WO2023140816A1 - Lanthanide (iii) oxide added bismuth (iii) oxide solid electrolyte material - Google Patents
Lanthanide (iii) oxide added bismuth (iii) oxide solid electrolyte material Download PDFInfo
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- WO2023140816A1 WO2023140816A1 PCT/TR2022/050947 TR2022050947W WO2023140816A1 WO 2023140816 A1 WO2023140816 A1 WO 2023140816A1 TR 2022050947 W TR2022050947 W TR 2022050947W WO 2023140816 A1 WO2023140816 A1 WO 2023140816A1
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- Prior art keywords
- iii
- electrolyte material
- solid electrolyte
- fuel cells
- oxide
- Prior art date
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- 239000000463 material Substances 0.000 title claims abstract description 34
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 18
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 title claims abstract description 14
- MSBGPEACXKBQSX-UHFFFAOYSA-N (4-fluorophenyl) carbonochloridate Chemical compound FC1=CC=C(OC(Cl)=O)C=C1 MSBGPEACXKBQSX-UHFFFAOYSA-N 0.000 title claims description 8
- 229910052747 lanthanoid Inorganic materials 0.000 title description 5
- 150000002602 lanthanoids Chemical class 0.000 title description 5
- 239000000446 fuel Substances 0.000 claims abstract description 32
- 239000007787 solid Substances 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 7
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 6
- 230000004913 activation Effects 0.000 claims abstract description 6
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(III) oxide Inorganic materials O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000005259 measurement Methods 0.000 claims abstract description 4
- 238000003825 pressing Methods 0.000 claims abstract description 4
- 238000004364 calculation method Methods 0.000 claims abstract description 3
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000002076 thermal analysis method Methods 0.000 claims abstract description 3
- 238000003384 imaging method Methods 0.000 claims abstract 2
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 abstract description 3
- 210000004027 cell Anatomy 0.000 description 19
- 239000003792 electrolyte Substances 0.000 description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 8
- 229910052684 Cerium Inorganic materials 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 5
- 229910000416 bismuth oxide Inorganic materials 0.000 description 5
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 239000002001 electrolyte material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011858 nanopowder Substances 0.000 description 3
- AHKZTVQIVOEVFO-UHFFFAOYSA-N oxide(2-) Chemical compound [O-2] AHKZTVQIVOEVFO-UHFFFAOYSA-N 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical group [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 230000018199 S phase Effects 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- YLSLSHTYFFBCKG-UHFFFAOYSA-N bismuth;oxomolybdenum Chemical class [Mo].[Bi]=O YLSLSHTYFFBCKG-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910021525 ceramic electrolyte Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 229910001938 gadolinium oxide Inorganic materials 0.000 description 1
- 229940075613 gadolinium oxide Drugs 0.000 description 1
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- -1 oxygen ion Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229910001848 post-transition metal Inorganic materials 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
- H01M8/1266—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing bismuth oxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the invention relates in particular to a thermodynamically and chemically stable solid electrolyte material with low electronic and high ionic conductivity used in solid oxide fuel cells and its manufacturing method.
- Solid oxide fuel cells are devices consisting of an anode, cathode, and electrolyte components that convert the chemical energy of fuel into electrical energy with high efficiency.
- a solid oxide fuel cell is characterized by the fact that it has a solid ceramic electrolyte, which is a metallic oxide.
- the cell reaction for a hydrogen-fueled SOFC is; H2+ 1 /2O2— >H2O + electric energy + heat.
- Zero carbon emissions here indicate that the fuel cell is a decently environmentally friendly power source.
- SOFC traditionally operates at high temperatures between 800 to 1000 O.
- the properties that the ideal SOFC electrolyte should have can be listed as follows; having sufficiently high oxide ion conductivity, low electronic conductivity, thermodynamic and chemical stability, chemical inertia against electrode materials, compatibility of the coefficient of thermal expansion with cell components, and reliable mechanical properties.
