CN105655605B - Solid oxide fuel cell cathod catalyst, composite cathode material and preparation method thereof - Google Patents
Solid oxide fuel cell cathod catalyst, composite cathode material and preparation method thereof Download PDFInfo
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- CN105655605B CN105655605B CN201610027063.5A CN201610027063A CN105655605B CN 105655605 B CN105655605 B CN 105655605B CN 201610027063 A CN201610027063 A CN 201610027063A CN 105655605 B CN105655605 B CN 105655605B
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- oxide
- cathode material
- composite cathode
- cathod catalyst
- doping
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- 239000010406 cathode material Substances 0.000 title claims abstract description 107
- 239000002131 composite material Substances 0.000 title claims abstract description 93
- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- 239000007787 solid Substances 0.000 title claims abstract description 33
- 239000000446 fuel Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 44
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 28
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 27
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 22
- 229910052802 copper Inorganic materials 0.000 claims abstract description 22
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 22
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 20
- 238000000498 ball milling Methods 0.000 claims abstract description 19
- 229910052742 iron Inorganic materials 0.000 claims abstract description 19
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 19
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 18
- 238000005245 sintering Methods 0.000 claims abstract description 9
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims description 50
- 229910052746 lanthanum Inorganic materials 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 31
- 239000011575 calcium Substances 0.000 claims description 30
- 229910052772 Samarium Inorganic materials 0.000 claims description 28
- 239000004020 conductor Substances 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 26
- 229910044991 metal oxide Inorganic materials 0.000 claims description 25
- 239000011777 magnesium Substances 0.000 claims description 24
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 23
- 229910052691 Erbium Inorganic materials 0.000 claims description 23
- 229910052693 Europium Inorganic materials 0.000 claims description 23
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 23
- 229910052689 Holmium Inorganic materials 0.000 claims description 23
- 229910052779 Neodymium Inorganic materials 0.000 claims description 23
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 23
- 229910052771 Terbium Inorganic materials 0.000 claims description 23
- 229910052775 Thulium Inorganic materials 0.000 claims description 23
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 23
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims description 20
- 229910052765 Lutetium Inorganic materials 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 17
- 150000004706 metal oxides Chemical class 0.000 claims description 17
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 14
- 229910000859 α-Fe Inorganic materials 0.000 claims description 13
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 11
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 11
- 229910052706 scandium Inorganic materials 0.000 claims description 11
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- ZIKATJAYWZUJPY-UHFFFAOYSA-N thulium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tm+3].[Tm+3] ZIKATJAYWZUJPY-UHFFFAOYSA-N 0.000 claims description 10
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 9
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims description 8
- 229910001940 europium oxide Inorganic materials 0.000 claims description 8
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 8
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 8
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 8
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 8
- PNEVPHWGBQXOBP-UHFFFAOYSA-N [Co].[Sr].[Mg] Chemical compound [Co].[Sr].[Mg] PNEVPHWGBQXOBP-UHFFFAOYSA-N 0.000 claims description 7
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000010189 synthetic method Methods 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- UPEMFLOMQVFMCZ-UHFFFAOYSA-N [O--].[O--].[O--].[Pm+3].[Pm+3] Chemical compound [O--].[O--].[O--].[Pm+3].[Pm+3] UPEMFLOMQVFMCZ-UHFFFAOYSA-N 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- GEZAXHSNIQTPMM-UHFFFAOYSA-N dysprosium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Dy+3].[Dy+3] GEZAXHSNIQTPMM-UHFFFAOYSA-N 0.000 claims description 6
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims description 6
- -1 holimium oxide Chemical compound 0.000 claims description 6
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims description 6
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 claims description 6
- SCRZPWWVSXWCMC-UHFFFAOYSA-N terbium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tb+3].[Tb+3] SCRZPWWVSXWCMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 206010058490 Hyperoxia Diseases 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical group [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- 229910001938 gadolinium oxide Inorganic materials 0.000 claims description 4
- 229940075613 gadolinium oxide Drugs 0.000 claims description 4
- 230000000222 hyperoxic effect Effects 0.000 claims description 4
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims description 4
- 229910003451 terbium oxide Inorganic materials 0.000 claims description 4
- 229910003454 ytterbium oxide Inorganic materials 0.000 claims description 4
- 229940075624 ytterbium oxide Drugs 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910016289 MxO2 Inorganic materials 0.000 claims description 3
- 229910052773 Promethium Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 3
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 3
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 3
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 claims description 3
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 3
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 claims description 3
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 3
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 3
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 62
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 51
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 28
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 21
- 229910052684 Cerium Inorganic materials 0.000 description 20
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 20
- 239000010949 copper Substances 0.000 description 20
- 239000011572 manganese Substances 0.000 description 20
- 229910052719 titanium Inorganic materials 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 239000003792 electrolyte Substances 0.000 description 11
- 230000007547 defect Effects 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- 150000001342 alkaline earth metals Chemical class 0.000 description 5
- 229910052747 lanthanoid Inorganic materials 0.000 description 5
- 150000002602 lanthanoids Chemical class 0.000 description 5
- 238000010248 power generation Methods 0.000 description 5
- 238000007650 screen-printing Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- 239000006257 cathode slurry Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910002367 SrTiO Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- ZXGIFJXRQHZCGJ-UHFFFAOYSA-N erbium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Er+3].[Er+3] ZXGIFJXRQHZCGJ-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 2
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910002080 8 mol% Y2O3 fully stabilized ZrO2 Inorganic materials 0.000 description 1
- 229910002561 K2NiF4 Inorganic materials 0.000 description 1
- 229910002273 La1–xSrxCoO3 Inorganic materials 0.000 description 1
- 229910002232 La2−xSrxNiO4 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910015494 Ni1-xFex Inorganic materials 0.000 description 1
- 229910003214 Ni1−xCux Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HBAGRTDVSXKKDO-UHFFFAOYSA-N dioxido(dioxo)manganese lanthanum(3+) Chemical compound [La+3].[La+3].[O-][Mn]([O-])(=O)=O.[O-][Mn]([O-])(=O)=O.[O-][Mn]([O-])(=O)=O HBAGRTDVSXKKDO-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- AHKZTVQIVOEVFO-UHFFFAOYSA-N oxide(2-) Chemical compound [O-2] AHKZTVQIVOEVFO-UHFFFAOYSA-N 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229910001954 samarium oxide Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Catalysts (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a kind of solid oxide fuel cell cathod catalysts, composite cathode material and preparation method thereof.The cathod catalyst is the strontium titanates of the perovskite structure of doping, meets following chemical general formulas: (Sr1‑xCx)1‑nTi1‑yDyO3, wherein C is Mg, Ca, one of Ba or a variety of, D Sc, V, Cr, Co, Mn, Ni, Fe, Cu, one of Zn or a variety of；X, y is the molar content of respective element, and 0≤x≤0.95,0 y≤0.95 <；0≤n≤0.08.Preparation method includes ball milling mixing step, sintering step, again ball milling step.The invention also discloses the composite cathode materials of the solid oxide fuel cell comprising above-mentioned cathod catalyst.The performance of solid oxide fuel cell after cathod catalyst of the present invention is added is substantially better than the performance for being not added with the solid oxide fuel cell of cathod catalyst.
Description
Technical field
The present invention relates to a kind of high-performance solid oxidate combined electrode of fuel cell material more particularly to a kind of solid oxygen
Compound cathode catalyst for fuel cell, composite cathode material and preparation method thereof.
Background technique
Solid oxide fuel cell is that one kind can be converted the chemical energy in fuel by way of electrochemical reaction
For all solid state energy conversion device of electric energy.It is mainly by anode, cathode and electrolyte composition.In general, the sky being passed through in cathode
Oxygen reduction reaction occurs at the three phase boundary of cathode internal for gas (oxygen), and the oxonium ion for reacting generation is passed by solid electrolyte
The three phase boundary for leading anode interior is in hydrogen and hydroxide reaction occurs, and the electronics for reacting generation passes through external current loop stream
Enter cathode and forms closed circuit power generation acting.
