promising, the Nafion-based fuel cells still face a number of obstacles to commercialization, one of which has been the severe dependence of catalysts on platinum (Pt), an expensive and scarce resource in the earth. Such dependence stems from the strong acidic nature of the protonexchange membrane; and thermodynamically, only noble metals can be relatively stable in this corrosive environment. Despite tremendous efforts devoted to the search for non-...
A current challenge to alkaline polymer electrolyte fuel cells (APEFCs) is the unexpectedly sluggish kinetics of the hydrogen oxidation reaction (HOR). A recently proposed resolution is to enhance the oxophilicity of the catalyst, so as to remove the H ad intermediate through reacting with OH ad , but this approach is questioned by other researchers.Here we report a clear and convincing test on this problem. By using PtRu/C as the HOR catalyst for APEFC, the peak power density is boosted to 1.0 W/cm 2 , in comparison to 0.6 W/cm 2 when using Pt/C in the anode. Such a remarkable improvement, however, can hardly be explained as an oxophilic effect, because, as monitored by CO stripping, reactive hydroxyl species can generate on certain sites of the Pt surface at more negative potentials than on the PtRu surface in KOH solution. Rather, the incorporation of Ru has posed an electronic effect on weakening the Pt-H ad interaction, as revealed by the voltammetric behavior and from density-functional calculations, which thus benefits the oxidative desorption of H ad , the rate determining step of HOR in alkaline media. These findings further our fundamental understanding of the HOR catalysis, and cast a new light on the exploration of better catalysts for APEFC. 5 process to monitor the generation of reactive hydroxyl species, for the anodic current of CO oxidation has to be triggered by reactive hydroxyl species. 31 As demonstrated in Figure 2, in 0.1 M H 2 SO 4 solution, the CO stripping on Pt/C takes on a single sharp peak at 0.85 V, and, upon alloying with Ru, the CO stripping peak is somewhat broadened and moves negatively by 0.3 V, showing that Ru does accelerate the formation of OH ad in acidic environment.However, the CO stripping on Pt/C behaves rather differently in 0.1 M KOH solution: multiple anodic peaks appear and the onset potential shifts to ~0.2 V, a potential even more negative than the onset of CO stripping on PtRu/C (~0.35 V) in either acid or alkaline media.Such a surprising finding indicates that, in alkaline environment, the reactive hydroxyl species, be it OH ad or OH ad − , can generate on certain sites of the Pt surface more favorably than on the PtRu surface; but when alloyed with Ru, the surface reactivity of Pt is suppressed, thereby no reactive hydroxyl species appearing at the potential region negative to 0.35 V.On the basis of the above observations, the promotion effect of Ru on catalyzing the HOR in alkaline media can hardly be explained as an oxophilic effect. The existence of reactive hydroxyl species on either Pt or PtRu surface at potentials negative to 0.2 V also seems unlikely, as revealed by Figure 2. On the other hand, the Ru has posed an obvious effect on weakening the Pt-H ad interaction, as a consequence of the suppressed surface reactivity of Pt. As illustrated in Figure 3a, in KOH solution, the hydrogen underpotential deposition (H-UPD) and subsequent desorption behavior on PtRu/C is clearly different from that on Pt/C: whereas strong H ad peaks are the major signal for Pt/C...
Although the polymer electrolyte fuel cell (PEFC) is a superior power source for electric vehicles, the high cost of this technology has served as the primary barrier to the large-scale commercialization. Over the last decade, researchers have pursued lower-cost next-generation materials for fuel cells, and alkaline polymer electrolytes (APEs) have emerged as an enabling material for platinum-free fuel cells. To fulfill the requirements of fuel cell applications, the APE must be as conductive and stable as its acidic counterpart, such as Nafion. This benchmark has proved challenging for APEs because the conductivity of OH(-) is intrinsically lower than that of H(+), and the stability of the cationic functional group in APEs, typically quaternary ammonia (-NR(3)(+)), is usually lower than that of the sulfonic functional group (-SO(3)(-)) in acidic polymer electrolytes. To improve the ionic conductivity, APEs are often designed to be of high ion-exchange capacity (IEC). This modification has caused unfavorable changes in the materials: these high IEC APEs absorb excessive amounts of water, leading to significant swelling and a decline in mechanical strength of the membrane. Cross-linking the polymer chains does not completely solve the problem because stable ionomer solutions would not be available for PEFC assembly. In this Account, we report our recent progress in the development of advanced APEs, which are highly resistant to swelling and show conductivities comparable with Nafion at typical temperatures for fuel-cell operation. We have proposed two strategies for improving the performance of APEs: self-cross-linking and self-aggregating designs. The self-cross-linking design builds on conventional cross-linking methods and works for APEs with high IEC. The self-aggregating design improves the effective mobility of OH(-) and boosts the ionic conductivity of APEs with low IEC. For APEs with high IEC, cross-linking is necessary to restrict the swelling of the membrane. In our self-cross-linking design, a short-range cross-linker, tertiary amino groups, is grafted onto the quaternary ammonia polysulfone (QAPS) so that the cross-linking process can only occur during membrane casting. Thus, we obtain both the stable ionomer solution and the cross-linked membrane. The self-cross-linked QAPS (xQAPS) possesses a tight-binding structure and is highly resistant to swelling: even at 80 °C, the membrane swells by less than 3%. For APEs with low IEC, the key is to design efficient OH(-) conducting channels. In our self-aggregating design, long alkyl side-chains are attached to the QAPS. Based on both the transmission electron microscopy (TEM) observations and the molecular dynamics (MD) simulations, these added hydrophobic groups effectively drive the microscopic phase separation of the hydrophilic and hydrophobic domains and produce enlarged and aggregated ionic channels. The ionic conductivity of the self-aggregated QAPS (aQAPS) is three-fold higher than that of the conventional QAPS and is comparable to that of Nafio...
Although the proton exchange membrane fuel cell (PEMFC) has made great progress in recent decades, its commercialization has been hindered by a number of factors, among which is the total dependence on Pt‐based catalysts. Alkaline polymer electrolyte fuel cells (APEFCs) have been increasingly recognized as a solution to overcome the dependence on noble metal catalysts. In principle, APEFCs combine the advantages of and alkaline fuel cell (AFC) and a PEMFC: there is no need for noble metal catalysts and they are free of carbonate precipitates that would break the waterproofing in the AFC cathode. However, the performance of most alkaline polyelectrolytes can still not fulfill the requirement of fuel cell operations. In the present work, detailed information about the synthesis and physicochemical properties of the quaternary ammonia polysulfone (QAPS), a high‐performance alkaline polymer electrolyte that has been successfully applied in the authors' previous work to demonstrate an APEFC completely free from noble metal catalysts (S. Lu, J. Pan, A. Huang, L. Zhuang, J. Lu, Proc. Natl. Acad. Sci. USA 2008, 105, 20611), is reported. Monitored by NMR analysis, the synthetic process of QAPS is seen to be simple and efficient. The chemical and thermal stability, as well as the mechanical strength of the synthetic QAPS membrane, are outstanding in comparison to commercial anion‐exchange membranes. The ionic conductivity of QAPS at room temperature is measured to be on the order of 10−2 S cm−1. Such good mechanical and conducting performances can be attributed to the superior microstructure of the polyelectrolyte, which features interconnected ionic channels in tens of nanometers diameter, as revealed by HRTEM observations. The electrochemical behavior at the Pt/QAPS interface reveals the strong alkaline nature of this polyelectrolyte, and the preliminary fuel cell test verifies the feasibility of QAPS for fuel cell applications.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.