- solid oxide fuel cell electrolyte materials When the literature and patent applications related to solid oxide fuel cell electrolyte materials are examined, it is seen that; a large number of different solid oxide electrolytes such as zirconium materials, cerium materials, lanthanum materials, bismuth oxide-based or pyrochlore-based materials appear to be used.
- the ideal electrolytes for high- temperature solid oxide fuel cells (HT-SOFC), intermediate temperature solid oxide fuel cells (IT-SOFC), and low-temperature solid oxide fuel cells (LT-SOFC) vary. The choice of an ideal electrolyte depends not only on the operating temperature but also on its physical parameters, such as the power density of the fuel cell, the type of fuel, and current density.
- YSZ yttrium- stabilized zirconium
- Yttria is added to stabilize the conductive cubic fluorite phase and also to increase the concentration of oxygen vacancies and thereby to increase ionic conductivity.
- scandium which has a higher conductivity than YSZ.
- ScSZ scandium stabilized zirconia
- Cerium forms the fluorite structure and is a common electrolyte material for SOFC.
- cerium Compared with zirconia, cerium has higher conductivity and lower polarization resistance, especially at low temperatures.
- the primary disadvantage of cerium is electronic conduction at low oxygen partial pressures.
- cerium is doped to increase conductivity, and again like zirconia, the highest conductivity occurs for ions with the lowest size mismatch, which are gadolinium and samarium for cerium.
- the conductivity of Cei-xGdxO2 (CGO) the most widely used cerium-based electrolyte, is compared to that of YSZ and ScSZ. Below 600 G, the conductivities of CGO are consistently higher than those of YSZ or ScSZ.
- Perovskite, LaGaOs, strontium, and magnesium can be doped with Lai-xSr x Gai- y Mg y O3 (LSGM) to produce a material with good oxygen ion conductivity at low temperature.
- the conductivity of LSGM is higher than the conductivity of YSZ and SCSZ and is close to or lower than the conductivity of CGO.
- LSGM does not have an easily reducible ion like Ce 4+ and is therefore superior to cerium-based gadolinium oxide (CGO) for use at low oxygen partial pressures.
- the highest ionic conductivities at 300-700 G are found in Bi 203-based electrolytes such as Bismuth metal vanadium oxide (BIMEVOX).
- the patent no. CN103904351 A relates to a scandium oxide doped bismuth oxide solid oxide fuel cell electrolyte and a preparation method thereof.
- the patent no. CN108134119A relates to a kind of solid oxide fuel cell bismuth oxide base electrolyte membrane preparation method. It uses tungsten oxide, yttrium oxide, and magnesia codoped bismuth oxide.
- the patent no. CN110165268A is related to a kind of calcium carbonate collaboration promotion bismuth oxide method for preparing composite solid electrolyte, is related to solid electrolyte ceramic technical field of material.
- FR2792306A1 relates to a substituted bismuth-molybdenum oxide solid solution composition has substituting elements selected for maintaining charge equilibrium and structure type.
- a novel composition comprises a substituted BI26M010O69 solid solution in which the substituting elements are selected for maintaining charge equilibrium and the structure type.
- Bismuth (Bi) is a post-transition metal with atomic number 83, an atomic mass of 208,980 g/mol, and a melting point of 271 .4 C, in the 15th group (5A) and 6th period in the periodic table.
- Bismuth (III) oxide (Bi20s) has a mass of 465.957 g/mol. Pure Bi20s has six different crystallographic structures depending on the temperature. These are; monoclinic a- phase, tetragonal p-phase, bcc-body-centered cubic y-phase, fcc-surface-centered cubic 5-phase, orthorhombic 5-phase, and triclinic w-phase.
- the electrolyte is expected to be in a stable fcc-surface centered cubic s-phase.
- the 6-phase of Bi20s which is stable only at high temperatures, exhibits an exceptionally high anionic conductivity ( ⁇ 100 Snr 1 ).
- This anionic conductor is considered a possible solid-state electrolyte for use in high- temperature oxygen pumps and different gas sensors.