The cathode material of solid oxide fuel cell mainly by electronic conductive material and oxygen-ion conductive material mixing and
At the oxygen-ion conductive material in cathode is usually made of electrolyte, and three categories electrolyte is after stablizing at present
Zirconium oxide (Stabilized-ZrO2), the cerium oxide (Doped-CeO of doping2) and Ishihara invention lanthanum gallate series (US
6844098B1)。
Electronic conductive material in cathode is usually made of five major class: the lanthanum manganate perovskite structural material (JB of doping
Goodenough,Theory of the Role of Covalence in the Perovskite-Type Manganites
[LaM(II)]MnO3, Physical Review, 1955,100 (2): 564), the cobalt acid lanthanum perovskite structural material (AN of doping
Petrov,OF Kononchuk,etc.,Crystal structure,electrical and magnetic properties
of La1-xSrxCoO3, Solid State Ionics, 199580 (95): 189), the cadmium ferrite perovskite structural material (Y of doping
Teraoka,etc.,Oxygen permeation Through Perovskite-Type Oxides,Chemistry
Letters,1985,14(11):1743；Structure and Electrical Properties of La1-xSrxCo1- yFeyO3.Part 1.The system La0.8Sr0.2Co1-yFeyO3,1995,76(3):259；Structure and
Electrical Properties of La1-xSrxCo1-yFeyO3.Part 2.The system La1- xSrxCo0.2Fe0.8O31995,76 (3): 273), nickel acid lanthanum perovskite structural material (the R Chiba, etc., An of doping
investigation of La Ni1-xFexO3 as a cathode material for solid oxide fuel
Cells, Solid State Ionics, 1999,124 (26): 281) and doping K2NiF4Type structure nickelate (SJ
Skinner,etc.,Oxygen diffusion and surface exchange in La2-xSrxNiO4 Solid State
Ionics,2000,135(1):709；A.Aguadero,etc.,Evalution of the La2Ni1-xCuxO4 system as
SOFC cathode materials with 8YSZ and LSGM as electrolyte,Solid State Ionics,
2008,179(11):393)。
Compared to current applicable combination electrode material, higher cathode performance means higher generating efficiency, from
And the cost of battery pile can be reduced, it is universal to the commercialization of solid oxide fuel cell play the role of it is vital.
Summary of the invention
In view of the drawbacks of the prior art, one of the objects of the present invention is to provide a kind of solid oxide fuel cell yin
Electrode catalyst, the cathode catalyst material can be added in the cathode of other all solids oxide fuel cells, reach raising
The purpose of chemical property.
The second object of the present invention is to provide a kind of preparation method of above-mentioned cathod catalyst.
The third object of the present invention is to provide a kind of solid oxide fuel cell use comprising above-mentioned cathod catalyst
Composite cathode material.
The fourth object of the present invention is to provide the preparation method of above-mentioned composite cathode material, and this method is simple and easy.
To achieve the goals above, the invention adopts the following technical scheme:
A kind of solid oxide fuel cell cathod catalyst, the cathod catalyst are the perovskite structures of doping
Strontium titanates meets following chemical general formulas: (Sr1-xCx)1-nTi1-yDyO3, wherein C is Mg, Ca, one of Ba or a variety of, and D is
One of Sc, V, Cr, Co, Mn, Ni, Fe, Cu, Zn or a variety of；X, y is the molar content of respective element, and 0≤x≤
0.95,0 y≤0.95 <；0≤n≤0.08.
In above-mentioned cathod catalyst, the granularity of the cathod catalyst is no more than 5 as a preferred implementation manner,
μm；It is highly preferred that the granularity of the cathod catalyst is 0.005~5 μm；Further, 0≤x≤0.3,0 y≤0.9 <, n=
0。
The preparation method of above-mentioned cathod catalyst, it is preferred to use prepared by solid-phase synthesis, it is highly preferred that the cathode
Catalyst fines specific the preparation method is as follows:
Ball milling mixing step: according to the molar content of various elements in prepared cathod catalyst by corresponding amount
Raw material SrCO3、TiO2Wet ball grinding is carried out with the oxide to doped chemical until raw material is sufficiently mixed uniformly；
Sintering step: it will be sintered 5~20 hours at 1100 DEG C~1500 DEG C after the product drying after the wet ball grinding；
Sintered product: being carried out wet ball grinding by ball milling step again again until particle diameter meets the requirements.
The composite cathode material of solid oxide fuel cell comprising above-mentioned cathod catalyst.
In above-mentioned composite cathode material, the composite cathode material further includes cathode as a preferred implementation manner,
Material and high oxygen-ion conductive material；It is highly preferred that the quality of the cathod catalyst is cathode material, high oxide ion conduction material
The 0.05-40% of material and cathod catalyst quality sum；Further, the quality of the high oxygen-ion conductive material is cathode
The 30-70% of material and high oxygen-ion conductive material quality sum.
In above-mentioned composite cathode material, the cathode material is perovskite structure as a preferred implementation manner,
The ferrite of the doping of the cobaltatess, perovskite structure of the doping of the manganite, perovskite structure of doping, perovskite structure
The nickelate and A of doping2NiO4One of nickelate of structure is a variety of.
In above-mentioned composite cathode material, the high oxygen-ion conductive material is metal as a preferred implementation manner,
One of lanthanum gallate of the stable zirconium oxide of oxide, the cerium oxide of doped metallic oxide and strontium magnesium cobalt codope is more
Kind.
In above-mentioned composite cathode material, the zirconium oxide of the metal oxide stability as a preferred implementation manner,
In, the metal oxide is calcium oxide, magnesia, scandium oxide, yttrium oxide, lanthana, praseodymium oxide, neodymia, promethium oxide, oxygen
Change one of samarium, europium oxide, gadolinium oxide, terbium oxide, dysprosia, holimium oxide, erbium oxide, thulium oxide, ytterbium oxide and luteium oxide
Or it is a variety of；It is highly preferred that the content of the metal oxide is 1- in the zirconium oxide of the metal oxide stability
20mol%.
In above-mentioned composite cathode material, the cerium oxide of the doped metallic oxide as a preferred implementation manner,
In, the metal oxide is calcium oxide, magnesia, scandium oxide, yttrium oxide, lanthana, praseodymium oxide, neodymia, promethium oxide, oxygen
Change one of samarium, europium oxide, gadolinium oxide, terbium oxide, dysprosia, holimium oxide, erbium oxide, thulium oxide, ytterbium oxide and luteium oxide
Or it is a variety of；It is highly preferred that the cerium oxide of the doped metallic oxide meets following chemical general formula: Ce1-xMxO2, wherein 0.05
≤ x≤0.3, M be one of calcium, magnesium, scandium, yttrium, lanthanum, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium or
It is a variety of；
Further, the lanthanum gallate of the strontium magnesium cobalt codope meets following chemical general formula: La0.8Sr0.2Ga0.8Mg0.2- xCoxO3, wherein 0≤x≤0.15.
The preparation method of the composite cathode material of above-mentioned solid oxide fuel cell, includes the following steps:
Cathode material powder and high oxygen-ion conductive material powder are mixed and are ground, it is compound to obtain two systems by step 1
Electrode；Wherein the quality of the hyperoxia ion conductive material powder is the 30%~70% of two system combination electrode gross masses；
Cathod catalyst powder is added into the two systems combination electrode, mixes and grinds, obtain three-system for step 2
The composite cathode material；Wherein the quality of the cathod catalyst powder is composite cathode material gross mass described in three-system
0.05-40%.
