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1.
La0.5(Ba0.75Ca0.25)0.5Co0.8Fe0.2O3-δ, a simple perovskite cathode material with high electrical conductivity (940 S cm?1 at 600 °C) and impressive surface catalytic activity, was prepared and used in proton-conducting solid oxide fuel cells. As its thermal expansion coefficient is higher than that of the electrolyte material BaZr0.1Ce0.7Y0.1Yb0.1O3-δ, they were combined and used as a composite cathode. The crystal structure, chemical compatibility, electrical conductivity, cell performance, and the oxygen reduction reaction of the cathode material were explored, and we found that the single fuel cell developed with the composite cathode achieved excellent electrochemical performance, with both a low polarization resistance and high peak power density (0.044 Ω cm2 and 1102 mW cm?2 at 750 °C, respectively). Outstanding stability was also achieved, as indicated by a long-term 100-h test. Additionally, the rate-limiting steps of the oxygen reduction reaction were the oxygen adsorption, dissociation, and diffusion processes.  相似文献   

2.
Heteropoly acids have been employed to increase the proton conductivity of phosphoric acid (PA) doped polymer membranes for high temperature polymer electrolyte membrane fuel cells (HT-PEMFCs). In this work, we develop a new composite membrane based on phosphotungstic acid (PWA) doped polyethersulfone-polyvinylpyrrolidone (PES-PVP) matrix, forming PWA/PES-PVP composite membrane for HT-PEMFCs. The homogeneous distribution of PWA on the PES-PVP membrane enhances its mechanical strength. In addition, there is a strong interaction between PWA and PA that is confirmed experimentally by the attenuated total reflectance Fourier Transform Infrared spectroscopy and semi-empirical quantum mechanics calculation. This enhances not only the PA uptake but also the proton conductivity of the PWA/PES-PVP composite membrane. 1H nuclear magnetic resonance spectroscopy results elucidate that the high proton conductivity of the PA doped PWA/PES-PVP membranes is due to their higher proton content and mobility compared to the pristine PA doped PES-PVP membrane. The best results are observed on the PES-PVP composite membrane with addition of 5 wt% PWA, reaching proton conductivity of 1.44 × 10?1 S cm?1 and a peak power density of 416 mW cm?2 at 160 °C and anhydrous conditions. PWA additives increase the proton conductivity and cell performance, demonstrating significantly positive effects on the acid-base composite membranes for high temperature polymer electrolyte membrane fuel cell applications.  相似文献   

3.
BaZr0.5Y0.5O3(BZY) electrolyte exhibited enormous potential for low temperature solid oxide fuel cell (SOFC) due to its proton dominant mobile carriers rather than oxygen ions during the electrochemical process. In order to enhance the ionic conductivity, triple conductor BaCo0.4Fe0.4Zr0.1Y0.1O3-δ (BCFZY) was composited with proton conductor BZY to form semiconductor-ionic conductor composite (SIM), which was applied as electrolyte to fabricate symmetrical fuel cell. The microstructural and electrochemical properties for BZY, BCFZY and BZY-BCFZY composites were studied. After optimizing the weight ratio of composite content, the ionic conductivity and electronic conductivity reached an equilibrium state to obtain the maximum cell performance, namely the highest output of 902.5 mW cm?2 and an open circuit voltage (OCV) of 1.043 V at 550 °C. The BZY-BCFZY cell also presented decent power output at low temperature, a power density of 265.625 mW cm?2 was received even at 500 °C, demonstrating that the BZY-BCFZY composite was a potential electrolyte for low temperature SOFCs.  相似文献   