- the manufactured materials were subjected to heat treatment (14) for 100 hours at 800 ⁇ C in an atmospheric environment.
- X-ray diffraction (XRD) analysis (21 ) was performed to examine the phase structure and crystallographic properties of the materials produced. In the XRD analysis, patterns indicating the delta phase were observed.
- thermogravimetric, differential thermogravimetric, and differential thermal (TG/DTG/DTA) analyses (22) were performed.
- a field emission scanning electron microscope (FESEM) image (23) was taken for the surface characterization of the materials.
- the temperature-dependent conductivity of the produced materials in the range of 25 C - 1 150 T was measured by DC 4-point conductivity measurement (24) technique, and the activation energy was calculated from the obtained data (25). The maximum conductivity was measured at 5.23 S/cm. This value is relatively high compared to the conductivity of similar samples in the literature.
Abstract
The invention relates particularly to a thermodynamically and chemically stable solid electrolyte material with low electronic and high ionic conductivity used in solid oxide fuel cells and its manufacturing method, wherein; the material comprises Bi2O3 (1), La2O3 (2), Nd2O3 (3), Eu2O3 (4), and Dy2O3 (5). The production method comprises the steps of mixing (11), grinding (12), pressing (13), and heat treatment (14) at specific stoichiometric ratios; and the study of the structural, thermal, and electrical properties of the material comprising X-Ray diffraction analysis (21), thermal analysis (22), electron microscope imaging (23), DC 4-Point conductivity measurement (24), and activation energy calculation (25) steps.
Description
DESCRIPTION
LANTHANIDE (III) OXIDE ADDED BISMUTH (III) OXIDE SOLID ELECTROLYTE MATERIAL
Technical Field:
The invention relates in particular to a thermodynamically and chemically stable solid electrolyte material with low electronic and high ionic conductivity used in solid oxide fuel cells and its manufacturing method.
Prior Art:
The growing population and technological developments are also constantly increasing the global need for energy. The burning of fossil fuels used to meet the energy needs brings along the problems of climate change, air pollution, and energy insecurity. Due to the common goals of economic growth, environmental protection, and energy security, the search for cheap and clean energy is gaining significant importance. The search for an energy source today is evolving toward producing electrical energy from many different sources. In this regard, fuel cells, which generate electrical energy by the electrochemical reaction of a suitable fuel and oxidizer, are critical power systems since there is no need for charging and can continuously generate electrical energy as long as fuel is supplied. Fuels such as hydrogen, butane, propane, ethane, ethanol, methane, methanol, biogas, and naphtha are generally used in fuel cells. Fuel cells are classified according to the type of electrolyte and fuel. Solid oxide fuel cells (SOFCs) are devices consisting of an anode, cathode, and electrolyte components that convert the chemical energy of fuel into electrical energy with high efficiency. A solid oxide fuel cell is characterized by the fact that it has a solid ceramic electrolyte, which is a metallic oxide. The cell reaction for a hydrogen-fueled SOFC is; H2+1/2O2— >H2O + electric energy + heat. Zero carbon emissions here indicate that the fuel cell is a decently environmentally friendly power source. SOFC traditionally operates at high temperatures between 800 to 1000 O. The properties that the ideal SOFC electrolyte should have can be listed as follows; having sufficiently high oxide ion conductivity, low electronic conductivity, thermodynamic and chemical stability, chemical inertia against electrode materials, compatibility of the coefficient of thermal expansion with cell components, and reliable mechanical properties.
When the literature and patent applications related to solid oxide fuel cell electrolyte materials are examined, it is seen that; a large number of different solid oxide electrolytes such as zirconium materials, cerium materials, lanthanum materials, bismuth oxide-based or pyrochlore-based materials appear to be used. The ideal electrolytes for high- temperature solid oxide fuel cells (HT-SOFC), intermediate temperature solid oxide fuel cells (IT-SOFC), and low-temperature solid oxide fuel cells (LT-SOFC) vary. The choice of an ideal electrolyte depends not only on the operating temperature but also on its physical parameters, such as the power density of the fuel cell, the type of fuel, and current density.