Compared with prior art, the invention has the following beneficial effects:
Cathode catalyst material of the invention can be added in the cathode of other all solids oxide fuel cells, thus
Improve chemical property.The performance of solid oxide fuel cell after cathod catalyst of the present invention is added, which is substantially better than, to be not added with
The performance of the solid oxide fuel cell of cathod catalyst.
Detailed description of the invention
Fig. 1 is the power generation performance figure of the monocell after the composite cathode material assembling prepared using the embodiment of the present invention 1；
Fig. 2 is the power generation performance figure of the monocell after the composite cathode material assembling prepared using the embodiment of the present invention 2；
Fig. 3 is the power generation performance figure of the monocell after the composite cathode material assembling prepared using the embodiment of the present invention 3.
Specific embodiment
It, below will present invention is described in further detail in order to keep feature of the invention, effect etc. clearer.
A kind of solid oxide fuel cell cathod catalyst provided by the invention, the cathod catalyst are doping
The strontium titanates of perovskite structure meets following chemical general formulas: (Sr1-xCx)1-nTi1-yDyO3, wherein C is Mg, Ca, one of Ba
Or a variety of, D Sc, V, Cr, Co, Mn, Ni, Fe, Cu, one of Zn or a variety of；X and y is the Mole percent of respective element
Content, and 0≤x≤0.95,0 y≤0.95 <；0≤n≤0.08.
Specifically, cathod catalyst is a kind of strontium titanates (the Doped SrTiO of the perovskite structure of doping3).Doping point
It is two kinds:
The first is only in the strontium titanates SrTiO of B location doping3, meet perovskite structure ABO3Or meets location A and lack
Sunken perovskite structure A1-nBO3(0≤n≤0.08).I.e. only when B location adulterates, the strontium titanates tool of the perovskite structure of doping
There is following chemical general formula: A1-nTi1-yDyO3(i.e. (Sr1-xCx)1-nTi1-yDyO3Middle x=0), wherein D be Sc, V, Cr, Co, Mn, Ni,
One of Fe, Cu, Zn or a variety of；0 y≤0.95 < (such as 0.01,0.05,0.1,0.15,0.2,0.25,0.3,0.35,
0.4,0.45,0.5,0.55,0.6,0.65,0.7,0.75,0.8,0.85 or 0.9).
Second is to adulterate to adulterate in B location again in location A.The strontium titanates of the perovskite structure adulterated at this time has as follows
Chemical general formula: (Sr1-xCx)1-nTi1-yDyO3, wherein C be Mg, Ca, one of Ba or a variety of, D Sc, V, Cr, Co, Mn, Ni,
One of Fe, Cu, Zn or a variety of, 0 x≤0.95 < (such as x be 0.01,0.05,0.1,0.15,0.2,0.25,0.3,
0.35,0.4,0.45,0.5,0.55,0.6,0.65,0.7,0.75,0.8,0.85 or 0.9), 0 y≤0.95 < (for example y is
0.01、0.05、0.1、0.15、0.2、0.25、0.3、0.35、0.4、0.45、0.5、0.55、0.6、0.65、0.7、0.75、0.8、
0.85 or 0.9)；0≤n≤0.08.
In summary two kinds of doping situations, cathod catalyst of the invention have following chemical general formulas: (Sr1-xCx)1- nTi1-yDyO3, wherein C be Mg, Ca, one of Ba or a variety of, D Sc, V, Cr, Co, Mn, Ni, Fe, Cu, one of Zn or
It is a variety of, 0≤x≤0.95,0 y≤0.95 <；0≤n≤0.08.
In order to realize good effect, the granularity of cathod catalyst of the present invention be preferably not greater than 5 μm (such as: 1-5
μm、0.5-4μm、0.01-0.1μm、0.05-0.2μm、0.001μm、0.05μm、0.3μm、1.5μm、2μm、2.5μm、3μm、3.5
μm,4μm,4.5μm,5μm).It is highly preferred that the granularity of the cathod catalyst is 0.005~5 μm.
In above-mentioned cathod catalyst, the x is preferred are as follows: 0≤x≤0.3, y are preferred are as follows: 0 y≤0.9 <, n are preferably 0.
Above-mentioned cathod catalyst can be by solid reaction process, solution combustion synthetic method, coprecipitation, hydrothermal synthesis method, colloidal sol
The tradition inorganic material synthetic method preparation such as gel synthetic method, polymer complex method.Preferably, above-mentioned cathod catalyst uses solid phase
It is prepared by reaction method, the specific process is as follows:
Ball milling mixing step: according to the molar content of various elements in prepared cathod catalyst by corresponding amount
Raw material SrCO3、TiO2It is straight that wet ball grinding is carried out with the oxide of element representated by the oxide, that is, C and/or D to doped chemical
It is sufficiently mixed uniformly to raw material；
Sintering step: by the product after the wet ball grinding it is dry after in 1100 DEG C~1500 DEG C (such as 1110 DEG C, 1150
DEG C, 1200 DEG C, 1250 DEG C, 1300 DEG C, 1350 DEG C, 1400 DEG C, 1450 DEG C, 1490 DEG C) under be sintered 5~20 hours (such as 6h,
8h,12h,15h,18h,19h)；
Sintered product: being carried out wet ball grinding by ball milling step again again until particle diameter meets the requirements, finally
Obtain cathod catalyst powder.
In the preparation method of above-mentioned cathod catalyst, as a preferred implementation manner, in the ball milling mixing step
The medium of the wet ball grinding is ethyl alcohol, ball material mass ratio be 30/1~50/1 (such as 32:1,38:1,42:1,45:1,48:
1), revolving speed is 200~400rpm (such as 210rpm, 250rpm, 300rpm, 320rpm, 340rpm, 360rpm, 380rpm), ball
Time consuming be 15-30h (such as 16h, 18h, 20h, for 24 hours, 26h, 28h, 29h).
In the preparation method of above-mentioned cathod catalyst, as a preferred implementation manner, in the ball milling step again
In, the medium of the wet ball grinding is ethyl alcohol, ball material mass ratio be 20/1~40/1 (such as 20:1,25:1,30:1,35:1,
40:1), revolving speed be 500~1000rpm (such as 510rpm, 560rpm, 600rpm, 700rpm, 800rpm, 850rpm,
950rpm), Ball-milling Time is 0.5-10h (such as 0.5h, 1h, 2h, 4h, 6h, 8h, 10h).
The preparation method of cathod catalyst of the present invention is simple, is uniformly mixed raw material by first time ball milling, later in sky
Sintering makes raw material that high temperature solid state reaction generation perovskite structure oxide ABO occur in gas3Or A1-nBO3, then ball milling again
Product after sintering is ground into fine particle powder cathod catalyst powder i.e. of the invention.
A kind of composite cathode material of the solid oxide fuel cell comprising above-mentioned cathod catalyst, the composite cathode
Material further includes cathode material and high oxygen-ion conductive material；Preferably, the quality of the cathod catalyst is cathode material, height
Oxygen-ion conductive material and cathod catalyst quality sum 0.15-40% (such as 0.16%, 0.2%, 0.3%, 0.4%,
0.8%, 1%, 2%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 39%)；The high oxygen-ion conductive material
Quality be cathode material and high oxygen-ion conductive material quality sum 30-70% (such as 31%, 35%, 40%, 45%,
50%, 55%, 60%, 65%, 69%).
In above-mentioned composite cathode material, the cathode material is the manganite (Doped of the doping of perovskite structure
Manganite-Based Perovskite), cobaltatess (the Doped Cobaltite-Based of the doping of perovskite structure
Perovskite), ferrite (Doped Ferrite-Based Perovskite), the perovskite knot of the doping of perovskite structure
The nickelate (Doped Nickelate-Based Perovskite) and A of the doping of structure2NiO4Nickelate (the A of structure2NiO4–
Type Nickelate) one of or it is a variety of.These types of typical existing cathode material is illustrated below.