4.
The interfacial properties of electrolyte materials have a crucial impact on the ionic conductivity of solid batteries and solid oxide fuel cells. Here we construct cuprospinel CuFe2O4 (CFO)–ZnO composite as a functional electrolyte for fuel cell device. In an optimal composition of 0.3CFO-0.7ZnO electrolyte fuel cell, the maximum power output of 675 mW cm?2 is obtained at 550 °C. The electrical properties and electrochemical performance are strongly dependent on the ratios between CFO and ZnO in CFO-ZnO composite. Notably, surprising fuel cell performance with high ionic conductivity is attained by constructing this p-type CFO composited with n-type ZnO. Proton conduction was further verified experimentally. The interfacial ionic conduction pathway between the two constituent phases plays a vital role to enhance the proton conductivity, and the bulk p-n heterojunction can block internal electronic pass. An excellent current and power densities of CFO-ZnO composite are observed along with a high conductivity of 0.35 S·cm-1 at 550 °C. This work opens a new perspective for the semiconductor materials that can widely be developed for electrolytes, based on their tunable band structure.  相似文献   

5.
An ionic-conducting electrolyte mainly governs the solid oxide fuel cell performance. In this work, a mixed conductor NdBa0.5Sr0.5Co1.5Fe0.5O5+δ was tuned as an electrolyte via compositing with a proton conductor BaZr0.3Ce0.6Y0.1O3- δ (BZCY), which realizes an ionic conductivity of 0.16 S cm?1 at 550 °C along with fuel cell power density of 470 mW cm?2. The 10 wt.% proton conducting BZCY can not only effectively block the electronic conductivity of NBSCF, but also greatly improve its ionic conductivity and the corresponding device's power output. The interfacial conduction could take a crucial role in the ion transporting process of BZCY-NBSCF composite. These interfaces or nanoscale grain boundaries formed amongst two phases keep excellent capability for designing and creating high performance electrochemical devices along with high-power density.  相似文献   

6.
To increase proton conductivity of chitosan (CS) based polymer electrolyte membranes, a novel nanofiller-solid superacide SO42--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.  相似文献   

7.
In order improve the fuel cell performance of a free-standing graphene oxide (GO) membrane, the impacts of both the additional oxidation of GO and the modification with vinilsulfonic acid were investigated. The modification with vinilsulfonic acid was conducted with and without adding potassium persulfate, K2S2O8, which is a radical initiator for the polymerization of vinylsulfonate. A total of six types of free-standing GO membranes with and without the oxidation and/or the modification were prepared. The oxidation and the modification additively increased the proton conductivity, and the oxidation significantly improved the durability of the fuel cell performance at 30 °C. The membrane of GOhvsi, of which GO was oxidized and modified with the initiator, showed very high in-plane proton conductivities at 30 °C, i.e., 0.54 S cm?1 at RH 100%. The H2–O2 fuel cell using GOhvsi showed maximum power densities as high as 136 mW cm?2 and 184 mW cm?2 at 30 °C and 50 °C, respectively. The performance at 30 °C was stable for more than 20 h. The improved durability by the oxidation was attributed to the increased defects of carbon based on an XPS analysis. The TPD-MS analysis suggested that the oxygenated functional groups at the defects would increase the binding strength.  相似文献   

8.
The objective of this work is to prepare a functional copolymer of poly(acrylonitrile)-co-poly(2-Acrylamido-2-methyl-1-propanesulfonic acid) (PAN-co-PAMPS) and impregnation of graphene oxide (GO) into the copolymer followed by crosslinking to prepare conetwork composite membranes by simple and cost effective solution casting method and evaluating their structural, morphological, thermal, and mechanical properties. The successful incorporation of different amounts of GO content (0.1–1 wt%) within the polymer matrix was confirmed by FT-IR spectroscopy, X-ray diffraction, transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The mechanical properties of the prepared crosslinked composite membranes are found to be greatly enhanced by the addition of GO in the copolymer matrix. The thermogravimetric analysis (TGA) demonstrated considerable improvements in thermal stability for the composite membrane with low GO content. The effect of loading of GO in the copolymer matrix on proton conductivity and fuel cell performance has been studied systematically. The membranes prepared by mixing with 0.5 wt% GO in the copolymer followed by crosslinking exhibited maximum ionic conductivity (Km), lower methanol permeability (PM), and higher relative selectivity. This observed PM value is much lower range from 3.02 × 10?7 to 11.9 × 10?7 cm2/s compared to the Nafion® 117 membrane (22 × 10?7 cm2/s). The fuel cell performance in terms of maximum power density and current density and the durability of the crosslinked composite membranes have also been evaluated here. Low PM, high Km, and high selectivity values show that functional co-polymer/GO crosslinked co-network composite membrane is a promising alternative membrane separator to replace the expensive Nafion® 117 for proton exchange membrane fuel cells (PEMFCs) application.  相似文献   