The most common solid electrolyte material used in solid oxide fuel cells is yttrium- stabilized zirconium (YSZ). Yttria is added to stabilize the conductive cubic fluorite phase and also to increase the concentration of oxygen vacancies and thereby to increase ionic conductivity. Although it is rarely used for zirconium, a promising additive is scandium, which has a higher conductivity than YSZ. The higher conductivity of scandium stabilized zirconia (ScSZ) is attributed to the more minor mismatch in size between Zr4+ and Sc3+ when compared to Zr4+ and Y3+. Like zirconia, cerium forms the fluorite structure and is a common electrolyte material for SOFC. Compared with zirconia, cerium has higher conductivity and lower polarization resistance, especially at low temperatures. The primary disadvantage of cerium is electronic conduction at low oxygen partial pressures. Like zirconia, cerium is doped to increase conductivity, and again like zirconia, the highest conductivity occurs for ions with the lowest size mismatch, which are gadolinium and samarium for cerium. The conductivity of Cei-xGdxO2 (CGO), the most widely used cerium-based electrolyte, is compared to that of YSZ and ScSZ. Below 600 G, the conductivities of CGO are consistently higher than those of YSZ or ScSZ. Perovskite, LaGaOs, strontium, and magnesium can be doped with Lai-xSrxGai-yMgyO3 (LSGM) to produce a material with good oxygen ion conductivity at low temperature. The conductivity of LSGM is higher than the conductivity of YSZ and SCSZ and is close to or lower than the conductivity of CGO. However, LSGM does not have an easily reducible ion like Ce4+ and is therefore superior to cerium-based gadolinium oxide (CGO) for use at low oxygen partial pressures. The highest ionic conductivities at 300-700 G are found in Bi 203-based electrolytes such as Bismuth metal vanadium oxide (BIMEVOX). At temperatures as low as 300 G, BIMEVOX electrolytes exhibit conductivity as high as YSZ at 800 G.
The patent no. CN103904351 A relates to a scandium oxide doped bismuth oxide solid oxide fuel cell electrolyte and a preparation method thereof. The patent no. CN108134119A relates to a kind of solid oxide fuel cell bismuth oxide base electrolyte membrane preparation method. It uses tungsten oxide, yttrium oxide, and magnesia codoped bismuth oxide. The patent no. CN110165268A is related to a kind of calcium carbonate collaboration promotion bismuth oxide method for preparing composite solid electrolyte, is related to solid electrolyte ceramic technical field of material. The patent no. FR2792306A1 relates to a substituted bismuth-molybdenum oxide solid solution composition has substituting elements selected for maintaining charge equilibrium and structure type. A novel composition comprises a substituted BI26M010O69 solid solution in which the substituting elements are selected for maintaining charge equilibrium and the structure type.
Bismuth (Bi) is a post-transition metal with atomic number 83, an atomic mass of 208,980 g/mol, and a melting point of 271 .4 C, in the 15th group (5A) and 6th period in the periodic table. Bismuth (III) oxide (Bi20s) has a mass of 465.957 g/mol. Pure Bi20s has six different crystallographic structures depending on the temperature. These are; monoclinic a- phase, tetragonal p-phase, bcc-body-centered cubic y-phase, fcc-surface-centered cubic 5-phase, orthorhombic 5-phase, and triclinic w-phase. The electrolyte is expected to be in a stable fcc-surface centered cubic s-phase. The 6-phase of Bi20s, which is stable only at high temperatures, exhibits an exceptionally high anionic conductivity (~ 100 Snr1). This anionic conductor is considered a possible solid-state electrolyte for use in high- temperature oxygen pumps and different gas sensors.