The manganite (Doped Manganite-Based Perovskite) of the doping of perovskite structure:
(1) the manganite perovskite AMnO of location A doping3Meet perovskite structure ABO3Or meet location A defect
Perovskite structure A1-nBO3(0≤n≤0.08).Wherein location A is the combination of lanthanide series and alkaline-earth metal, i.e., only in location A
When doping, the manganite perovskite of location A doping meets following chemical general formula: (Ln1-xCx)1-nMnO3, wherein Ln be La, Ce,
One of Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or a variety of, C Mg, Ca, Sr, one of Ba or
It is a variety of；0 < x≤0.95,0≤n≤0.08.
(2) the manganite perovskite AMn of B location doping1-yDyO3Meet perovskite structure ABO3Or location A defect
Perovskite structure A1-nBO3(0≤n≤0.08).Wherein B location is the combination of manganese element and variable valency metal, i.e., only mixes in B location
When miscellaneous, the manganite perovskite of B location doping meets following chemical general formula: A1-nMn1-yDyO3, wherein D be Sc, Ti, V, Cr,
One of Fe, Co, Ni, Cu, Zn or a variety of；A is La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu
One of or it is a variety of；0 < y≤0.95,0≤n≤0.08.
(3) when A and B location adulterate simultaneously, the manganite of the doping of perovskite structure meets following chemical general formula:
(Ln1-xCx)1-nMn1-yDyO3, wherein Ln is La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, one in Yb, Lu
Kind or a variety of, C Mg, Ca, Sr, one of Ba or a variety of, D Sc, Ti, V, Cr, Fe, Co, Ni, Cu, one of Zn or
It is a variety of；0 < x≤0.95,0 < y≤0.95,0≤n≤0.08.
In summary three kinds of doping situations, the manganite of the doping for the perovskite structure that the present invention uses preferably satisfy with
Lower chemical general formula: (Ln1-xCx)1-nMn1-yDyO3, wherein Ln be La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm,
One of Yb, Lu or a variety of, C Mg, Ca, Sr, one of Ba or a variety of, D Sc, Ti, V, Cr, Fe, Co, Ni, Cu, Zn
One of or it is a variety of；X, y be respective element molar content, and 0≤x≤0.95 (such as x be 0.01,0.05,0.1,
0.15,0.2,0.25,0.3,0.35,0.4,0.45,0.5,0.55,0.6,0.65,0.7,0.75,0.8,0.85 or 0.9), 0 <
Y≤0.95 (such as y be 0.01,0.05,0.1,0.15,0.2,0.25,0.3,0.35,0.4,0.45,0.5,0.55,0.6,
0.65,0.7,0.75,0.8,0.85 or 0.9), 0≤n≤0.08, x and y are not zero simultaneously.
The cobaltatess (Doped Cobaltite-Based Perovskite) of the doping of perovskite structure:
(1) the cobaltatess perovskite ACoO of location A doping3Meet perovskite structure ABO3Or meet the calcium of location A defect
Perovskite like structure A1-nBO3(0≤n≤0.08).Wherein location A is the combination of lanthanide series and alkaline-earth metal, i.e., only mixes in location A
When miscellaneous, the cobaltatess of the doping of perovskite structure meet following chemical general formula: (Ln1-xCx)1-nCoO3, wherein Ln be La, Ce, Pr,
One of Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or a variety of；C is Mg, Ca, Sr, one of Ba or more
Kind；0 x≤0.95 <.
(2) the cobaltatess perovskite ACo of B location doping1-yDyO3Meet perovskite structure ABO3Or meet location A defect
Perovskite structure A1-nBO3(0≤n≤0.08).Wherein B location is the combination of cobalt element and variable valency metal, i.e., only in B location
When doping, the cobaltatess of the doping of perovskite structure meet following chemical general formula: A1-nCo1-yDyO3, wherein A be La, Ce, Pr,
One of Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or a variety of, D Sc, Ti, V, Cr, Mn, Fe, Ni, Cu,
One of Zn or a variety of；0 < y≤0.95,0≤n≤0.08.
(3) when A and B location adulterate simultaneously, the cobaltatess of the doping of perovskite structure meet following chemical general formula:
(Ln1-xCx)1-n Co1-yDyO3, wherein Ln is La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, one in Yb, Lu
Kind or a variety of, C Mg, Ca, Sr, one of Ba or a variety of, D Sc, Ti, V, Cr, Mn, Fe, Ni, Cu, one of Zn or
It is a variety of；0 < x≤0.95,0 < y≤0.95,0≤n≤0.08.
In summary three kinds of doping situations, the cobaltatess of the doping for the perovskite structure that the present invention uses preferably satisfy following
Chemical general formula: (Ln1-xCx)1-n Co1-yDyO3, wherein Ln be La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm,
One of Yb, Lu or a variety of, C Mg, Ca, Sr, one of Ba or a variety of, D Sc, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn
One of or it is a variety of；X, y be respective element molar content, and 0≤x≤0.95 (such as x be 0.01,0.05,0.1,
0.15,0.2,0.25,0.3,0.35,0.4,0.45,0.5,0.55,0.6,0.65,0.7,0.75,0.8,0.85 or 0.9), 0 <
Y≤0.95 (such as y be 0.01,0.05,0.1,0.15,0.2,0.25,0.3,0.35,0.4,0.45,0.5,0.55,0.6,
0.65,0.7,0.75,0.8,0.85 or 0.9) 0≤n≤0.08, x and y are not zero simultaneously.
The ferrite (Doped Ferrite-Based Perovskite) of the doping of perovskite structure:
(1) the ferrite perovskite AFeO of location A doping3Meet perovskite structure ABO3Or meet the calcium of location A defect
Perovskite like structure A1-nBO3(0≤n≤0.08).Wherein location A is the combination of lanthanide series and alkaline-earth metal, i.e., only mixes in location A
When miscellaneous, the ferrite of the doping of perovskite structure meets following chemical general formula: (Ln1-xCx)1-nFeO3, wherein Ln be La, Ce, Pr,
One of Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or a variety of；C is Mg, Ca, Sr, one of Ba or more
Kind；0 x≤0.95 <.
(2) the ferrite perovskite AFe of B location doping1-yDyO3Meet perovskite structure ABO3Or meet location A defect
Perovskite structure A1-nBO3(0≤n≤0.08).Wherein B location is the combination of ferro element and variable valency metal, i.e., only in B location
When doping, the ferrite of the doping of perovskite structure meets following chemical general formula: A1-nFe1-yDyO3, wherein A be La, Ce, Pr,
One of Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or a variety of；D is Sc, Ti, V, Cr, Co, Mn, Ni, Cu,
One of Zn or a variety of；0 y≤0.95 <；
(3) when A and B location adulterate simultaneously, the ferrite of the doping of perovskite structure meets following chemical general formula:
(Ln1-xCx)1-nFe1-yDyO3, wherein Ln is La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, one in Yb, Lu
Kind is a variety of；C is Mg, Ca, Sr, one of Ba or a variety of；D is Sc, Ti, V, Cr, Co, Mn, Ni, Cu, one of Zn or
It is a variety of；0 x≤0.95 <；0 y≤0.95 <；0≤n≤0.08.
In summary three kinds of doping situations, the ferrite of the doping for the perovskite structure that the present invention uses preferably satisfies following
Chemical general formula: (Ln1-xCx)1-n Fe1-yDyO3, wherein Ln be La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm,
One of Yb, Lu or a variety of, C Mg, Ca, Sr, one of Ba or a variety of, D Sc, Ti, V, Cr, Co, Mn, Ni, Cu, Zn
One of or it is a variety of；；X, y be respective element molar content, and 0≤x≤0.95 (such as x be 0.01,0.05,
0.1,0.15,0.2,0.25,0.3,0.35,0.4,0.45,0.5,0.55,0.6,0.65,0.7,0.75,0.8,0.85 or
0.9), 0 y≤0.95 < (such as y be 0.01,0.05,0.1,0.15,0.2,0.25,0.3,0.35,0.4,0.45,0.5,
0.55,0.6,0.65,0.7,0.75,0.8,0.85 or 0.9) 0≤n≤0.08, x and y are not zero simultaneously.
