| 1. |
- Bu, Junfu, 1982-
(författare)
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Advanced BaZrO3-BaCeO3 Based Proton Conductors Used for Intermediate Temperature Solid Oxide Fuel Cells (ITSOFCs)
- 2015
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- In this thesis, the focus is on studying BaZrO3-BaCeO3 based proton conductors due to that they represent very promising proton conductors to be used for Intermediate Temperature Solid Oxide Fuel Cells (ITSOFCs). Here, dense BaZr0.5Ce0.3Y0.2O3-δ (BZCY532) ceramics were selected as the major studied materials. These ceramics were prepared by different sintering methods and doping strategies. Based on achieved results, the thesis work can simply be divided into the following parts:1) An improved synthesis method, which included a water-based milling procedure followed by a freeze-drying post-processing, was presented. A lowered calcination and sintering temperature for a Hf0.7Y0.3O2-δ (YSH) compound was achieved. The value of the relative density in this work was higher than previously reported data. It is also concluded that this improved method can be used for mass-production of ceramics.2) As the solid-state reactive sintering (SSRS) represent a cost-effective sintering method, the sintering behaviors of proton conductors BaZrxCe0.8-xLn0.2O3-δ (x = 0.8, 0.5, 0.1; Ln = Y, Sm, Gd, Dy) during the SSRS process were investigated. According to the obtained results, it was found that the sintering temperature will decrease, when the Ce content increases from 0 (BZCLn802) to 0.3 (BZCLn532) and 0.7 (BZCLn172). Moreover, the radii of the dopant ions similar to the radii of Zr4+ or Ce4+ ions show a better sinterability. This means that it is possible to obtain dense ceramics at a lower temperature. Moreover, the conductivities of dense BZCLn532 ceramics were determined. The conductivity data indicate that dense BZCY532 ceramics are good candidates as either oxygen ion conductors or proton conductors used for ITSOFCs.3) The effect of NiO on the sintering behaviors, morphologies and conductivities of BZCY532 based electrolytes were systematically investigated. According to the achieved results, it can be concluded that the dense BZCY532B ceramics (NiO was added during ball-milling before a powder mixture calcination) show an enhanced oxygen and proton conductivity. Also, that BZCY532A (NiO was added after a powder mixture calcination) and BZCY532N (No NiO was added in the whole preparation procedures) showed lower values. In addition, dense BZCY532B and BZCY532N ceramics showed only small electronic conductivities, when the testing temperature was lower than 800 ℃. However, the BZCY532A ceramics revealed an obvious electronic conduction, when they were tested in the range of 600 ℃ to 800 ℃. Therefore, it is preferable to add the NiO powder during the BZCY532 powder preparation, which can lower the sintering temperature and also increase the conductivity.4) Dense BZCY532 ceramics were successfully prepared by using the Spark Plasma Sintering (SPS) method at a temperature of 1350 ℃ with a holding time of 5 min. It was found that a lower sintering temperature (< 1400 ℃) and a very fast cooling rate (> 200 ℃/min) are two key parameters to prepare dense BZCY532 ceramics. These results confirm that the SPS technique represents a feasible and cost-effective sintering method to prepare dense Ce-containing BaZrO3-BaCeO3 based proton conductors.5) Finally, a preliminary study for preparation of Ce0.8Sm0.2O2-δ (SDC) and BZCY532 basedcomposite electrolytes was carried out. The novel SDC-BZCY532 based composite electrolytes were prepared by using the powder mixing and co-sintering method. The sintering behaviors, morphologies and ionic conductivities of the composite electrolytes were investigated. The obtained results show that the composite electrolyte with a composition of 60SDC-40BZCY532 has the highest conductivity. In contrast, the composite electrolyte with a composition of 40SDC-60BZCY532 shows the lowest conductivity.In summary, the results show that BaZrO3-BaCeO3 based proton-conducting ceramic materials represent very promising materials for future ITSOFCs electrolyte applications.
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| 2. |
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| 3. |
- Bu, Junfu, et al.
(författare)
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Dense and translucent BaZrxCe0.8-xY0.2O3-delta (x=0.5, 0.6, 0.7) proton conductors prepared by spark plasma sintering
- 2015
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Ingår i: Scripta Materialia. - : Elsevier BV. - 1359-6462 .- 1872-8456. ; 107, s. 145-148
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Tidskriftsartikel (refereegranskat)abstract
- Dense and translucent BaZrxCe0.8-xY0.2O3-delta (x = 0.5, 0.6, 0.7) proton conductors were firstly and successfully prepared by Spark Plasma Sintering (SPS) at a temperature of 1350 degrees C without sintering aids' addition. XRD, SEM and EDS were applied to determine the phase purity, morphology and element composition of prepared pellets, respectively. Moreover, the sintering behaviors of these proton conductors were monitored and analyzed through the on-line sintering curves. The obtained results indicate that a lowered sintering temperature (<1400 degrees C) and a fast cooling rate (>= 200 degrees C/min) represent two key parameters to prepare dense Ce-containing BaZrO3-BaCeO3 based proton conductors.