The Purpose of Invention:
The search for the ideal electrolyte with high ionic conductivity at low temperature, as well as minimal electronic conductivity and low activation energy, is ongoing in the industry, especially for solid oxide fuel cells. Studies conducted in this context indicate that Bi20s- based electrolytes will meet a critical need. To achieve this goal, the invention provides the following technical solutions;
• Sufficiently high oxide-ion conductivity (0.1 S/cm at operating temperature).
• Low electronic conductivity (<1 O'3 S/cm).
• Thermodynamic and chemical stability.
• Chemical inertness to electrode materials.
• Compatibility of the coefficient of thermal expansion with the components of the cell.
• Having reliable mechanical properties.
The benefits of the invention in comparison with the prior art are as follows;
• Sufficiently high oxide-ion conductivity (approximately 5 S/cm at operating temperature).
• Low electronic conductivity (<1 O'6 S/cm).
• Thermodynamic and chemical stability (obtaining samples with stable structure in the delta phase)
Description of Figures:
The details of the invention called Lanthanide (III) Oxide Added Bismuth (III) Oxide Solid Electrolyte Material are shown in the attached figures. In these figures;
Figure 1 : Lanthanide (III) Oxide Added Bismuth (III) Oxide Solid Electrolyte Material
Figure 2: The X-Ray Diffraction Pattern of a Sample
Figure 3: The Graph of the Thermal Analysis of a Sample
Figure 4: Field Emission Scanning Electron Microscope Image of a Sample
Figure 5: A Graph of the Temperature-Dependent Conductivity of a Sample
Figure 6: Activation Energy of a Sample
Description of the References in the Figures:
1 : Bismuth (III) Oxide: Bi20s
2: Lanthanum (III) Oxide: La2Os
3: Neodymium (III) Oxide: Nd20a
4: Europium (III) Oxide: EU2O3
5: Dysprosium (III) Oxide: Dy20s
Methods Applied in the Production of Materials:
11 : Mixing
12: Grinding
13: Pressing
14: Heat Treatment
Methods of Analysis of Manufactured Materials:
21 : X-Ray Diffraction (XRD) Analysis
22: Thermal (TG/DTG/DTA) Analysis
23: Field Emission Scanning Electron Microscope (FESEM) Image
24: DC 4-Point Conductivity Measurement
25: Calculation of Activation Energy
Description of the Invention:
Characterized by the chemical formula (Bi2O3)i-x-y-z-t(Eu2O3)x(La2O3)y(Nd2O3)z(Dy2O3)t, nano powder La2O3(2), Nd2O3(3), Eu2O3(4), Dy20s(5) added nano powder Bi2O3(1 ) materials were mixed in molar ratios of x,y,z,t=[5%-20%]. (II) A large number of mixtures of different stoichiometric ratios were grounded (12). Solid oxide electrolyte materials were produced in the required geometric shapes and sizes by pressing (13) the nanopowder materials under a pressure of around 750 MPa. The manufactured materials were subjected to heat treatment (14) for 100 hours at 800 <C in an atmospheric environment. X-ray diffraction (XRD) analysis (21 ) was performed to examine the phase structure and crystallographic properties of the materials produced. In the XRD analysis, patterns indicating the delta phase were observed. In order to study the thermal properties of the materials, thermogravimetric, differential thermogravimetric, and differential thermal (TG/DTG/DTA) analyses (22) were performed. A field emission scanning electron microscope (FESEM) image (23) was taken for the surface characterization of the materials. The temperature-dependent conductivity of the produced materials in the range of 25 C - 1 150 T was measured by DC 4-point conductivity measurement (24) technique, and the activation energy was calculated from the obtained data (25). The maximum conductivity was measured at 5.23 S/cm. This value is relatively high compared to the conductivity of similar samples in the literature.
Industrial Application of the Invention:
Lanthanide (III) Oxide Added Bismuth (III) Oxide Solid Electrolyte Material, which is the subject of the invention, is suitable for mass production, particularly to be used as an electrolyte in high temperature and medium temperature solid oxide fuel cells.