The nickelate (Doped Nickelate-Based Perovskite) of the doping of perovskite structure:
(1) the nickelate perovskite ANiO of location A doping3Meet perovskite structure ABO3Or meet the calcium of location A defect
Perovskite like structure A1-nBO3(0≤n≤0.08).Wherein location A is the combination of lanthanide series and alkaline-earth metal, i.e., only mixes in location A
When miscellaneous, the nickelate of the doping of perovskite structure meets following chemical general formula: (Ln1-xCx)1-nNiO3, wherein Ln be La, Ce, Pr,
One of Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or a variety of；C is Mg, Ca, Sr, one of Ba or more
Kind；0 x≤0.95 <.
(2) the ferrite perovskite ANi of B location doping1-yDyO3Meet perovskite structure ABO3Or meet location A defect
Perovskite structure A1-nBO3(0≤n≤0.08).Wherein B location is the combination of nickel element and variable valency metal, i.e., only in B location
When doping, the ferrite of the doping of perovskite structure meets following chemical general formula: A1-nNi1-yDyO3, wherein A be La, Ce, Pr,
One of Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or a variety of；D is Sc, Ti, V, Cr, Co, Mn, Fe, Cu,
One of Zn or a variety of；0 y≤0.95 <；
(3) when A and B location adulterate simultaneously, the nickelate of the doping of perovskite structure meets following chemical general formula:
(Ln1-xCx)1-nNi1-yDyO3, wherein Ln is La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, one in Yb, Lu
Kind is a variety of；C is Mg, Ca, Sr, one of Ba or a variety of；D is Sc, Ti, V, Cr, Co, Mn, Fe, Cu, one of Zn or
It is a variety of；0 x≤0.95 <；0 y≤0.95 <；0≤n≤0.08.
In summary three kinds of doping situations, the nickelate of the doping for the perovskite structure that the present invention uses preferably satisfies following
Chemical general formula: (Ln1-xCx)1-n Ni1-yDyO3, wherein Ln be La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm,
One of Yb, Lu or a variety of, C Mg, Ca, Sr, one of Ba or a variety of, D Sc, Ti, V, Cr, Co, Mn, Fe, Cu, Zn
One of or it is a variety of；；X, y be respective element molar content, and 0≤x≤0.95 (such as x be 0.01,0.05,
0.1,0.15,0.2,0.25,0.3,0.35,0.4,0.45,0.5,0.55,0.6,0.65,0.7,0.75,0.8,0.85 or
0.9), 0 y≤0.95 < (such as y be 0.01,0.05,0.1,0.15,0.2,0.25,0.3,0.35,0.4,0.45,0.5,
0.55,0.6,0.65,0.7,0.75,0.8,0.85 or 0.9), 0≤n≤0.08, x and y are not zero simultaneously.
A2BO4Nickelate (the A of structure2NiO4- type Nickelate):
(1) the nickelate A of location A doping2NiO4Meet structure A2BO4Or meet the structure (A of location A defect2)1-nBO4
(0≤n≤0.08).Wherein location A is the combination of lanthanide series and alkaline-earth metal, i.e., only when location A adulterates, A2BO4Structure
Nickelate meets following chemical general formula: (Ln2-xCx)1-nNiO4, wherein Ln be La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy,
One of Ho, Er, Tm, Yb, Lu or a variety of；C is Mg, Ca, Sr, one of Ba or a variety of；0 x≤1.8 <.
(2) the nickelate A of B location doping2NiO4Meet structure A2BO4Or meet the structure (A of location A defect2)1-nBO4
(0≤n≤0.08).Wherein B location is the combination of nickel element and variable valency metal, i.e., only when B location adulterates, A2BO4The nickel of structure
Hydrochlorate meets following chemical general formula: A2Ni1-yDyO4, wherein A be La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm,
One of Yb, Lu or a variety of, D Sc, Ti, V, Cr, Co, Mn, Fe, Cu, one of Zn or a variety of；0 y≤0.95 <.
(3) when A and B location adulterate simultaneously, A2BO4The nickelate of structure meets following chemical general formula: (Ln2-xCx)1- nNi1-yDyO4, wherein Ln is La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, one of Lu or a variety of；C
For Mg, Ca, Sr, one of Ba or a variety of；D is Sc, Ti, V, Cr, Co, Mn, Fe, Cu, one of Zn or a variety of；0 < x≤
1.8；0 y≤0.95 <；0≤n≤0.08.
In summary three kinds of doping situations, the A that the present invention uses2BO4It is logical that the nickelate of structure preferably satisfies following chemistry
Formula: (Ln2-xCx)1-nNi1-yDyO4, wherein Ln is La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, in Yb, Lu
It is one or more, C Mg, Ca, Sr, one of Ba or a variety of, D Sc, Ti, V, Cr, Co, Mn, Fe, Cu, one of Zn
Or it is a variety of；X, y be respective element molar content, and 0≤x≤1.8 (such as x be 0.01,0.05,0.1,0.15,0.2,
0.25、0.3、0.35、0.4、0.45、0.5、0.55、0.6、0.65、0.7、0.75、0.8、0.85、0.9、1、1.1、1.2、1.3、
1.4,1.5,1.6,1.7), 0 y≤0.95 < (such as y is 0.01,0.05,0.1,0.15,0.2,0.25,0.3,0.35,0.4,
0.45,0.5,0.55,0.6,0.65,0.7,0.75,0.8,0.85 or 0.9), 0≤n≤0.08, x and y are not zero simultaneously.
In above-mentioned composite cathode material, the high oxygen-ion conductive material be preferably metal oxide stability zirconium oxide,
One of lanthanum gallate of the cerium oxide of doped metallic oxide and strontium magnesium cobalt codope is a variety of.Below to these three hyperoxia from
Subconductivity material is discussed in detail.
Zirconium oxide (the Stabilized ZrO of metal oxide stability2) in, common metal oxide is calcium oxide
(CaO), one of magnesia (MgO) and some rare earth oxides or a variety of, the rare earth oxide such as oxygen
Change yttrium (Y2O3), scandium oxide (Sc2O3), lanthana (La2O3), praseodymium oxide (Pr2O3), neodymia (Nd2O3), promethium oxide (Pm2O3)、
Samarium oxide (Sm2O3), europium oxide (Eu2O3), gadolinium oxide (Gd2O3), terbium oxide (Tb2O3), dysprosia (Dy2O3), holimium oxide
(Ho2O3), erbium oxide (Er2O3), thulium oxide (Tm2O3), ytterbium oxide (Yb2O3), luteium oxide (Lu2O3).Preferably, in the gold
Belong in the stable zirconium oxide of oxide, the content of the metal oxide be 1-20mol% (such as 2mol%, 4mol%,
5mol%, 6mol%, 7mol%, 8mol%, 9mol%, 10mol%, 11mol%, 12mol%, 13mol%, 14mol%,
15mol%, 17mol%, 19mol%).Specifically, general material has 8mol%Y2O3The ZrO of doping2[(Y2O3)0.08
(ZrO2)0.92], 10mol%Sc2O3The ZrO of doping2[(Sc2O3)0.1(ZrO2)0.9], 10mol%Sc2O3And 1mol%CeO2Doping
ZrO2[(Sc2O3)0.1(CeO2)0.01(ZrO2)0.89], 10mol%Sc2O3And 1mol%Al2O3The ZrO of doping2[(Sc2O3)0.1
(Al2O3)0.01(ZrO2)0.89], 6mol%Sc2O3And 1mol%Al2O3The ZrO of doping2[(Sc2O3)0.06(Al2O3)0.01
(ZrO2)0.93]。
Cerium oxide (the Doped CeO of doped metallic oxide2) in, common metal oxide is calcium oxide (CaO), oxygen
Change one of magnesium (MgO) and some rare earth oxides or a variety of.The rare earth oxide can be yttrium oxide
(Y2O3), scandium oxide (Sc2O3), lanthana (La2O3), praseodymium oxide (Pr2O3), neodymia (Nd2O3), promethium oxide (Pm2O3), oxidation
Samarium (Sm2O3), europium oxide (Eu2O3), gadolinium oxide (Gd2O3), terbium oxide (Tb2O3), dysprosia (Dy2O3), holimium oxide (Ho2O3)、
Erbium oxide (Er2O3), thulium oxide (Tm2O3), ytterbium oxide (Yb2O3), luteium oxide (Lu2O3).These metal oxides MO or M2O3
CeO after doping2Are as follows: Ce1-xMxO2(0.05≤x≤0.3), M be above-mentioned metallic element, that is, calcium, magnesium, yttrium, scandium, lanthanum, praseodymium, neodymium,
One of promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium are a variety of.