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| 4. |
- Bu, Junfu, et al.
(författare)
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Electrical conductivities of translucent BaZr(X)Ce0.8-XY0.2O3-delta (x=0.5, 0.6, 0.7) ceramics
- 2016
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Ingår i: Scripta Materialia. - : Elsevier. - 1359-6462 .- 1872-8456. ; 115, s. 87-90
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Tidskriftsartikel (refereegranskat)abstract
- The electrical conductivities of translucent BaZr0.5Ce0.3Y0.2O3-delta (x = 0.5, BZCY532), BaZr0.6Ce0.2Y0.2O3-delta (x = 0.6, BZCY622) and BaZr0.7Ce0.1Y0.2O3-delta(x = 0.7, BZCY712) proton conductors were investigated systematically in different atmospheres and also at different oxygen partial pressures. The obtained results indicate that translucent BZCY532, BZCY622 and BZCY712 ceramics are pure oxygen-ion and proton conductors without unfavorable electronic conduction. In addition, they represent promising proton conductors to be used as intermediate temperature solid oxide fuel cell electrolytes.
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| 5. |
- Bu, Junfu
(författare)
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Exploratory Study of Novel Materials Used for Intermediate Temperature Solid Oxide Fuel Cell (IT-SOFC) Electrolytes
- 2014
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Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Currently, yttria-stabilized zirconia (YSZ) is still the dominant electrolyte material in commercial SOFC applications. But it has severe drawbacks due to its high operating temperatures. In present work, two electrolyte materials: Hf0.69Y0.31O2-δ (YSH) used as oxygen ion conductor and BaZr0.5Ce0.3Ln0.2O3-δ (BZCLn532, Ln=Y, Sm, Gd, Dy) used as protonic conductors were studied at intermediate temperatures (IT, 500-700 ℃). The work is focused on the following parts:1) A pure and well-crystallized YSH powder was successfully synthesized by using a modified solid state reaction method. The obtained YSH is in a fluorite cubic structure with a lattice parameter 5.140674 Å from the Rietveld refinement analysis. A YSH ceramic material with a relative density of 97.5% is obtained by a conventional sintering at a temperature of 1650 ℃. The oxygen ion conductivity of the YSH ceramic is 3.65×10-5 S cm-1 at a temperature of 700 ℃, which is too low for oxygen ion conductor applications. In contrast, there is an obvious enhancement of the protonic conductivity, when the testing temperature is higher than 600 ℃. The conductivity that tested in a moist atmosphere at a temperature of 700 ℃ is 5.19×10-5 S cm-1, which is 1.4 times higher than the oxygen ion conductivity.2) BaZr0.5Ce0.3Ln0.2O3-δ (BZCLn532, Ln=Y, Sm, Gd, Dy) based electrolytes were successfully synthesized by using a cost-effective solid state reactive sintering (SSRS) method with 1 wt.% NiO as a sintering aid. Based on the obtained conductivities of BZCLn532 compounds measured in a dry air atmosphere and a moist air atmosphere, BaZr0.5Ce0.3Y0.2O3-δ (BZCY532) and BaZr0.5Ce0.3Dy0.2O3-δ (BZCD532) compounds are demonstrated to be good candidates for both oxygen ion conductor and proton conductor materials for solid oxide fuel cells operating at intermediate temperatures.In summary, proton conducting ceramic materials represent one type of promising materials for future IT-SOFCs electrolyte applications.
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| 6. |
- Bu, Junfu, et al.
(författare)
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Ionic conductivity of dense BaZr(0.5)Ce(0.3)Ln(0.2)O(3-delta) (Ln = Y, Sm, Gd, Dy) electrolytes
- 2014
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Ingår i: Journal of Power Sources. - : Elsevier BV. - 0378-7753 .- 1873-2755. ; 272, s. 786-793
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Tidskriftsartikel (refereegranskat)abstract
- BaZr(0.5)Ce(0.3)Ln(0.2)O(3-delta) (BZCLn532, Ln = Y, Sm, Gd, Dy) based electrolytes were successfully synthesized by a cost-effective solid-state reactive sintering (SSRS) method while using 1.0 wt.% NiO as a sintering aid. Dense pellets of BZCLn532 compounds can be prepared at sintering temperatures of 1600 degrees C (BZCY532) and 1400 degrees C (BZCS532, BZCG532 and BZCD532). The conductivities of the dense BZCLn532 ceramics were tested in dry and wet air at temperatures of 700 degrees C-200 degrees C. On the basis of the obtained results, it could be concluded that the BZCY532-based electrolyte show promise for use as oxygen-ion conductors and proton conductors in intermediate temperature solid oxide fuel cells (ITSOFCs).