9.
Recent advances in composite materials, especially semiconductor materials incorporating ionic conductor materials, have led to significant improvements in the performance of low-temperature fuel cells. In this paper, we present a semiconductor LNCA (LiNi0.8Co0.15Al0.05O2-δ) which is often used as electrode material and ionic Sm-doped ceria (SDC; Ce0.8Sm0.2O2-δ) composite electrolyte, sandwiched between LNCA thin-layer electrodes in a configuration of Ni-LNCA/SDC-LNCA/LNCA-Ni. The incorporation of the semiconductor LNCA into the SDC electrolyte with optimized weight ratios resulted in a significant power improvement, from 345 mW cm?2 with a pure SDC electrolyte to 995 mW cm?2 with the ionic-semiconductor SDC-LNCA one where the corresponding ionic conductivity reaches 0.255 S cm?1 at 550 °C. Interestingly, the coexistence of ionic and electron conduction in the SDC-LNCA membrane displayed not any electronic short-circuiting but enhanced the device power outputs. This study demonstrates a new fuel cell working principle and simplifies technologies of applying functional ionic-semiconductor membranes and symmetrical electrodes to replace conventional electrolyte and electrochemical technologies for a new generation of fuel cells, different from the conventional complex anode, electrolyte, and cathode configuration.  相似文献   

10.
Direct ethanol fuel cells (DEFCs) emerge as the new research energy field since fast production of electricity, high efficiency conversion, and simple fabrication process. The production cost, conductivity properties, and ethanol permeability of membrane were the main problem that limited the DEFC performance and commercialization. In this study, a low cost, good ionic conductivity and low ethanol permeability of an anion exchange membrane based on incorporation KOH‐doped quaternized poly(vinyl alcohol) (QPVA) membrane (designed as QPVA/KOH) is synthesized and cross‐linked with glutaraldehyde solution. The membrane is expected to cut the production cost and enhance the performance. In this work, an optimum of alkali‐doped concentration has influence the membrane performance. The membrane has reveal high chemical stability even doped with 8‐M KOH solution in 100°C. The morphology of membranes remained unbreakable and achieved high range of ionic conductivity (~10?2 S cm?1). The membranes present maximum ionic conductivity 1.29 × 10?2 S cm?1 at 30°C and 3.07 × 10?2 S cm?1 at 70°C. The ethanol permeability of membrane is lower compared with the commercial membranes. Power density of alkaline DEFCs with platinum‐based catalyst by using cross‐linked QPVA/KOH membrane is 5.88 mW cm?2, which is higher than commercial membranes at 30°C temperature. At 70°C, power density has increased up to 11.28 mW cm?2 and significantly increased up to 22.82 mW cm?2 via the nonplatinum‐based catalyst. Moreover, according to the durability test, the performance of passive alkaline DEFC by using cross‐linked QPVA/KOH membrane has maintained at 36.2% level. With such efficiency, the stack current density has been able to stay above 120 mA cm?2 for over 1000 hours, at 70°C.  相似文献   