Lanthanum gallate (Sr, Mg, and Co the co-doped LaGaO of strontium magnesium cobalt codope3) in, the strontium magnesium cobalt codope
Lanthanum gallate meet following chemical general formula: La0.8Sr0.2Ga0.8Mg0.2-xCoxO3(0≤x≤0.15, for example, x be 0,0.05,
0.1、0.12、0.14)。
Above-mentioned cathode material powder and high oxygen-ion conductive material powder can be by the anti-methods of solid phase, solution combustion synthetic method, altogether
The tradition inorganic material synthetic method preparation such as the precipitation method, hydrothermal synthesis method, collosol and gel synthetic method, polymer complex method.It can also be straight
It connects from companies such as Fuel Cell Materials and buys.
The preparation method of the composite cathode material of above-mentioned solid oxide fuel cell, includes the following steps:
Cathode material powder and high oxygen-ion conductive material powder are mixed and are ground, it is compound to obtain two systems by step 1
Electrode；Wherein the quality of the hyperoxia ion conductive material powder is the 30%~70% of two system combination electrode gross masses；
Above-mentioned cathod catalyst powder is added into the two systems combination electrode, mixes and grinds, obtain three for step 2
Composite cathode material described in system；Wherein the quality of the cathod catalyst powder is the total matter of composite cathode material described in three-system
The 0.05-40% of amount.
In the preparation method of above-mentioned composite cathode material, as a preferred implementation manner, in said step 1, institute
State cathode material powder particle partial size be 0.3~1.5 μm (such as: 0.4 μm, 0.5-1 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8
μm,0.9μm,1.2μm,1.3μm,1.4μm)；The powder particle partial size of the high oxygen-ion conductive material is 0.3~1.5 μm of (ratio
Such as: 0.3-0.5 μm, 0.5-1 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1.0 μm, 1.1 μm, 1.4 μm).
In the preparation method of above-mentioned composite cathode material, as a preferred implementation manner, in the step 2, institute
State the partial size of cathod catalyst powder no more than 5 μm (such as: 1-5 μm, 0.5-4 μm, 0.01-0.1 μm, 0.05-0.2 μm,
0.001μm,0.05μm,0.3μm,1.5μm,2μm,2.5μm,3μm,3.5μm,4μm,4.5μm,5μm,).It is highly preferred that described
The granularity of cathod catalyst is 0.005~5 μm.
In the preparation method of above-mentioned composite cathode material, as a preferred implementation manner, in the step 1 and institute
It states in step 2, the grinding is wet ball grinding, specific process parameter are as follows: 200~400rpm of the range of speeds (such as
210rpm, 250rpm, 28rpm, 310rpm, 330rpm, 360rpm, 390rpm), ball material quality is than (the ratio of range 20/1~40/1
Such as 20:1,25:1,30:1,35:1,40:1), medium is ethyl alcohol, Ball-milling Time 20-24h (such as 21h, 22h, 23h).This two
Grinding in step is mainly used for for various materials being uniformly mixed.
The application method of above-mentioned three-system composite cathode material, comprising: firstly, by above-mentioned three-system composite cathode material with
Organic bond is mixed and made into electrode slurry；Then, the electrode slurry is printed in electrolyte using the method for silk-screen printing
Surface, thickness of electrode are controlled at 10~100 μm；According to the difference of type of electrodes, by the electrode in 900 DEG C~1300 DEG C (ratios
Such as: 910 DEG C, 950 DEG C, 1000 DEG C, 1100 DEG C, 1200 DEG C, 1250 DEG C, 1290 DEG C) in sintering 1h~10h (such as: 2h, 3h,
5h、6h、7h、8h、9h)。
Below with manganite-metal oxide stability zirconium oxide-cathod catalyst system of the doping of perovskite structure
For column composite cathode material, it was demonstrated that add the feature performance benefit of the composite cathode material of catalyst, specifically tested using full battery
The generated output of method test solid oxide fuel cell monocell.It is also provided with the normal cell of comparison in embodiments,
(the Sc that the electrolyte of the contrast standard battery uses with a thickness of 200 μm2O3)0.10(CeO2)0.01(ZrO2)0.89Electrolyte, electrode
Material powder is obtained from Fuel Cell Materials company.In addition, using the method for silk-screen printing in electrolyte sheet side
Print the NiO- (Sc of top surface area 0.64cm2O3)0.10(CeO2)0.01(ZrO2)0.89Anode slurry as anode, it is dry after
Sintering 1~5 in 1100 DEG C~1400 DEG C (contrast standard battery used in the following embodiment is carried out at 1300 DEG C)
Hour (contrast standard battery used in the following embodiment has been sintered 4h).Silk-screen printing is used in the other side of electrolyte sheet
Method printing top surface area 0.64cm (La0.8Sr0.2)0.98MnO3-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89Cathode slurry
As standard cathode, at 1100 DEG C~1300 DEG C, (contrast standard battery used in the following embodiment is 1200 after drying
Carried out at DEG C) 1~5 hour (contrast standard battery used in the following embodiment has been sintered 4h) of middle sintering.
The monocell performance test methods of following embodiment and normal cell are as follows: monocell is carried out under 800 DEG C of furnace temperature
Performance test, anode are passed through the hydrogen for being mixed with 3vol% vapor, and cathode is passed through air.
The manganite of the doping of various perovskite structures used in the following embodiment and metal oxide stability
Zirconium oxide is purchased from Fuel Cell Materials.
Embodiment 1
(1) strontium titanates of the perovskite structure of Fe2O3 doping is synthesized with solid-phase synthesis, chemical formula is as follows: SrTi1- yFeyO3；Y=0.35.
A. by the SrCO of purity >=99.9%3、TiO2、Fe2O3Three kinds of raw materials are according to chemical formula SrTi0.65Fe0.35O3Middle gold
Belong to the mixing of element molar percentage, and ball milling 24 hours in ethanol medium, revolving speed 300rpm, ball material mass ratio 40/1.
B. the product after ball milling is dry, it is sintered 10 hours in 1400 DEG C later.
C. after being sintered, in alcoholic media, revolving speed 800rpm, ball milling 10 hours under conditions of ball material mass ratio 35/1
Grain average grain diameter is 0.06 μm.