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| 7. |
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| 8. |
- Bu, Junfu, et al.
(författare)
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Preparation of 30 mol.% Y-doped hafnia (Hf0.7Y0.3O2-delta) using a modified solid-state reaction method
- 2015
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Ingår i: Ceramics International. - : Elsevier BV. - 0272-8842 .- 1873-3956. ; 41:2, s. 2611-2615
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Tidskriftsartikel (refereegranskat)abstract
- A pure and well-crystallized Hf0.7Y0.3O2-delta (YSH) powder was synthesized using a modified solid-state reaction method. Water-based milling and freeze drying process were implemented to facilitate powder synthesis and final densification process. The improved powder performance, in aspects of phase development and sintering behaviour, was investigated by systematic comparison between different powder processing procedures. Dense YSH ceramic material with a relative density of 0.975 was successfully obtained using conventional sintering at 1650 degrees C for 10 h. XRD, SEM and EDS were employed to characterize the synthesized powder and dense YSH ceramics. Dense YSH ceramic possesses a fluorite cubic structure with an a value of 5.1406 angstrom, and the ionic radius of Y3+ in YSH was determined to be 0.1006 nm.
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| 9. |
- Bu, Junfu, et al.
(författare)
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Preparation of Potential Protonic Conductor Yttria Doped Hafnia by Using the Modified Solid State Reaction Method
- 2014
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Ingår i: ECS Transactions. - : The Electrochemical Society. - 1938-5862 .- 1938-6737. ; , s. 315-320
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Konferensbidrag (refereegranskat)abstract
- A pure and well crystalized yttrium doped hafnium oxide Hf0.69Y0.31O2-δ (YSH) is obtained by using a modified solid state reaction method, where a water-based milling medium and freeze drying are implemented to reduce the agglomeration. The mean sizes of the YSH powder, which is obtained through a traditional alcohol-based milling method, is more than 1 um. However, the powder size can be reduced to 100 nm by using the water-based milling method. In addition, the calcination temperature can be lowered 200 °C to get a pure phase by using the water-based milling method, compared to the alcohol-based milling method. The relative density of YSH ceramic materials can reach to 97.5% by conventional sintering at 1650 °C after during 10 h.
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| 10. |
- Bu, Junfu, et al.
(författare)
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Preparation of Protonic Conductor BaZr0.5Ce0.3Ln0.2O3-δ (Ln = Y, Sm, Gd, Dy) by using a Solid State Reactive Sintering Method
- 2014
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Konferensbidrag (refereegranskat)abstract
- A pure and well crystalized yttrium doped hafnium oxide Hf0.69Y0.31O2-δ (YSH) is obtained by using a modified solid state reaction method, where a water-based milling medium and freeze drying are implemented to reduce the agglomeration. The mean sizes of the YSH powder, which is obtained through a traditional alcohol-based milling method, is more than 1 um. However, the powder size can be reduced to 100 nm by using the water-based milling method. In addition, the calcination temperature can be lowered 200 ℃ to get a pure phase by using the water-based milling method, compared to the alcohol-based milling method. The relative density of YSH ceramic materials can reach to 97.5% by conventional sintering at 1650 ℃ after during 10 h.
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| 11. |
- Bu, Junfu, et al.
(författare)
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Sintering behaviour of the protonic conductors BaZr(x)Ce(0.8-x)Ln(0.2)O(3-delta) (x=0.8, 0.5, 0.1; Ln=Y, Sm, Gd, Dy) during the solid-state reactive-sintering process
- 2015
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Ingår i: Ceramics International. - : Elsevier BV. - 0272-8842 .- 1873-3956. ; 41:2, s. 2558-2564
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Tidskriftsartikel (refereegranskat)abstract
- The protonic conductors BaZr(x)Ce(0.8-x)Ln(0.2)O(3-delta) (x=0.8, 0.5, 0.1; Ln=Y, Sm, Gd, Dy) were successfully prepared using a solid-state reactive-sintering method. NiO (1 wt.%) was added as a sintering aid, and it was proven that NiO produced tremendous enhancement in the densification process. The morphologies of the variously doped BaZr(0.8)Ln(0.2)O(3-delta), BaZr(0.5)Ce(0.3)Ln(0.2)O(3-delta) and BaZr(0.1)Ce(0.7)Ln(0.2)O(3-delta) ceramics, as well as their sintering behaviour, were investigated. The results show that the Ce content in the BaZr(0.8)Ln(0.2)O(3-delta), BaZr(0.5)Ce(0.3)Ln(0.2)O(3-delta) and BaZr(0.1)Ce(0.7)Ln(0.2)O(3-delta) compounds influences the sintering temperature significantly, and a larger Ce content will lead to a lower sintering temperature. In addition, ionic radii of the dopants that are similar to the ionic radii of the B-site will also result in a lowered sintering temperature. Based on the present study, NiO has no influence on the lattice parameters.