11.
In our previous work, phosphorylated chitosan was modified through polymer blending with poly(vinyl alcohol) (PVA) polymer to produce N-methylene phosphonic chitosan/poly(vinyl alcohol) (NMPC/PVA) composite membranes. The aim of this work is to further investigate the effects of a propylammonium nitrate (PAN) ionic liquid and/or silicon dioxide (SiO2) filler on the morphology and physical properties of NMPC/PVA composite membranes. The temperature-dependent ionic conductivity of the composite membranes with various ionic liquid and filler compositions was studied by varying the loading of PAN ionic liquid and SiO2-PAN filler in the range of 5–20 wt%. As the loading of PAN ionic liquid increased in the NMPC/PVA membrane matrix, the ionic conductivity value also increased with the highest value of 0.53 × 10?3 S cm?1 at 25 °C and increased to 1.54 × 10?3 S cm?1 at 100 °C with 20 wt% PAN. The NMPC/PVA-PAN (20 wt%) composite membrane also exhibited the highest water uptake and ion exchange capacity, with values of 60.5% and 0.60 mequiv g?1, respectively. In addition, in the single-cell performance test, the NMPC/PVA-PAN (20 wt%) composite membrane displayed a maximum power density, which was increased by approximately 14% compared to the NMPC/PVA composite membrane with 5 wt% SiO2-PAN. This work demonstrated that modified NMPC/PVA composite membranes with ionic liquid PAN and/or SiO2 filler showed enhanced performance compared with unmodified NMPC/PVA composite membranes for proton exchange membrane fuel cells.  相似文献   

12.
Novel Sm2O3?NiO composite was prepared as the functional electrolyte for the first time. The total electrical conductivity of Sm2O3?NiO is 0.38 S cm?1 in H2/air condition at 550 °C. High performance, e.g. 718 mW cm?2, was achieved using Sm2O3?NiO composite as an electrolyte of solid oxide fuel cells operated at 550 °C. The electrical properties and electrochemical performance are strongly depended on Sm2O3 and NiO constituent phase of the compositions. Notably, surprisingly high ionic conductivity and fuel cell performance are achieved using the composite system constituting with insulating Sm2O3 and intrinsic p-type conductive NiO with a low conductivity of 4 × 10?3 S cm?1. The interfacial ionic conduction between two phases is a dominating factor giving rise to significantly enhanced proton conduction. Fuel cell performance and further ionic conduction mechanisms are under investigation.  相似文献   

13.
Semiconductor-based electrolytes have significant advantages than conventional ionic electrolyte fuel cells, especially for high ionic conductivity and power outputs at low temperatures (<600 °C). This work reports a p-n heterojunction composite electrolyte developed by a p-type La0.8Sr0.2Co0.8Fe0.2O3-δ (LSCF) and n-type Li2TiO3 (LTO). It achieved a power output of 350 mW cm?2 at 550 °C using LSCF-LTO heterostructure as the electrolyte. On the other hand, pure LSCF and Li2TiO3 were made as the fuel cell electrolyte as well. The former resulted immediately a short circuiting problem and exhibited no device voltage because of high electron (hole) conductivity. While the Li2TiO3 can reach an open circuit voltage (OCV) but deliver too low power output, 37 mW cm?2 at 550 °C. Scanning Electron Microscope (SEM) combined with High-Resolution Transmission Electron Microscope (HR-TEM) clearly proved the formation of heterogeneous interface. Also, Fourier Transform Infrared Spectroscopy (FTIR) was performed to demonstrate the functional group of the synthesized materials. The results demonstrate clearly the semiconductor heterostructure effect. By adjusting apriority composition of the n-type and p-type components, electronic conduction is well suppressed in the membrane electrolyte. Meanwhile, by constructing p-n heterostructure and build-in field, we have succeeded in high ionic conductivity, high current and power outputs for the low temperature fuel cells. The results are interesting in general that to construct a p-n heterostructure electrolyte can be an effective and common way in developing low temperature ceramic fuel cells.  相似文献   