(2) in two system composite cathode material of standard
(La0.8Sr0.2)0.98MnO3-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89(wherein (Sc2O3)0.10(CeO2)0.01
(ZrO2)0.89Quality account for entire standard composite cathode material quality 50%, average particle size is 1.2 μm) in above-mentioned cathode be added urge
Agent is mixed and is ground, and grinding condition is as follows: ball milling 24 hours in ethanol medium, revolving speed 300rpm, ball material mass ratio 40/1,
Finally obtain the composite cathode material powder of three-system.Wherein, above-mentioned cathod catalyst accounts for the composite cathode material powder of three-system
The mass percent at end is 10% (i.e. SrTi0.65Fe0.35O3/(La0.8Sr0.2)0.98MnO3-(Sc2O3)0.10(CeO2)0.01
(ZrO2)0.89=1/9.
It is tested using performance of the following methods to the composite cathode material powder of the three-system:
Firstly, organic bond is added into above-mentioned composite cathode powder is made composite cathode slurry, wherein above-mentioned compound
The mass ratio of cathode powder and organic binder is 5:5.
Then, (the Sc using the method for silk-screen printing at 200 μm2O3)0.10(CeO2)0.01(ZrO2)0.89Electrolyte sheet one
NiO- (the Sc of side printing top surface area 0.64cm2O3)0.10(CeO2)0.01(ZrO2)0.89Anode slurry as anode, it is dry after
It is sintered 4 hours in 1300 DEG C.The upper of top surface area 0.64cm is printed using the method for silk-screen printing in the other side of electrolyte sheet
Composite cathode slurry is stated as cathode, is sintered 4 hours in 1200 DEG C after dry.
Fig. 1 shows addition 10%SrTi0.65Fe0.35O3(the La of powder0.8Sr0.2)0.98MnO3-(Sc2O3)0.10
(CeO2)0.01(ZrO2)0.89The monocell power generation performance of composite cathode, it can be seen from the figure that two system composite cathode of standard
10%SrTi is added in material0.65Fe0.35O3Battery performance is better than normal cell performance afterwards, the maximum power density of battery from
501mWcm-2Increase to 600mWcm-2。
Embodiment 2
In three-system composite cathode material manufactured in the present embodiment, except the cathod catalyst SrTi of addition0.65Fe0.35O3's
Content is different from other than embodiment 1, other are same as Example 1, in the present embodiment, cathod catalyst
SrTi0.65Fe0.35O3The mass percent for accounting for the composite cathode material powder of three-system is 20% (i.e. SrTi0.65Fe0.35O3/
(La0.8Sr0.2)0.98MnO3-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89=2/8.
To the performance methodology of the composite cathode material powder of three-system manufactured in the present embodiment with embodiment 1.As a result referring to
Fig. 2, as shown, 20%SrTi is added into two system composite cathode material of standard0.65Fe0.35O3Battery performance is better than mark afterwards
Quasi- battery performance, the maximum power density of battery is from 501mWcm-2Increase to 822mWcm-2。
Embodiment 3
In three-system composite cathode material manufactured in the present embodiment, except the cathod catalyst SrTi of addition0.65Fe0.35O3's
Content is different from other than embodiment 1, other are same as Example 1, in the present embodiment, cathod catalyst
SrTi0.65Fe0.35O3The mass percent for accounting for the composite cathode material powder of three-system is 40% (i.e. SrTi0.65Fe0.35O3/
(La0.8Sr0.2)0.98MnO3-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89=4/6.
To the performance methodology of the composite cathode material powder of three-system manufactured in the present embodiment with embodiment 1.As a result referring to
Fig. 3, as shown, 40%SrTi is added into two system composite cathode material of standard0.65Fe0.35O3Battery performance is better than mark afterwards
Quasi- battery performance, the maximum power density of battery is from 501mWcm-2Increase to 540mWcm-2。
Embodiment 4
In three-system composite cathode material manufactured in the present embodiment, except the cathod catalyst SrTi of addition0.95Fe0.05O3's
Chemical composition and content are different from other than embodiment 1, other are same as Example 1, in the present embodiment, cathod catalyst
SrTi0.95Fe0.05O3The mass percent for accounting for the composite cathode material powder of three-system is 20% (i.e. SrTi0.95Fe0.05O3/
(La0.8Sr0.2)0.98MnO3-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89=2/8.
To the performance methodology of the composite cathode material powder of three-system manufactured in the present embodiment with embodiment 1.The results show that
20%SrTi is added into two system composite cathode material of standard0.95Fe0.05O3Battery performance is better than normal cell performance, electricity afterwards
The maximum power density in pond is 720mWcm-2。
Embodiment 5
In three-system composite cathode material manufactured in the present embodiment, except the cathod catalyst SrTi of addition0.1Fe0.9O3Change
It learns composition and content is different from other than embodiment 1, other are same as Example 1, in the present embodiment, cathod catalyst
SrTi0.1Fe0.9O3The mass percent for accounting for the composite cathode material powder of three-system is 20% (i.e. SrTi0.1Fe0.9O3/
(La0.8Sr0.2)0.98MnO3-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89=2/8.
To the performance methodology of the composite cathode material powder of three-system manufactured in the present embodiment with embodiment 1.The results show that
20%SrTi is added into two system composite cathode material of standard0.1Fe0.9O3Battery performance is better than normal cell performance, battery afterwards
Maximum power density be 542mWcm-2。
Embodiment 6
In three-system composite cathode material manufactured in the present embodiment, except the cathod catalyst of addition
Sr0.8Ba0.2Ti0.65Fe0.35O3Chemical composition and content be different from embodiment 1 other than, other are same as Example 1, this
In embodiment, cathod catalyst Sr0.8Ba0.2Ti0.65Fe0.35O3Account for the mass percent of the composite cathode material powder of three-system
For 20% (i.e. Sr0.8Ba0.2Ti0.65Fe0.35O3/(La0.8Sr0.2)0.98MnO3-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89=2/
8。
To the performance methodology of the composite cathode material powder of three-system manufactured in the present embodiment with embodiment 1.The results show that
20%Sr is added into two system composite cathode material of standard0.8Ba0.2Ti0.65Fe0.35O3Battery performance is better than normal cell afterwards
Can, the maximum power density of battery is 540mWcm-2。
Embodiment 7
In three-system composite cathode material manufactured in the present embodiment, except the cathod catalyst of addition
Sr0.8Ca0.2Ti0.65Fe0.35O3Chemical composition and content be different from embodiment 1 other than, other are same as Example 1, this
In embodiment, cathod catalyst Sr0.8Ca0.2Ti0.65Fe0.35O3Account for the mass percent of the composite cathode material powder of three-system
For 20% (i.e. Sr0.8Ca0.2Ti0.65Fe0.35O3/(La0.8Sr0.2)0.98MnO3-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89=2/
8。
To the performance methodology of the composite cathode material powder of three-system manufactured in the present embodiment with embodiment 1.The results show that
20%Sr is added into two system composite cathode material of standard0.8Ca0.2Ti0.65Fe0.35O3Battery performance is better than normal cell afterwards
Can, the maximum power density of battery is 538mWcm-2。
Embodiment 8
In three-system composite cathode material manufactured in the present embodiment, except the cathod catalyst of addition
Sr0.8Mg0.2Ti0.65Fe0.35O3Chemical composition and content be different from embodiment 1 other than, other are same as Example 1, this
In embodiment, cathod catalyst Sr0.8Mg0.2Ti0.65Fe0.35O3Account for the mass percent of the composite cathode material powder of three-system
For 20% (i.e. Sr0.8Mg0.2Ti0.65Fe0.35O3/(La0.8Sr0.2)0.98MnO3-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89=2/
8。
To the performance methodology of the composite cathode material powder of three-system manufactured in the present embodiment with embodiment 1.The results show that
20%Sr is added into two system composite cathode material of standard0.8Mg0.2Ti0.65Fe0.35O3Battery performance is better than normal cell afterwards
Can, the maximum power density of battery is 571mWcm-2。
Comparative example 1
In the three-system composite cathode material of this comparison preparation, except the cathod catalyst SrTi of addition0.65Fe0.35O3Amount
Other than embodiment 1, other are same as Example 1, in the present embodiment, cathod catalyst SrTi0.65Fe0.35O3It accounts for
The mass percent of the composite cathode material powder of three-system is 0.1% (i.e. SrTi0.65Fe0.35O3/(La0.8Sr0.2)0.98MnO3-
(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89=0.01/9.99.