Claims
CLAIMS The invention relates particularly to a thermodynamically and chemically stable solid electrolyte material with low electronic and high ionic conductivity used in solid oxide fuel cells and its manufacturing method, characterized by comprising; Bismuth (III) Oxide: Bi20a (1 ), Lanthanum (III) Oxide: La20a (2), Neodymium (III) Oxide: Nd20a (3), Europium (III) Oxide: EU2O3 (4), and Dysprosium (III) Oxide: Dy20a (5). The invention relates particularly to a thermodynamically and chemically stable solid electrolyte material with low electronic and high ionic conductivity used in solid oxide fuel cells and its manufacturing method, according to Claim 1 , characterized by comprising; Bi20s (1 ) at a molar ratio ranging from 20% to 80%. The invention relates particularly to a thermodynamically and chemically stable solid electrolyte material with low electronic and high ionic conductivity used in solid oxide fuel cells and its manufacturing method, according to Claim 1 , characterized by comprising; La20s (2) at a molar ratio ranging from 5% to 20%. The invention relates particularly to a thermodynamically and chemically stable solid electrolyte material with low electronic and high ionic conductivity used in solid oxide fuel cells and its manufacturing method, according to Claim 1 , characterized by comprising; Nd20s (3) at a molar ratio ranging from 5% to 20%. The invention relates particularly to a thermodynamically and chemically stable solid electrolyte material with low electronic and high ionic conductivity used in solid oxide fuel cells and its manufacturing method, according to Claim 1 , characterized by comprising; EU2O3 (4) at a molar ratio ranging from 5% to 20%. The invention relates particularly to a thermodynamically and chemically stable solid electrolyte material with low electronic and high ionic conductivity used in solid oxide fuel cells and its manufacturing method, according to Claim 1 , characterized by comprising; Dy20s (5) at a molar ratio ranging from 5% to 20%. The invention relates particularly to a thermodynamically and chemically stable solid electrolyte material with low electronic and high ionic conductivity used in solid oxide fuel cells and its manufacturing method, characterized in that; the production method comprises the steps of mixing (1 1 ), grinding (12), pressing
(13) and heat treatment (14) at specific stoichiometric ratios. The invention relates particularly to a thermodynamically and chemically stable solid electrolyte material with low electronic and high ionic conductivity used in solid oxide fuel cells and its manufacturing method, characterized in that; the study of the structural, thermal and electrical properties of the material comprises
X-Ray diffraction analysis (21 ), thermal analysis (22), electron microscope imaging (23), DC 4-Point conductivity measurement (24), and activation energy calculation (25) steps.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
TR2022/000825 TR2022000825A1 (en) | 2022-01-24 | LANTHANIDE (III) OXIDE ADDED BISMUTH (III) OXIDE SOLID ELECTROLYTE MATERIAL | |
TR2022000825 | 2022-01-24 |
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WO2023140816A1 true WO2023140816A1 (en) | 2023-07-27 |
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5298235A (en) * | 1991-12-16 | 1994-03-29 | The Trustees Of The University Of Pennsylvania | Electrochemical devices based on single-component solid oxide bodies |
US20030160216A1 (en) * | 2000-04-07 | 2003-08-28 | Francois Goutenoire | Compounds derived from la2mo2o9 and their use as ionic conductors |
TW200929675A (en) * | 2007-12-21 | 2009-07-01 | Univ Nat Cheng Kung | High stability bismuth oxide-based ionic conductor |
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2022
- 2022-09-06 WO PCT/TR2022/050947 patent/WO2023140816A1/en active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5298235A (en) * | 1991-12-16 | 1994-03-29 | The Trustees Of The University Of Pennsylvania | Electrochemical devices based on single-component solid oxide bodies |
US20030160216A1 (en) * | 2000-04-07 | 2003-08-28 | Francois Goutenoire | Compounds derived from la2mo2o9 and their use as ionic conductors |
TW200929675A (en) * | 2007-12-21 | 2009-07-01 | Univ Nat Cheng Kung | High stability bismuth oxide-based ionic conductor |
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