14.
The composite perovskites are promising low/intermediate-temperature solid oxide fuel cell (LT/IT-SOFC) cathode materials, which can combine the complementary advantages of multi-components. Here, novel liquid self-assembly (SA) is compared with nanosolid mechanical-mixing (MM) for the high-performance nanostructured composite. The same composition of the active BaCo0.96Zr0.04O2.6+δ (12hBC, 38 mol%) with the stable BaZr0.82Co0.18O3-δ (BZC, 62 mol%) is designed to compare the effects of different syntheses on composite properties. The BZC-12hBC (SA) can achieve molecular-level contact of multiple phases, which exhibits superior electrical conductivity, surface and heterointerface activity to those of BZC-12hBC (MM). When further applied on LT/IT-SOFC, the cell with BZC-12hBC (SA) cathode achieves the remarkable peak power densities of 2.06–0.24 W cm?2 at 700–500 °C, while the cell with BZC-12hBC (MM) cathode only exhibits 0.63–0.11 W cm?2. The electrochemical analysis reveals that BZC-12hBC (SA) cathode possesses better oxygen dissociative adsorption and species transportation than those of the BZC-12hBC (MM) cathode.  相似文献   

15.
As a promising electrolyte material for solid oxide fuel cells (SOFCs), BaZr0.1Ce0.7Y0.1Yb0.1O3-δ (BZCYYb) often surfers from its high sintering temperature, which causes Ba evaporation and sluggish grain growth, thus reducing the electrical conductivity. In this work, densified BZCYYb electrolytes were fabricated at temperatures as low as 1400 °C using the microwave sintering technique. Comparing with the conventional sintered ones, a temperature decrease of 150 °C is achieved. The Ba evaporation is effectively suppressed, and large grain sizes of ~4 μm are obtained. The total conductivity for microwave sintered symmetric cell measured in wet air at 700 °C is 3.8 × 10?2 S cm?1, benefiting from both enhanced bulk conductivities by 1–2 times and grain boundary conductivities by 50 times. With the microwave sintered BZCYYb as electrolyte, an anode-supported cell reaches a maximum power density of 0.64 W cm?2 at 700 °C.  相似文献   

16.
Sulfonated branched polymer membranes have been gaining immense attention as the separator in energy‐related applications especially in fuel cells and flow batteries. Utilization of this branched polymer membranes in direct methanol fuel cell (DMFC) is limited because of large free volume and high methanol permeation. In the present work, sulfonated fullerene is used to improve the methanol barrier property of the highly branched sulfonated poly(ether ether ketone sulfone)s membrane without sacrificing its high proton conductivity. The existence of sulfonated fullerene with larger size and the usage of small quantity in the branched polymer matrix effectively prevent the methanol transportation channel across the membrane. The composite membrane with an optimized loading of sulfonated fullerene displays the highest proton conductivity of 0.332 S cm?1 at 80°C. Radical scavenging property of the fullerene improves the oxidative stability of the composite membrane. Composite membrane exhibits the peak power density of 74.38 mW cm?2 at 60°C, which is 30% larger than the commercial Nafion 212 membrane (51.78 mW cm?2) at the same condition. From these results, it clearly depicts that sulfonated fullerene‐incorporated branched polymer electrolyte membrane emerges as a promising candidate for DMFC applications.  相似文献   

17.
Nowadays, semiconductor ionic materials have drawn significant attention for developing new electrolytes in low temperature solid oxide fuel cells (LT-SOFCs). Here we investigate the effect of nickel doping on ionic conductivity of Sm2O3 as an electrolyte material for low temperature SOFCs. The amount of Ni ion doping has an intense effect on the electrochemical properties and power generation. An optimized composition of 10 mol% nickel doped samarium oxide (10NSO) as an electrolyte in the fuel cell has a high open circuit voltage (OCV) of 1.09 V and a notable power output of 1080 mW cm?2 at 520 °C. Further investigation revealed that the 10NSO displays a superior ionic conduction up to 0.26 S cm?1 at 520 °C. Moreover, the cell demonstrates high stability up to 80 h. The high electrochemical property and good stability recommend that the NSO is a favorable candidate for symmetrical SOFC electrolyte.  相似文献   