To the performance methodology of the composite cathode material powder of three-system manufactured in the present embodiment with embodiment 1.The results show that
0.1%SrTi is added into two system composite cathode material of standard0.65Fe0.35O3Afterwards battery performance substantially with normal cell performance
Maintain an equal level, the maximum power density of battery is 502mWcm-2。
Comparative example 2
By cathod catalyst SrTi0.65Fe0.35O3It is added to (Sc2O3)0.10(CeO2)0.01(ZrO2)0.89(average particle size is
1.2 μm) in, wherein cathod catalyst and (Sc2O3)0.10(CeO2)0.01(ZrO2)0.89Mass ratio be 2:8, by the two mix simultaneously
Grinding, grinding condition are as follows: ball milling 24 hours in ethanol medium, revolving speed 300rpm, ball material mass ratio 40/1 finally obtain compound
Cathode material powder.
It uses and is surveyed with performance of the identical method of embodiment 1 to composite cathode material powder prepared by this comparative example
Examination, the maximum power density of battery are 350mWcm-2。
Claims (13)
1. a kind of composite cathode material of solid oxide fuel cell, which is characterized in that the composite cathode material includes
Cathod catalyst, cathode material and high oxygen-ion conductive material；
The cathod catalyst is the strontium titanates of the perovskite structure of doping, meets following chemical general formulas: (Sr1-xCx)1-nTi1- yDyO3, wherein C is Mg, Ca, one of Ba or a variety of, D Sc, V, Cr, Co, Mn, Ni, Fe, Cu, one of Zn or more
Kind；X, y is the molar content of respective element, and 0≤x≤0.95,0 y≤0.95 <；0≤n≤0.08；
The granularity of the cathod catalyst is no more than 5 μm；
The quality of the cathod catalyst is cathode material, high oxygen-ion conductive material and cathod catalyst quality sum
0.2-40%；
The cathode material is cobaltatess, the perovskite of the doping of the manganite, perovskite structure of the doping of perovskite structure
The nickelate and A of the doping of the ferrite, perovskite structure of the doping of structure2NiO4One of nickelate of structure is a variety of.
2. composite cathode material according to claim 1, which is characterized in that the quality of the high oxygen-ion conductive material is yin
The 30-70% of pole material and high oxygen-ion conductive material quality sum.
3. composite cathode material according to claim 1 or claim 2, which is characterized in that the granularity of the cathod catalyst is 0.005
~5 μm.
4. composite cathode material according to claim 1 or claim 2, which is characterized in that the chemical general formula of the cathod catalyst
(Sr1-xCx)1-nTi1-yDyO3In, 0≤x≤0.3,0 y≤0.9 <, n=0.
5. composite cathode material according to claim 1 or claim 2, which is characterized in that the cathod catalyst powder uses solid phase
It is prepared by synthetic method.
6. composite cathode material according to claim 5, which is characterized in that the specific preparation side of the cathod catalyst powder
Method is as follows:
Ball milling mixing step: according to the molar content of various elements in prepared cathod catalyst by the raw material of corresponding amount
SrCO3、TiO2Wet ball grinding is carried out with the oxide to doped chemical until raw material is sufficiently mixed uniformly；
Sintering step: it will be sintered 5~20 hours at 1100 DEG C~1500 DEG C after the product drying after the wet ball grinding；
Sintered product: being carried out wet ball grinding by ball milling step again again until particle diameter meets the requirements.
7. composite cathode material according to claim 1 or 2, which is characterized in that the high oxygen-ion conductive material is gold
Belong to one of lanthanum gallate of the stable zirconium oxide of oxide, the cerium oxide of doped metallic oxide and strontium magnesium cobalt codope or more
Kind.
8. composite cathode material according to claim 7, which is characterized in that the zirconium oxide of the metal oxide stability
In, the metal oxide is calcium oxide, magnesia, scandium oxide, yttrium oxide, lanthana, praseodymium oxide, neodymia, promethium oxide, oxygen
Change one of samarium, europium oxide, gadolinium oxide, terbium oxide, dysprosia, holimium oxide, erbium oxide, thulium oxide, ytterbium oxide and luteium oxide
Or it is a variety of.
9. composite cathode material according to claim 8, which is characterized in that in the zirconium oxide of the metal oxide stability
In, the content of the metal oxide is 1-20mol%.
10. composite cathode material according to claim 7, which is characterized in that the cerium oxide of the doped metallic oxide
In, the metal oxide is calcium oxide, magnesia, scandium oxide, yttrium oxide, lanthana, praseodymium oxide, neodymia, promethium oxide, oxygen
Change one of samarium, europium oxide, gadolinium oxide, terbium oxide, dysprosia, holimium oxide, erbium oxide, thulium oxide, ytterbium oxide and luteium oxide
Or it is a variety of.
11. composite cathode material according to claim 10, which is characterized in that the cerium oxide of the doped metallic oxide
Meet following chemical general formula: Ce1-xMxO2, wherein 0.05≤x≤0.3, M be calcium, magnesium, scandium, yttrium, lanthanum, praseodymium, neodymium, promethium, samarium, europium,
One of gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium are a variety of.
12. composite cathode material according to claim 7, which is characterized in that the lanthanum gallate of the strontium magnesium cobalt codope is full
The following chemical general formula of foot: La0.8Sr0.2Ga0.8Mg0.2-xCoxO3, wherein 0≤x≤0.15.
13. a kind of method for the composite cathode material for preparing any solid oxide fuel cell of claim 1-12,
It is characterized by comprising the following steps:
Cathode material powder and high oxygen-ion conductive material powder are mixed and are ground, obtain two system combination electrodes by step 1；
Wherein the quality of the hyperoxia ion conductive material powder is the 30%~70% of two system combination electrode gross masses；
Cathod catalyst powder is added into the two systems combination electrode, mixes and grinds, obtain described in three-system for step 2
Composite cathode material；Wherein the quality of the cathod catalyst powder is the 0.2- of composite cathode material gross mass described in three-system
40%.
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| CN108091884B (en) * | 2016-11-21 | 2020-04-28 | 中国科学院大连化学物理研究所 | A solid oxide fuel cell cathode and its application |
| CN107425205A (en) * | 2017-07-18 | 2017-12-01 | 新奥科技发展有限公司 | A kind of anode of solid oxide fuel cell material and its fuel cell |
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| CN111229219B (en) * | 2018-11-29 | 2023-07-11 | 中国科学院大连化学物理研究所 | A kind of tail gas combustion catalyst and its preparation and application |
| CN113258086B (en) * | 2021-04-30 | 2022-09-27 | 南京工业大学 | A three-phase conductor proton conductor composite cathode material and preparation method thereof |
| CN114267847B (en) * | 2021-12-15 | 2024-01-23 | 常州大学 | Bimetallic oxygen reduction electrocatalyst |
| CN115739115B (en) * | 2022-11-25 | 2024-09-20 | 南京航空航天大学 | A B-site double-ion doped strontium titanate nanocomposite photocatalytic material and preparation method thereof |
| CN118073584B (en) * | 2024-03-12 | 2025-06-03 | 中国矿业大学 | Composite cathode material, preparation method thereof and medium-low temperature solid oxide fuel cell |
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| CN102751508A (en) * | 2011-04-19 | 2012-10-24 | 三星电子株式会社 | Cathode material for a fuel cell, cathode including the cathode material, and a solid oxide fuel cell including the cathode material |
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