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| 12. |
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| 13. |
- Bu, Junfu, et al.
(författare)
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The effect of NiO on the conductivity of BaZr0.5Ce0.3Y0.2O3-delta based electrolytes
- 2016
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Ingår i: RSC Advances. - : Royal Society of Chemistry (RSC). - 2046-2069. ; 6:67, s. 62368-62377
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Tidskriftsartikel (refereegranskat)abstract
- The effects of NiO on the sintering behaviors, morphologies and conductivities of BaZr0.5Ce0.3Y0.2O3-delta (BZCY532) based electrolytes were systematically investigated. 1 wt% NiO powder was added by different methods during the sample preparation: (i) added during ball-milling before a powder mixture calcination (named BZCY(Ni) 532), (ii) no NiO addition in the whole preparation procedure (named BZCY532) and (iii) added after a powder mixture calcination (named BZCY532(Ni)). The conductivities of these three kinds of dense BZCY532 ceramics were investigated in dry air, wet N-2 and wet H-2 atmospheres, respectively. Moreover, the electronic contributions to the total conductivities were also identified in a broad oxygen partial pressure range. According to the achieved results, it can be concluded that the dense BZCY(Ni) 532 ceramics showed the best enhanced oxygen and proton conductivities, followed by the BZCY532(Ni) and BZCY532 ceramics. Furthermore, the BZCY(Ni) 532 and BZCY532 ceramics showed a tiny electronic conductivity, when the testing temperatures were lower than 800 degrees C. However, the BZCY532(Ni) ceramics revealed an obvious electronic conduction when they were tested at temperatures of 600-800 degrees C. Therefore, it is preferable to add the NiO during powder preparation, which can lower the sintering temperature and also increase the conductivity of BZCY532-based electrolytes.
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| 14. |
- Bu, Junfu, et al.
(författare)
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Transport properties of BaZr0.5Ce0.3Y0.2O3-δ proton conductor prepared by spark plasma sintering
- 2016
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Ingår i: Ceramics International. - : Elsevier. - 0272-8842 .- 1873-3956. ; 42:3, s. 4393-4399
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Tidskriftsartikel (refereegranskat)abstract
- Dense BaZr0.5Ce0.3Y0.2O3-δ (BZCY532) proton conductors were prepared by a spark plasma sintering method. Their conductivities were determined in different atmospheres: dry air, wet N2 and wet H2. Moreover, the potential electronic conductivity contribution to the total conductivity was also identified by testing their total conductivities at different oxygen partial pressures (1-10-24 atm) in combination with an XPS analysis. It is found that the prepared dense BZCY532 ceramics are good proton conductors at 600 °C. In addition, the Ce3+ concentration in the dense BZCY532 ceramics is around 3.5 atm% of the total Ce element, and the electronic contribution to the total conductivity can be neglected after a postheat treatment.
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| 15. |
- Bu, Junfu, et al.
(författare)
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Yttrium doped hafnium oxide Hf0.69Y0.31O2-δ used for solid oxide fuel cell electrolytes and electronic materials
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Annan publikation (övrigt vetenskapligt/konstnärligt)abstract
- An Yttrium doped hafnium oxide Hf0.69Y0.31O2-δ (YSH orYDH) is obtained by a modified solid state reactionmethod, where freeze drying is implemented to reduce theagglomeration. Refinement result shows that YSH is influorite cubic crystal with lattice parameter a = b = c =5.140674 Å (Figure 1). Based on this, the ionic radius ofY3+ in YSH for 8 coordination is 0.1006 nm, confirms theprevious prediction that it should be smaller than 0.1015nm. The YSH ceramic material with relative density of>97.5% can be obtained by conventional sintering at 1650℃ for 10hrs. Its conductivity is only 3.65×10-5 s cm-1 at700 ℃ (Figure 2), which is too low for solid oxide fuelcell application. However, its high dielectric constant22.03 (Figure 3a, average value, which is 1.4 times largerthan the pure Hafnia) and low dielectric loss over a widefrequency range and DC potential make it very promisingfor the microelectronic device application.
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