18.
The sudden drop of ionic conductivity of GDC (Gd0.1Ce0·9O1.95) electrolyte in ceramic fuel cells with NCAL (Ni0·8Co0·15Al0·05LiO2) as electrode at low temperature was studied. It is found that the peak power density (PPD) of the cell with GDC electrolyte decreases linearly with the decreasing of the operation temperature above 400 °C. However, when the operation temperature drops to 400 °C, the cell PPD decreases significantly. EIS results show that the ionic conductivity of the electrolyte decreases linearly with the decrease of cell operating temperature. When the temperature decreases to approximately 400 °C, the ionic conductivity of the electrolyte decreases from 0.251 S cm?1 at 425 °C to 0.026 S cm?1 at 400 °C. The rapid decrease of the electrolyte ionic conductivity is considered to be the direct cause of the sudden decrease of the PPD. According to the results of XPS, FTIR and TG-DSC, LiOH/Li2CO3 formed in the NCAL anode diffuses into the electrolyte and melts at 419 °C or above, which is the reason for the high ionic conductivity of the electrolyte. The reason for the sudden drop of ionic conductivity is that LiOH/Li2CO3 and other compounds solidify in molten salts below 419 °C.  相似文献   

19.
NdSrCo2O5+δ (NSCO) is a perovskite with an electrical conductivity of 1551.3 S cm−1 at 500 °C and 921.7 S cm−1 at 800 °C and has a metal-like temperature dependence. This perovskite is used as the cathode material for Ce0.8Gd0.2O2-δ (GDC)-supported microtubular solid oxide fuel cells (MT-SOFCs). The MT-SOFCs fabricated in this study consist of a bilayer anode, comprising a NiO–GDC composite layer and a NiO layer, and a NSCO–GDC composite cathode. Three cell designs with different outer tube diameters, GDC thicknesses, and NSCO/GDC ratios are designed. The MT-SOFC with an outer tube diameter of 1.86 mm, an electrolyte thickness of 180 μm, and a 5NSCO–5GDC composite cathode presents the best performance. The flexural strength of the aforementioned cell is 177 MPa, which is sufficient to confer mechanical integrity to the cell. Moreover, the ohmic and polarization resistance values of the cell are 0.22 and 0.09 Ω cm2 at 700 °C, respectively, and 0.15 and 0.03 Ω cm2 at 800 °C, respectively. These results indicate that the NSCO-GDC composite exhibits high electrochemical activity. The maximum power densities of the cell at 700 and 800 °C are 0.46 and 0.67 W cm−2, respectively, exceeding those of existing electrolyte-supported MT-SOFCs with similar electrolyte thicknesses.  相似文献   

20.
The use of ceramic semiconductors to serve as an efficient proton conductor is an evolving approach in the novel emerging field of semiconductor protonic fuel cells (SPFCs). One of the most critical challenges in SPFCs is to design a sufficient proton-conductivity of 0.1 S cm?1 below <600 °C. Here we report to tune the perovskite BaSnO3 (BSO), a semiconductor single-phase material, to be applied as a proton-conducting electrolyte for SPFC. It was found that the oxygen vacancies play a vital role to promote proton transport while the electronic short-circuiting issue of BSO semiconductor has been justified by the Schottky junction mechanism at the anode/electrolyte interface. We have demonstrated a SPFC device to deliver a maximum power density of 843 mW cm?2 with an ionic conductivity of 0.23 S cm?1 for BSO at 550 °C. The oxygen vacancy formation by increasing the annealing temperature helps to understand the proton transport mechanism in BSO and such novel low-temperature SPFC (LT-SPFC).  相似文献   

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